Programme and Book of Abstracts

Transcription

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#png2016atKTH
Cover photos by:
Kungl. Ingenjörsvetenskapsakademien
Yanan Li
23rd Polymer Networks Group meeting
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Welcome to PNG2016!
Dear Colleagues,
It is a great pleasure for me to deliver the greeting to the 23rd Polymer Networks Group Meetings,
PNG2016, Stockholm.
Founded in 1975, PNG is an independent international organization for the promotion of international
contacts and stimulation of research in the important field of polymer networks. This is mainly done
through PNG biannual meetings, which, during the past four decades, have brought into contact a large
number of scientists and engineers from many countries, and stimulated scientific exchanges between
the East and the West.
PNG Meetings have a long history over 40 years, starting in 1975 jointly at CRM Strasbourg by Profs.
H. Benoit, G. Hild and at Freiburg by Profs. W. Burchard, H. J. Cantow. Please note that 1975 was
the next year Prof. Paul J. Flory was awarded to Nobel Prize in Chemistry (1974). It is well known that
Prof. Flory was one of the pioneers of chemistry and physics of polymer networks, such as theories
of gelation, rubber elasticity, swelling equilibrium. He himself gave distinguished contributions to PNG
meetings. Since then, polymer science became a world-wide well-recognized science, and the science
on polymer networks did too. PNG meetings have been a gateway-to-success as well as saloon for the
community of scientists interested in polymer networks.
Today, sciences and technologies on polymer networks are growing rapidly, covering not only
fundamental chemistry and physics, but also biology, pharmacy, agriculture, medicine, food science,
civil engineering, and so on. Furthermore, interdisciplinary sciences related to polymer networks have
shed a light in various fields of sciences and industries.
Last, but not the least, I would like to express my sincere thanks to the chairman of PNG2016, Prof. Eva
Malmström Jonsson and the members of the organizing committee.
Mitsuhiro Shibayama
Professor
Chairman PNG
The University of Tokyo, Japan
www.polymernetworksgroup.org
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Organization
Organizing committee
International advisory board
Eva Malmström (Chair)
KTH Royal Institute of Technology, Sweden
Ferenc Horkay
NIH, USA
Linda Fogelström (Co-chair)
KTH Royal Institute of Technology, Sweden
Costas S Patrickios
University of Cyprus, Cyprus
Søren Hvilsted
DTU, Denmark
Olga E Philippova
Moscow State University, Russia
Bjørn Torgeir Stokke
NTNU, Norway
Mitsuhiro Shibayama
University of Tokyo, Japan
Heikki Tenhu
Helsinki University, Finland
Local organizing committee
Working group
Mats Johansson
Alexandra Holmgren
Anders Hult
Tahani Kaldéus
Mikael Hedenqvist
Marcus Jawerth
Joakim Engström
Sara Brännström
Jonna Holmqvist
Martin Wåhlander
Andrea Träger
Samer Nameer
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Table of contents
General information........................................................................................10
Scientific Programme....................................10
Exhibition.......................................................10
Lunches.........................................................10
Coffee breaks................................................10
Travel information.........................................10
Internet access .............................................10
Conference map.............................................................................................11
Social programme...........................................................................................12
Get-together..................................................12
Reception in the Stocholm City Hall..............12
Poster session...............................................12
Conference dinner.........................................12
Travel directions............................................13
Conference programme..................................................................................14
Detailed conference schedule........................................................................16
Abstracts.........................................................................................................23
List of abstracts.............................................24
Plenary lectures............................................ 30
Keynote lectures...........................................40
Oral presentations.........................................49
Posters..........................................................99
Upcoming conferences...................................................................... 133
List of participants...........................................................................................134
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General information
Scientific programme
Plenary lectures, keynote lectures and oral presentations, as well as the poster session, will be held in
close proximity to each other in the E-building, entrance from Lindstedtsvägen 3 or Osquars backe 2.
Poster contributions are welcome. The size of the poster screens is 90 x 190 cm (portrait; W 90 cm, H
190 cm). Posters presenters are encouraged to put up their posters already on Monday June 20 and
leave them up until the closing of the conference.
Exhibition
The exhibition will be held in close proximity to the conference in the E-building, entrance from
Lindstedtsvägen 3 or Osquars backe 2.
Lunches
Conference lunches will be served at Restaurant Q, Osquldas väg 4.
Coffee breaks
Coffee breaks will be held in the mornings and in the afternoons in close proximity to the conference in
the E-building, entrance from Lindstedtsvägen 3 or Osquars backe 2.
Travel information
Information about local transportation: buses, metro (“tunnelbana”), commuter trains (“pendeltåg”).
How to travel with bus/metro/commuter trains:
Option 1: Buy an electronic card and load any number of single tickets or passes (24 h, 48 h, 72 h,
weekly passes). Electronic cards are 20 SEK to buy (debit or credit card only) at SL Center
(T-Centralen station and other major stations like Slussen, Fridhemsplan, and Tekniska högskolan),
as well as in convenience stores such as Pressbyrån inside the train stations (always check for the SL
logo!).
Option 2: Buy a single ticket at a vending machine in the stations within Stockholm (debit or credit only,
no cash).
Option 3: Buy tickets at the metro/commuter train booth (more expensive than Option 1).
How to plan your journey (enter either a metro station or an address): www.sl.se/en/
Internet access
To gain internet access please find the network “KTH Conference”.
Use the password “hHgF3bSa” to log in.
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Map KTH Campus
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Social programme
Get-together
On Sunday, June 19, there will be a get-together at 18.00 at the restaurant “Syster O Bror”, Drottning
Kristinas väg 24, on KTH Campus.
http://www.systerobror.se/
Reception in the Stocholm City Hall
On Monday, June 20, the City of Stockholm is hosting a reception in the Stockholm City Hall to honour
the Conference delegates.
The Stockholm City Hall, situated in the heart of Stockholm city at Hantverkargatan 1, is probably the
city’s most famous landmark with its 106 meter high tower, created by the architect Ragnar Östberg,
featuring the Swedish coat of arms, three crowns, on top. The City Hall was inaugurated on
Midsummer’s Eve in 1923 and is considered as one of the prime examples of national romantic spirit in
Sweden. It is the home of the Municipal Council but also the host of hundreds of events and celebrations
each year. The most famous event hosted in the City Hall is the world famous Noble Prize Banquet,
which is held each year on December 10 in the magnificent Blue Hall.
The reception organized for PNG2016 is free of charge but you will have to bring the ticket which is
provided upon arrival to Stockholm.
Poster session
On Tuesday, June 21, there will be a poster session with snacks and refreshments, organized in close
proximity to the Conference on Campus KTH.
Conference dinner
On Wednesday, June 22, the PNG2016 Conference dinner will take place at Tekniska museet,
Museivägen 7.
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Travel directions
To City Hall (Stadshuset) from Tekniska högskolan (KTH):
Address to City Hall: Hantverkargatan 1, Stockholm
Take the metro, red line 14 towards Fruängen going south from Tekniska högskolan.
Exit at T-centralen and take the escalators up to Centralstationen, Vasagatan.
Walk to Hantverkargatan 1 or take bus 50 going towards Hornsberg at bus stop Centralen
(Vasagatan) outside the entrance of Centralstationen.
Exit the bus at stop Stadshuset (next stop after Centralen).
To Tekniska museet:
Address to Tekniska museet: Museivägen 7, Stockholm
- From T-centralen and Centralstationen:
Take bus 69 going towards Blockhusudden/Kaknästornet from bus stop Centralstationen
(Klarabergsviadukten). Exit at bus stop Museiparken.
- From Tekniska högskolan/Östra station (KTH):
Take bus 67 from Östra station across the street (Valhallavägen) from KTH towards Skansen.
Exit at bus stop Strandvägen.
Cross Strandvägen to the bus stop and take bus 69 towards Blockhusudden/Kaknästornet.
Exit at bus stop Museiparken.
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Conference programme
SUNDAY June 19
18.00 - ca 20.00
Get-together, Restaurant Syster O Bror
MONDAY June 20
08.00 - 09.00
09.00 - 09.30
09.30 - 10.15
10.15 - 10.45
10.45 - 12.05
12.05 - 13.20
13.20 - 14.05
14.05 - 14.35
14.35 - 14.40
14.40 - 15.20 15.20 - 15.50
15.50 - 16.35
16.35 - 17.05
17.05 - 17.25
18.30 - Registration
Opening, E1
Plenary lecture, E1
Coffee
Oral presentations, E1 & E2
Lunch
Plenary lecture, E1
Keynote lecture, E1
Break
Coffee
Plenary lecture, E1
Keynote lecture, E1
Oral presentations, E1
Reception, City Hall
TUESDAY June 21
09.00 - 09.45
09.45 - 10.15
10.15 - 10.45
10.45 - 12.05
12.05 - 13.20
13.20 - 14.05
14.05 - 14.35
14.35 - 14.40
14.40 - 15.20 15.20 - 15.50
15.50 - 16.35
16.35 - 17.35
17.45 - 19.45
Plenary lecture, E1
Keynote lecture, E1
Coffee
Lunch
Plenary lecture, E1
Keynote lecture, E1
Break
Coffee
Plenary lecture, E1
Poster session
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WEDNESDAY June 22
09.00 - 09.45
09.45 - 10.15
10.15 - 10.45
10.45 - 12.05
12.05 - 13.20
13.20 - 14.05
14.05 - 14.35
14.35 - 15.05
15.05 - 15.35
15.35 - 17.15 19.00 - Plenary lecture, E1
Keynote lecture, E1
Coffee
Lunch
Plenary lecture, E1
Keynote lecture, E1
Keynote lecture, E1
Coffee
Conference dinner
THURSDAY June 23
09.00 - 09.45
09.45 - 10.15
10.15 - 10.45
10.45 - 11.45
11.45 - 12.05
12.05 - 13.20
Plenary lecture, E1
Keynote lecture, E1
Coffee
Closing
Lunch
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Detailed conference schedule
Monday, June 20
08.00 - 09.00
Registration
Opening/Plenary session, E1
Chair: Eva Malmström
09.00 - 09.30
Opening
Prof. Per Berglund, Vice Dean of Faculty
09.30 - 10.15
PL-1 Mitsuhiro Shibayama
“Exploration of Ideal Polymer Networks”
10.15 - 10.45
Coffee
Oral session I, E1
Oral session II, E2
10.45 - 11.05
O-1 Li Jia
”Particulate Beta-Sheet NanocrystalReinforced Supramolecular Elastomers”
O-5 Ferenc Horkay
”Gel-like Properties of Cartilage
Proteoglycans”
11.05 - 11.25
O-2 Anders Egede Daugaard
”Thiol-ene thermosets exploiting surface
reactivity for layer-by-layer structures
and control of penetration depth for
selective surface reactivity”
O-6 Bjørn Torger Stokke
”A new strategy for ionotropic alginate gelation
applied in microfluidic assisted homogeneous
bead synthesis and cell immobilization”
11.25 - 11.45
O-3 Karel Dusek
”Polymer Networks from Nanosized
Multifunctional Precursors”
O-7 Stevin Gehrke
”Chitin-binding proteins induce
buimacromolecular microparticle formation:
inspirations from insect cuticle for
hierarchical self-assembly”
11.45 - 12.05
O-4 Xiang Li
”Dynamics of nano-particles in polymer
networks near gelation point”
O-8 Oshiaki Yuguchi
”Structural formation and gelation of neutral polysaccharides as observed by small angle
X-ray scattering”
Chair: Dominique Hourdet
Chair: Olga Philippova
Lunch
12.05 - 13.20
Plenary/Keynote session, E1
Chair: Ferenc Horkay
13.20 - 14.05
PL-2 Béla Iván
”Amphiphilic Conetworks as a New Material Platform of Bicontinuous Nanophasic
Macromolecular Assemblies, Intelligent Gels and Unique Organic-Inorganic Nanohybrids”
14.05 - 14.35
K-1 Filip Du Prez
”New Generation of Vitrimers: Permanent Polymeric Networks with Glass-like Fluidity”
14.35 - 14.40
Break
Oral session I, E1
14.40-15.00
15.00 - 15.20
Oral session II, E2
Chair: Mikael Hedenqvist
Chair: Anders Egede Duagaard
O-9 Miroslava Duskova-Smrckova
”Interpenetrating Network Hydrogels: Roles
and Fates of Network 1 and Network 2”
O-11 Orsolya Czakkel
”Mechanical and thermoresponsive properties of
PNIPA - graphene-oxide composite gels”
O-10 Bradley Olsen
”Anomalous Self-Diffusion in Physical Polymer
Gels”
O-12 Pitchaya Treenate
”Crosslinker Effects on Properties of
Hydroxyethylacryl Chitosan/Sodium Alginate
Hydrogel Films”
Coffee
15.20 - 15.50
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Chair: Heikki Tehnu
15.50 - 16.35
PL-3 James Lewicki
”A Multi-scale Experimental and Computational Approach to Studying Network Dynamics in
Complex Polysiloxane Elastomers”
16.35 - 17.05
K-2 Jürgen Groll
”Dynamic Polymer Networks for Biofabrication: General Strategies and Specific Examples”
Oral session, E1
Chair: Heikki Tehnu
17.05 - 17.25
18.30 -
O-13 Nobuyuki Takahashi
”Mesoscopic structural order in hydrogen bonding liquid”
Reception, City Hall
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Tuesday, June 21
Chair: Filip Du Prez
09.00 - 09.45
PL-4 Chi Wu
“Single-Particle Tracking Micro-rheometer – Magnetic Tweezer Marries Total
Internal Reflection Microscope”
09.45 - 10.15
K-3 Anne Skov
”Interpenetrating networks based on covalent and ionic networks facilitating self-healing”
10.15 - 10.45
Coffee
Oral session I, E1
Oral session II, E2
Chair: Kazunari Akiyoshi
Chair: Marco Sangermano
10.45 - 11.05
O-14 Sebastian Seiffert
”Soft Sensitive Matter: Structure, Dynamics,
and Function of Supramolecular Polymer Gels”
O-18 David Diaz Diaz
”Gel networks as confined microenvironments
for photochemical reactions that are
inaccessible in solution under mild conditions”
11.05 - 11.25
O-15 Patrice Bourson
”Advantages to do in-situ measurements by
Raman spectroscopy and coupling with other
techniques for the determination of
physico-chemical properties of polymers”
O-19 Viktor Granskog
“Linear-Dendritic Macromolecules as components
in Biomedical Soft Tissue Adhesives”
11.25 - 11.45
O-16 Juan Baselga
”Chemically modified hybrid thermosets: elastic
behavior in
O-20 Morten Jarlstad Olesen
”Hydrogels as hosts for Substrate Mediated
Enzyme Prodrug Therapy”
11.45 - 12.05
O-17 Pierre Millereau
”Enhanced mechanical properties in multiple
network elastomers”
O-21 Felix Schacher
”Interface Design using Block Copolymers:
Crosslinking and Interpolyelectrolyte
Complexation”
Lunch
12.05 - 13.20
Chair: Anders Hult
13.20 - 14.05
PL-5 Dominique Hourdet
”Macromolecular assemblies in aqueous media: from controlled rheology of polymer solutions to
mechanical reinforcement of covalent hydrogels”
14.05 - 14.35
K-4 Kazunari Akiyoshi
”Self-Assembled Nanogel Tectonics for Advanced Biomaterials”
14.35 - 14.40
Break
Oral session I, E1
Oral session II, E2
14.40 - 15.00
O-22 Kenji Urayama
”Rheological Behavior of Dense Suspensions of
Thermo-Responsive Microgels”
O-24 Geng Hua
“Biobased hydrogels for metal ion waste water
treatment”
15.00 - 15.20
O-23 Tobias Ingverud
”Hydrogel composites of cellulose nanofibrils and
thermoresponsive cationic block copolymers as
electrostatic macrocrosslinker”
O-25 Masaki Nakahata
”Highly Flexible, Tough, and Self-Healable
Supramolecular Polymeric Materials Using
Host–Guest Interaction”
Chair: Berit Løkensgard Strand
Chair: Karin Odelius
Coffee
15.20 - 15.50
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Plenary session, E1
Chair: Costas Patrickios
15.50 - 16.35
PL-6 Molly Stevens
”New polymer based approaches for biosensing and regenerative medicine”
Oral session, E1
Chair: Costas Patrickios
16.35 - 16.55
O-26 Ben Bin Xu
”A new microfluidic switch technique by controllably buckling Stimuli-responsive polyelectrolyte
hydrogel thin layer”
16.55 - 17.15
O-27 Daisuke Aoki
”Synthesis of Rotaxane-Cross-Linked Polymers Using Macromolecular [2]Rotaxane Having
Hydrophilic Axle Component as a Vinylic cross-linker”
17.15 - 17.35
O-28 Apichaya Jianprasert
”Study on crosslinked structure and thermal properties of polymer networks based on Tung oil and
PVA with different catalytic systems”
17.45 - 19.45
Poster Session
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Wednesday, June 22
Chair: Søren Hvilsted
09.00 - 09.45
PL-7 Francoise Winnik
”Biological responses to chitosans substituted with zwitterionic groups”
09.45 - 10.15
K-5 Alexander Zelikin
”Poly(vinyl alcohol) physical hydrogels: New Vista on a Long Serving Biomaterial”
10.15 - 10.45
Coffee
Oral session I, E1
Oral session II, E2
10.45 - 11.05
O-29 Yoshinori Takashima
”Photo stimuli responsive supramolecular and
topological materials using host-guest complexes”
O-33 Zhansaya Sadakbayeva
”IPN hydrogels of poly(2-hydroxyethyl
methacrylate) and poly(2,3-dihydroxypropyl
methacrylate) with tunable deformation
responses”
11.05 - 11.25
O-30 Eleonora Parelius Jonasova
”Studying processes leading to swelling of
DNA-responsive hydrogels”
O-34 Constantinos Tsitsilianis
”Recent trends in telechelic amphiphilic gelators:
the use of random copolymers as building blocks
for tuning the network properties”
11.25 - 11.45
O-31 Takashi Miyata
”Rational Design of Molecularly Stimuli-responsive
Hydrogels Using Supramolecular Crosslinks”
O-35 Rémi Absil
”Ultrafast gelation of injectable reactive
microgels: The power of TAD click chemistry”
11.45 - 12.05
O-32 Heikki Tenhu
”Gold-decorated poly(N-vinylcaprolactam)
gel particles”
O-36 Stevin Gehrke
“Engineering glycosaminoglycan hydrogels to
control swelling, moduli and fracture properties”
Chair: Alexander Zelikin
Chair: Anne Skov
Lunch
12.05 - 13.20
Chair: Bjørn Torgeir Stokke
13.20 - 14.05
PL-8 Olli Ikkala
”Supramolecular functionalization of molecular and colloidal networks”
14.05 - 14.35
K-6 Jacqueline Forcada
”Multi-stimuli-responsive nanogels for bio-applications”
14.35 - 15.05
K-7 Marco Sangermano
”Cationically UV-cured functional polymeric networks”
15.05 - 15.35
Coffee
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Oral session I, E1
Oral session II, E2
Chair: Mats Johansson
Chair: Miroslava Duskova-Smrckova
15.35 - 15.55
O-37 Chris Lowe
”Modelling Thermo-mechanical Aspects of
Thermosetting Polymers and How Monomer
Composition Impacts Properties”
O-42 Olga Philippova
”Self-assembled nanogels of chitosan”
15.55 - 16.15
O-38 Per-Erik Sundell
”Multilayer coil coating - placing properties”
O-43 Sami Hietala
”UCST-LCST double thermosensitive block
copolymers”
16.15 - 16.35
O-39 Steve Howdle
”Acrylate and Methacrylate Polymers and
Coatings Derived from Terpenes”
O-44 Sada-Atsu Mukai
”Ring shape formation of nanogel-crosslinked
matrials by using non-equilibrium process”
16.35 - 16.55
O-40 Dirk W. Schubert
”Magnetic Liquid Silicone Rubber”
O-45 Gaio Paradossi
”Temperature tuning of hybrid nanogels
surfaces”
16.55 - 17.15
O-41 Aslihan Argun
”Nonionic Double and Triple Network Hydrogels”
O-46 Aleksey Drozdov
”Structure-property relations for equilibrium
swelling of cationic polyelectrolyte hydrogels”
19.00 -
Conference dinner, Tekniska museet
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Thursday, June 23
Chair: Mitsuhiro Shibayama
09.00 - 09.45
PL-9 Zhigang Suo
”Hydrogel as Tough Water”
K-8 Berit Løkensgard Strand
09.45 - 10.15
“Tailoring alginates for tissue engineering applications by chemoenzymatic modification”
10.15 - 10.45
Coffee
Oral session, E1
Chair: Michael Malkoch
10.45 - 11.05
O-47 Tim Bowden
“Nucleophilic Polymers - formation of hydrogels, particles and scavenging of inflammatory
mediators”
11.05 - 11.25
O-48 Martin Wåhlander
“Next-Generation Matrix-Free Graphene Composites with Tuneable Orientation and Shape-Memory
Effect”
11.25 - 11.45
O-49 Jean-Paul Chapel
”Early Stage Kinetics and structure of Polyelectrolyte Complexes Studied by
Stopped-Flow and Neutron scattering”
11.45 - 12.05
Closing session, E1
12.05 - 13.20
Lunch
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Abstracts
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List of abstracts
Plenary lectures
PL-1
PL-2
PL-3
PL-4
PL-5
PL-6
PL-7
PL-8
PL-9
Mitsuhiro Shibayama
Béla Iván
“Amphiphilic Conetworks as a New Material Platform of Bicontinuous
Nanophasic Macromolecular Assemblies, Intelligent Gels and Unique
Organic-Inorganic Nanohybrids”
James Lewicki
“A Multi-scale Experimental and Computational Approach to Studying Network
Dynamics in Complex Polysiloxane Elastomers”
Chi Wu
“Single-Particle Tracking Micro-rheometer – Magnetic Tweezer Marries Total
Internal Reflection Microscope”
Dominique Hourdet
“Macromolecular assemblies in aqueous media: from controlled rheology of
polymer solutions to mechanical reinforcement of covalent hydrogels”
Molly Stevens
“New polymer based approaches for biosensing and regenerative medicine”
Francoise Winnik
“Biological responses to chitosans substituted with zwitterionic groups”
Olli Ikkala
“Supramolecular functionalization of molecular and colloidal networks”
Zhigang Suo
“Hydrogel as Tough Water”
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33
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35
36
37
38
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Keynote lectures
K-1
K-2
K-3
K-4
K-5
K-6
K-7
K-8
Filip Du Prez
“New Generation of Vitrimers: Permanent Polymeric Networks with Glass-like
Fluidity”
Jürgen Groll
“Dynamic Polymer Networks for Biofabrication: General Strategies and Specific Examples”
Anne Skov
“Interpenetrating networks based on covalent and ionic networks facilitating
self-healing”
Kazunari Akiyoshi
“Self-Assembled Nanogel Tectonics for Advanced Biomaterials”
Alexander Zelikin
“Poly(vinyl alcohol) physical hydrogels: New Vista on a Long Serving
Biomaterial”
Jacqueline Forcada
“Multi-stimuli-responsive nanogels for bio-applications”
Marco Sangermano
“Cationically UV-cured functional polymeric networks”
Berit Løkensgard Strand
“Tailoring alginates for tissue engineering applications by chemoenzymatic
modification”
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41
42
43
44
45
46
47
48
Oral presentations
O-1
O-2
O-3
O-4
O-5
O-6
O-7
O-8
O-9
O-10
O-11
O-12
O-13
O-14
O-15
O-16
O-17
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Li Jia
”Particulate Beta-Sheet Nanocrystal-Reinforced Supramolecular Elastomers”
51
Anders Egede Daugaard
”Thiol-ene thermosets exploiting surface reactivity for layer-by-layer structures
and control of penetration depth for selective surface reactivity”
Karel Dusek
”Polymer Networks from Nanosized Multifunctional Precursors”
Xiang Li
”Dynamics of nano-particles in polymer networks near gelation point”
Ferenc Horkay
”Gel-like Properties of Cartilage Proteoglycans”
Bjørn Torger Stokke
”A new strategy for ionotropic alginate gelation applied in microfluidic assisted
homogeneous bead synthesis and cell immobilization”
Stevin Gehrke
“Insectchitin-binding proteins induced biomacromolecular micropraarticle
formation in biomacromolecule solutions: inspirations from insect cuticle for
heiierarchical self-assembly using components of the insect cuticle system”
Yoshiaki Yuguchi
”Structural formation and gelation of neutral polysaccharides as observed by
small angle X-ray scattering”
Miroslava Duskova-Smrckova
”Interpenetrating Network Hydrogels: Roles and Fates of Network 1 and
Network 2”
Bradley Olsen
”Anomalous Self-Diffusion in Physical Polymer Gels”
Orsolya Czakkel
”Mechanical and thermoresponsive properties of PNIPA - graphene-oxide
composite gels”
Pitchaya Treenate
”Crosslinker Effects on Properties of Hydroxyethylacryl Chitosan/Sodium
Alginate Hydrogel Films”
Nobuyuki Takahashi
”Mesoscopic structural order in hydrogen bonding liquid”
Sebastian Seiffert
”Soft Sensitive Matter: Structure, Dynamics, and Function of Supramolecular
Polymer Gels”
Patrice Bourson
”Advantages to do in-situ measurements by Raman spectroscopy and
coupling with other techniques for the determination of physico-chemical
properties of polymers”
Juan Baselga
”Chemically modified hybrid thermosets: elastic behavior in the plateau regime
of polyaminosiloxane-nitrile-DGEBA”
Pierre Millereau
”Enhanced mechanical properties in multiple network elastomers”
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52
53
54
55
56
57
58
59
60
61
62
63
64
65
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O-18
O-19
O-20
O-21
O-22
O-23
O-24
O-25
O-26
O-27
O-28
O-29
O-30
O-31
O-32
O-33
O-34
O-35
David Diaz Diaz
”Gel networks as confined microenvironments for photochemical reactions
that are inaccessible in solution under mild conditions”
Viktor Granskog
“Linear-Dendritic Macromolecules as components in Biomedical Soft Tissue
Adhesives”
Morten Jarlstad Olesen
”Hydrogels as hosts for Substrate Mediated Enzyme Prodrug Therapy”
Felix Schacher
”Interface Design using Block Copolymers: Crosslinking and Interpolyelectrolyte Complexation”
Kenji Urayama
”Rheological Behavior of Dense Suspensions of Thermo-Responsive Microgels”
Tobias Ingverud
”Hydrogel composites of cellulose nanofibrils and thermoresponsive cationic
block copolymers as electrostatic macrocrosslinker”
Geng Hua
“Biobased hydrogels for metal ion waste water treatment”
Masaki Nakahata
”Highly Flexible, Tough, and Self-Healable Supramolecular Polymeric Materials Using Host–Guest Interaction”
Ben Bin Xu
“A new microfluidic switch technique by controllably buckling Stimuli-responsive polyelectrolyte hydrogel thin layer”
Daisuke Aoki
”Synthesis of Rotaxane-Cross-Linked Polymers Using Macromolecular [2]
Rotaxane Having Hydrophilic Axle Component as a Vinylic cross-linker”
Apichaya Jianprasert
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Yoshinori Takashima
”Photo stimuli responsive supramolecular and topological materials using
host-guest complexes”
Eleonora Parelius Jonasova
”Studying processes leading to swelling of DNA-responsive hydrogels”
Takashi Miyata
”Rational Design of Molecularly Stimuli-responsive Hydrogels Using
Supramolecular Crosslinks”
Heikki Tenhu
”Gold-decorated poly(N-vinylcaprolactam) gel particles”
Zhansaya Sadakbayeva
”IPN hydrogels of poly(2-hydroxyethyl methacrylate) and poly(2,3-dihydroxypropyl methacrylate) with tunable deformation responses”
Constantinos Tsitsilianis
”Recent trends in telechelic amphiphilic gelators: the use of random
copolymers as building blocks for tuning the network properties”
Rémi Absil
”Ultrafast gelation of injectable reactive microgels : The power of TAD click
chemistry””
78
”Crosslinker Effects on Properties of Hydroxyethylacryl Chitosan/Sodium Alginate
Hydrogel Films”
26
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O-37
O-38
O-39
O-40
O-41
O-42
O-43
O-44
O-45
O-46
O-47
O-48
O-49
Stevin Gehrke
Engineering glycosaminoglycan hydrogels to control swelling, moduli and
fracture properties
Chris Lowe
”Modelling Thermo-mechanical Aspects of Thermosetting Polymers and How
Monomer Composition Impacts Properties”
Per-Erik Sundell
”Multilayer coil coating - placing properties”
Steve Howdle
”Acrylate and Methacrylate Polymers and Coatings Derived from Terpenes”
Dirk W. Schubert
”Magnetic Liquid Silicone Rubber”
Aslihan Argun
”Nonionic Double and Triple Network Hydrogels”
Olga Philippova
”Self-assembled nanogels of chitosan”
Sami Hietala
”UCST-LCST double thermosensitive block copolymers”
Sada-Atsu Mukai
”Ring shape formation of nanogel-crosslinked matrials by using nonequilibrium process”
Gaio Paradossi
”Temperature tuning of hybrid nanogels surfaces”
Aleksey Drozdov
”Structure-property relations for equilibrium swelling of cationic polyelectrolyte
hydrogels”
Tim Bowden
”Nucleophilic Polymers - formation of hydrogels, particles and scavenging of
inflammatory mediators”
Martin Wåhlander
”Next-Generation Matrix-Free Graphene Composites with Tuneable
Orientation and Shape-Memory Effect”
Jean-Paul Chapel
”Early Stage Kinetics and structure of Polyelectrolyte Complexes Studied by
Stopped-Flow and Neutron scattering”
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90
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95
96
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98
Posters
P-1
P-2
P-3
P-4
P-5
Takehiko Gotoh
“New Metal Ion Recovery Method Using Protanated Hydrogel”
Wei Liu
“An improved one-particle microrheometer by a combination of magnetic
tweezers and total internal reflection microscope in living cells”
Kazuya Matsumoto
“Design of Drug-Loaded Polypeptide Hydrogels via Molecular Imprinting and
Their Controlled Release by Helix-Coil Transition”
Beata Mossety-Leszczak
“Carbon composites based on liquid crystalline epoxy resin”
Beata Mossety-Leszczak
“Formation of the hydrophobic thermosetting polyurethane powder clear coatings”
27
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101
102
103
104
P-6
P-7
P-8
P-9
P-10
P-11
P-12
P-13
P-14
P-15
P-16
P-17
P-18
P-19
P-20
P-21
P-22
P-23
Koji Nagahama
“Nanohybrid Injectable Gels Composed of Polymer Micelles, Clay Nanodisk,
and Doxorubicin for Efficient Focal Tumor Treatment”
Yoshimi Seida
“Adsorption and desorption properties of acrylate-acrylic acid gel for VOC
observed by QCM-A”
Ahmet Erdem
“Synthesis of grafted pH and thermo responsive hydrogels via ring opening
polymerization of polyethyleneoxide bis(glycidyl ether) with
monoamino/diamino Jeffamine”
Ki-Hwang Hwang
“3D hydrogel scaffold combined with piezoelectric nanorods grown on fabric
fibers”
Ki-Hwan Hwang
“Ice adhesion affected by counterion exchange on core/shell microgels”
Ki-Hwang Hwang
“Alginate-based electroconductive hydrogels via UV-mediated thiol-ene reaction”
Esra Su
“Supramolecular polyampholyte hydrogels formed via hydrophobic and ionic
interactions”
Akifumi Kawamura
“Preparation of pH/Redox-responsive Gel Particles as Smart Carriers for
Intracellular Delivery”
Won Kyu Kim
“Effect of fluctuations on tracer diffusion in networks and liquids”
Kohei Otani
“Preparation of supramolecular polymeric materials using host-guest interaction between cyclodextrin and alkyl chain modified with viologen”
Kateryna Khairulina
“Development of polyethylene glycol-graphene oxide hydrogel composite and
its application in electrophoresis of double stranded DNA”
105
Muchao Qu
“Conductivity of Melt-Spun PMMA Composites with Aligned Carbon Fibers”
Mathias Rohn
“Photo crosslinked defined tetra-PEG networks”
Yuki Sawa
“Toughness and Self-healing Materials Cross-linked by Cyclodextrin-guest
Complexes”
Jun Sawada
“Polymer Chain Mobility-Dependent Property of Cross-Linked Polymer Synthesized with Rotaxane Cross-Linker”
Ayaka Takemoto
“Living” Smart Gels Made by Bioorthogonal Cross-Linking Reactions of
Azide-Modified Cells with Alkyne-Modified Biocompatible Polymers”
Jonas Daenicke
“Influence of crosslinking and penetrant size on the diffusion properties of
cyclic siloxanes through silicone elastomers”
Gaio Paradossi
“Quasi-2D polymer networks as shells of acoustic responsive microvesicles
and microbubbles”
116
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118
119
120
121
122
P-24
Maja Finnveden
“One-Component Thiol-Alkene Functional Oligoester Resins Utilizing Lipase
Catalysis”
123
P-25
Olga Ryazanova
“Network-like structure formed by inorganic polyphosphate through pi-stacked
cationic porphyrins”
Matej Kanduc
“Adsorption of reactants on a PNIPAM polymer”
Samer Nameer
“Self-catalyzed thermal crosslinking of fully bio-based epoxy resins”
Costas Patrickios
“Double Networks Bearing the Mechano-Responsive Moiety of Spiropyran”
124
Costas Patrickios
“Amphiphilic Polymer Conetworks: Prediction of Their Ability for Oil
Solubilization”
Costas Patrickios
“Amphiphilic Dynamic Covalent Hydrogels: Synthesis and Characterization”
Costas Patrickios
“Synthesis and Characterization of End-linked Amphiphilic Polymer Conetworks Based on ABA Triblock Copolymers”
Andrea Träger
Strong and Tunable Wet Adhesion with Rationally Designed Layer-by-Layer
Assembled Triblock Copolymer Films!
Sara Brännström
“Renewable UV-curable Polyesters Based on Itaconic Acid: Synthesis and
characterization”
128
P-26
P-27
P-28
P-29
P-30
P-31
P-32
P-33
29
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126
127
129
130
131
132
Plenary Speakers
Mitsuhiro Shibayama
University of Tokyo, Japan
Bela Iván
“Amphiphilic Conetworks as a New Material Platform of
Bicontinuous Nanophasic Macromolecular Assemblies, Intelligent
Gels and Unique Organic-Inorganic Nanohybrids”
Research Centre for Natural Sciences, Hungarian Academy of
Sciences, Budapest, Hungary
James Lewicki
“A Multi-scale Experimental and Computational Approach to
Studying Network Dynamics in Complex Polysiloxane
Elastomers”
Lawrence Livermore National Laboratory, CA, USA
Chi Wu
“A Novel Microrheometer - Total Internal Reflection Microscope
Marries Magnetic Tweezers”
The Chinese University of Hong Kong, Hong Kong
Dominique Hourdet
“Macromolecular assemblies in aqueous media: from controlled
rheology of polymer solutions to mechanical reinforcement of
covalent hydrogels”
Molly Stevens
“Designing Bio-inspired Materials for Biosensing and
Regenerative Medicine”
Imperial College, London, UK
Françoise M. Winnik
“Biological Responses to Chitosan Substituted With Zwitterionic
Groups”
University of Montreal, Montreal, Canada
Olli Ikkala
“Supramolecular Functionalization of Molecular Colloids and
Colloidal Networks”
Aalto University, Helsinki, Finland
Zhigang Suo
“Soft Materials and Soft Machines”
Harvard John A. Paulson School of Engineering and Applied
Sciences, Boston, USA
30
Plenary
PL-1
Exploration of Ideal Polymer Networks
Mitsuhiro Shibayama
Institute for Solid State Physics, The University of Tokyo 5-1-5 Kashiwanoha, Kashiwa,
Chiba 277-8581, Japan
[email protected]
There is a long history in preparation/development of polymer networks and gels (Fig. 1).
Vulcanization of natural rubber was invented in 19th century. In the beginning of the last century,
the first man-made plastic, the so-called “bakelite” (phenolic resin), was
invented. Today, polymer networks, such as rubbers, thermosets, and
polymer gels are made by radical polymerization or polymer cross-linking.
As a natural consequence, it had been desired to prepare “ideal polymer
networks”consisting of equi-length subchains beween cross-links and of
carrying neither defects nor entanglements. Though trials along this concept
started in 1970s as “model networks”,[1] it had never been achieved
because of difficulty in controlling polymerization and cross-link reaction,
side reaction, topological complexity of polymer network structure, etc. We
developed a novel class of hydrogels by “cross-end-coupling”of two
types of tetra-arm poly(ethylene glycol) (PEG) prepolymers that have
mutually reactive amine (Tetra-PEG-NH2) and activated ester (TetraPEG-NHS) terminal groups, respectively.[2] From small-angle neutron
scattering (SANS) measurements on Tetra-PEG gel, it was confirmed
that Tetra-PEG gels have a near-ideal network.[3,4] Because of their
network homogeneity and biocompatibility, Tetra-PEG gels are now a
potential candidate for biomedical applications and structural materials.
However, it has been an open question why Tetra-PEG gel is so homogeneous. In order to answer this question, we investigated the gelation
kinetics and structure evolution of Tetra-PEG gel.[5] Fig. 2 shows
that Tetra-PEG gelation is reaction-limited reaction.[5] Furthermore, we
carried out (1) the network structure of defect-controlled polymer
networks,[6] and (2) experimental and theoretical aspects of the mechanical properties of tetra-functional polymer networks.[7,8] Some practical
applications of ideal networks including high performance uniform ion gels
will be demonstrated.
References:
[1] P. –H. Soug and J. E. Mark, Makromol. Chem. 180, Suppl. 2, 82 (1979),
[2] T. Sakai, et al., Macromolecules 41, 5379 (2008),
[3,4] T. Matsunaga, et al., Macromolecules 42, 1344 (2009), ibid 42, 6245-6252 (2009),
[5] K. Nishi, et al., Macromolecules 47, 3274 (2014),
[6] K. Nishi, et al., Macromolecules 47, 1801-1809 (2014),
[7] K. Nishi, et al., J. Chem. Phys. 137, 224903 (2012), [8] K. Nishi, et al., J. Chem. Phys. 143, 184905
(2015).
31
Plenary
PL-2
Amphiphilic Conetworks as a New Material Platform of Bicontinuous
Nanophasic Macromolecular Assemblies, Intelligent Gels and Unique
Organic-Inorganic Nanohybrids
Béla Iván1, Csaba Fodor1, Márton Haraszti1, Péter Mezey1, Tímea Stumphauser1, Ákos Szabó1,
Bence Varga1, Ralf Thomann2, Yi Thomann2, Rolf Mülhaupt2
Polymer Chemistry Research Group, Institute of Materials and Environmental Chemistry,
Research Centre for Natural Sciences, Hungarian Academy of Sciences H-1117 Budapest,
Magyar tudósok krt. 2, Hungary
2
Freiburg Material Research Center and Institute for Macromolecular Chemistry,
University of Freiburg, Stefan Meier Str. 31, D-79104 Freiburg, Germany
1
E-mail: [email protected]
Amphiphilic conetworks (APCNs) (see e.g. refs. 1-10) composed of covalently bonded otherwise immiscible
hydrophilic and hydrophobic chains belong to a new group of rapidly emerging nanostructured materials. The structure and morphology of APCNs are shown in Figure 1.
Hydrophobic Polymer
Hydrophilic Polymer
Figure 1. Schematic structure of an amphiphilic conetwork (APCN) and an AFM image of the bicontinuous nanophasic
morphology.
Due to the strong chemical bonds, unique bicontinuous nanophase separated morphology exists in
APCNs in a broad composition window. This is the basis for the preparation of various specialty
new intelligent (responsive) gels and organic-inorganic nanohybrids by applying one of the nanophases as
nanoreactor. The resulting novel materials have a variety of high added-value potential applications from
nanocatalysis and photonics to biomaterials etc.
Acknowledgements. Support of this research by the National Research, Development and Innovation
Office (K112094) and the National Development Agency (KTIA-AIK-12-1-2012-0014) is acknowledged.
References
1. B. Iván, J. P. Kennedy, P. W. Mackey, ACS Symp. Ser.1991, 469, 194-202; ibid. 1991, 469, 203-212
2. B. Iván, J. P. Kennedy, P. W. Mackey, US Patent1991, 5,073,381
3. J. Scherble, R. Thomann, B. Iván, R. Mülhaupt, J. Polym. Sci., Part B: Polym. Phys.2001, 39, 14291436
4. B. Iván, K. Almdal, K. Mortensen, I. Johannsen, J. Kops, Macromolecules2001, 34, 1579-1585
5. A. Domján, G. Erdődi, M. Wilhelm, M. Neidhöfer, K. Landfester, B. Iván, H. W. Spiess, Macromolecules2003, 36, 9107-9114
6. N. Bruns, J. Scherble, L. Hartmann, R. Thomann, B. Iván, R. Mülhaupt, J. C. Tiller, Macromolecules,
2005, 38, 2431-2438
7. B. Iván, M. Haraszti, G. Erdődi, J. Scherble, R. Thomann, R. Mülhaupt, Macromol. Symp., 2005, 227,
265-274
8. M. Haraszti, E. Tóth, B. Iván, Chem. Mater.2006, 18, 4952-4958
9. Cs. Fodor, A. Domján, B. Iván, Polym. Chem.2013, 4, 3714-3724
10. Cs. Fodor, J. Bozi, M. Blazsó, B. Iván, RSC Advances 2015, 5, 17413-17423
32
Plenary
PL-3
A Multi-scale Experimental and Computational Approach to Studying Network
Dynamics in Complex Polysiloxane Elastomers
James P. Lewicki, Robert S. Maxwell, Todd Weisgraber, Amitesh Maiti, Sarah C, Chinn, Thomas S.
Wilson, Long Dinh, Ward Small, Cynthia T. Alviso, Jennifer N. Rodriguez, April Sawvel.
Lawrence Livermore Natl. Laboratory, 7000 East Ave. L-231, Livermore, CA 94550, US
[email protected]
Linear polysiloxanes show remarkable and often highly ideal behavior from a polymer physics standpoint.
The polydimethylsiloxane (PDMS) chain is extremely flexible and translationally mobile. PDMS has a large
molar volume and the polymer chains can coil and uncoil very freely over ambient temperatures and reasonable timescales of study As such, linear PDMS is often the ‘polymer of choice’ for magnetic resonance based
polymer physics studies into the fundamentals of chain dynamics and large scale cooperative processes in
polymer melts. However, polysiloxanes are often employed in application not as simple linear polymers but
as complex, hierarchical network composites. See Figure 1.
Figure 1. Polysiloxane network elastomers are complex multi-component systems - incorporating multi-modal distributions of chain lengths, varied crosslink topologies/densities, chemically modified free chain ends, non-stoichiometric
excesses of reactive moieties, and often large volume fractions of a variety of reactive and/or passive filler materials
These complex and often ill-defined polymer networks present both an experimental/computational challenge and an opportunity to develop our knowledge and skillset in polymer network theory. At LLNL we are
invested in making accurate assessments and predictions of polysiloxane network based materials performance and lifetimes over a broad range of environmental conditions, therefore we are actively studying and
modeling the relationships between underlying network architecture, dynamics, physical properties, materials performance, stability and lifetime. In this lecture we will discuss a combined multilevel experimental &
computational approach towards understanding structure property relationships in polysiloxane networks
through; experimental solid state NMR, thermal, and mechanical analysis - in conjunction with network and
finite element modeling & simulation.
This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore
National Laboratory under Contract DE-AC52-07NA27344.
33
Plenary
PL-4
Single-Particle Tracking Micro-rheometer –
Magnetic Tweezer Marries Total Internal Reflection Microscope
Chi Wu,1,2 Xiangjun Gong,3 Wei Liu,4 To Ngai4
Department of Chemistry, The Chinese University of Hong Kong, Hong Kong
Hefei National Laboratory for Physical Sciences at Microsacle, Department of Chemical Physics,
University of Science and Technology of China, Anhui, China
3
School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510640,
China
4
Department of Physics, The Chinese University of Hong Kong, Hong Kong, China
1
2
Viscoelastic properties of soft matters, including polymer gel networks, can be determined by a variety of types
of rheometers. Recently, rheological responses over a small length-scale (~10 mm) can be quantitatively
measured by different micro-rheometers that are particularly useful in probing soft physical gels because the
interaction is often so weak that macroscopic mechanic perturbation inevitably disturbs the gel structure. We
will demonstrate a new and unique micro-rheometer by incorporating a magnetic tweezer into a total internal
reflection microscope (TIRM), as shown in the right figure, and how it can be used to measure rheological
properties of soft materials, including complex fluids,
polymer gels and biologic samples1. The basic principle
of such a micro-rheometer will be outlined as follows. In
TIRM, an evanescent wave is generated from the total
internal reflection of an incident laser light at a solid (glass
slide)/liquid interface. The light intensity of such a wave
exponentially decays with the distance away from the
interface. When a probe magnetic bead (~mm) is placed
close to the interface within ~102 nm, it scatters the light.
As expected, the scattered light intensity exponentially
decays as the bead moves away from the interface,
extremely sensitive even for tracking the thermal
fluctuation of an embedded bead particle, i.e., measuring the weak van der Waals force (~10-13 N)2,3. Further,
by placing two sets of four electromagnetic pole pieces symmetrically above and below the sample cell, we
are able to control and move the bead in three dimensions. By applying an oscillated electrical field on the
embedded magnetic bead and monitoring its response, we are able to precisely measure a force as weak as
~10-15 N and a displacement as small as ~1 nm. Few examples will be used to illustrate how this novel microrheometer can be used to study the kinetics of the sol-gel transition of hydrogels made of spherical poly(Nisopropylacrylamide) (PNIPAM) microgels, biopolymer chitosan, and buvine serum albumin (BSA) protein,
respectively, and measure rheological and mechanical properties of soft matters at the microscales, resulting
in deeper understanding of interaction and dynamics of macromolecules in soft materials.
1. Gong, X.; Hua, L.; Wu, C.; Ngai, T. Review of Scientific Instruments 2013, 84, 033702.
2. Prieve, D. C. Advances in Colloid and Interface Science 1999, 82, 93.
3. Gong, X.; Wang, Z.; Ngai, T. Chemical Communications 2014, 50, 6556.
34
PL-5
Plenary
Macromolecular assemblies in aqueous media: from controlled rheology of
polymer solutions to mechanical reinforcement of covalent hydrogels.
Dominique Hourdet1,2
1
Sorbonne Universités, UPMC Univ Paris 06, Sciences et Ingénierie de la Matière Molle, CNRS
UMR 7615, 10 rue Vauquelin, F-75005, Paris, France.
2
École Supérieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI),
ParisTech, PSL Research University, SIMM, 10 rue Vauquelin, F-75005 Paris, France.
e-mail : [email protected]
By working at the molecular level with physical interactions taking place in polymer solutions, it is possible to
drive and to finely tune macromolecular assemblies in order to improve the performance of soft formulations
under specified environments. This strategy, that has been successfully applied in the development of complex fluids with important applications in oil, cosmetics and biomedical industries, finds actually new potentialities in the design of tough hydrogels. Indeed, the combination of both covalent and physical cross-links
within the same architecture is actually one of the most promising strategies in this field.
At the border between these two domains (liquids and solids), we will present in this lecture different functionalities that can be used to control macromolecular assemblies in aqueous formulations and describe how
these functionalities can be used to design covalent hydrogels with improved mechanical properties.
Based on a simple toolbox including a macromolecular backbone and polymer side-chains, adding covalent
cross-links and/or inorganic particles, we will demonstrate the versatility of this approach for the design of
reversible and even responsive assemblies with a special emphasis on the structure/properties relationships.
References
Petit L., Bouteiller L., Brûlet A., Lafuma F., Hourdet D. Langmuir 2007, 23, 147-158.
Siband E., Tran Y., Hourdet D. Macromolecules 2011, 44, 8185-8194.
Rose S., Dizeux A., Narita T., Hourdet D., Marcellan A. Macromolecules 2013, 46, 4095−4104.
Guo H., Brûlet A., Rajamohanan P. R., Marcellan A., Sanson N., Hourdet D. Polymer 2015, 60, 164175.
35
Plenary
PL-6
New polymer based approaches for biosensing and regenerative
medicine
M. M. Stevens
Department of Materials and Department of Bioengineering, Imperial College London,
London, UK
Bio-responsive nanomaterials are of growing importance with potential applications including drug
delivery, diagnostics and tissue engineering (1-3). A disagreeable side effect of longer life-spans is the
failure of onepart of the body – the knees, for example – before the body as a wholeis ready to surrender.
The search for replacement body parts hasfuelled the highly interdisciplinary field of tissue engineering
and regenerative medicine. This talk will describe our research on the design of new materials to
direct stem cell differentiation for regenerative medicine. This talk will also provide an overview of our
recent developments in the design of materials for ultrasensitive biosensing. We are applying these
biosensing approaches both in high throughput drug screening and to diagnose diseases ranging from
cancer to global health applications.References
[1] Stevens MM, George JH, Exploring and engineering the cell surface interface, Science, 2005, 310,
1135.
[2] Place ES, Evans ND, Stevens MM, Complexity in biomaterials for tissue engineering., Nature Materials,
2009, 8, 457.
[3] Howes P, Chandrawati R, Stevens MM. Colloidal nanoparticles as advanced biological sensors. Science. 2014, 346, 6205.
36
Plenary
PL-7
Biological responses to chitosans substituted with zwitterionic groups
Françoise M. Winnik,1,2,3 Baowen Qi,1 Grégory Beaune,2 and Piotr Kujawa2
1
2
University of Montreal, Department of Chemistry, Montreal, QC, Canada
WPI International Center of Materials Nanoarchitectoniocs, (MANA) National Institute for Materials
Science, Tsukuba, Japan
3
University of Helsinki, Department of Chemistry and Faculty of Pharmacy, Helsinki, Finland
[email protected]
Chitosan (CH), a polysaccharide derived from natural chitin, is a ubiquitous component of biomaterials in
important medical fields, particularly as a substrate in tissue engineering and in drug delivery. Chitosan substituted with phosphorylcholine groups (CH-PC), which is soluble under physiological conditions, was used
as a prodrug substrate and in protective coatings for medical devices and cells. In biological environments
CH-PC coatings exhibit the bioadhesive properties of CH as well as the non-fouling characteristics of PC.
Hence the CH-PC architecture is ideally suited to modulate cell spreading and aggregation.1 This concept
will be illustrated in the presentation. The physical and biological properties of CH-PC films, will be described
with views on their physico-chemical properties and biological applications.
Figure 1: Structure and properties of Phosphorylcholine films in the presence of proteins (left) and cells (right)
(1) B. Qi et al, Macromol. Biosci., 2015, 15, 490-500;
37
Plenary
PL-8
Supramolecular functionalization of molecular and colloidal networks
Olli Ikkala,
Aalto University, Department of Applied Physics, Molecular materials, P.O. Box 15100, FIN-00076 Aalto,
Espoo, Finland
Supramolecular concepts allow a great versatility in tailoring self-assemblies and networks. This is because
they can allow tuning of the interaction strength and also exchange kinetics towards synergistic properties,
i.e. properties that usually are considered to be competing. In this talk we will discuss selected examples on
molecular and colloidal networks with functional properties by tailored crosslinks. In molecular level networks,
hydrogen bonding is a classic example for supramolecular crosslinks, facilitating directionality, strength, and
rapid exchange rate. Recently, halogen bonds have been progressed as another Lewis-pair based supramolecular interaction (1). Here we first show nano-confined halogen-bond supramolecular crosslinking in block
copolymer complexes, where the system shows well-defined hierarchical supramolecular self-assembled
network structure in the nanometer and tens of nanometer length scales (2). In the colloidal level networks,
the dynamics can be suppressed, limiting possibilities for functionalities, esp. aiming at high mechanical
properties combining with healing. Here we show that in nanocellulose-based physical hydrogels, supramolecular cucurbituril units allow rapid exchange kinetics to allow rapid healing and bridging dynamically the
gel components over the length scales (3-4). In some applications permanent crosslinking is needed, for
example to achieve sufficient wet strength to allow surgical threads based on nanocellulose fibers. They are
attractive as they allow stem-cell growth (5). In some applications water penetration can even be converted
towards functionality, as in humidity-based reversible actuation in nanocellulose-based films (6). Finally, we
discuss nanocellulose-based dried networks to form aerogels, which can be coated with electrically conducting carbon nanotube networks (7). Such materials can be useful templates for soft devices.
1. G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimägi, G. Resnati, G. Terraneo, Chem. Rev. 116, 2478
(2016).
2. R. Milani, N. Houbenov, G. Cavallo, F. Fernandez-Palacio, A. Luzio, J. Haataja, M. Saccone, A. Priimagi,
G. Resnati, P. Metrangolo, O. Ikkala, submitted.
3. J. R. McKee, E. A. Appel, J. Seitsonen, E. Kontturi, O. A. Scherman, O. Ikkala, Adv. Funct. Mater, 24, 2706
(2014).
4. E.-R. Janecek, J. R. McKee, C. S. Y. Tan, A. Nykänen, M. Kettunen, J. Laine, O. Ikkala, O. A. Scherman,
Angew. Chem., Int. Ed., 54, 5473 (2015).
5. H. Mertaniemi, C. Escobedo-Lucea, A. Sanz-García, C. Gandía, A. Mäkitie, J. Partanen, O. Ikkala, M. Yliperttula, Biomaterials, 82, 208 (2016).
6. M. Wang, X. Tian, R. H. A. Ras, O. Ikkala, Adv. Mater. Interf., 2, 1500080 (2015).
7. M. S. Toivonen, A. Kaskela, O. J. Rojas, E. I. Kauppinen, O. Ikkala, Adv. Funct. Mater., 25, 6618 (2015).
38
Plenary
PL-9
Hydrogel as Tough Water
Zhigang Suo
School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138
[email protected]
Several recent findings show that hydrogels can achieve properties and applications well beyond previously
imagined [1-7]. Most existing hydrogels, like Jell-O and tofu, are fragile and dry out in open air. We have
made hydrogels as tough as rubber, and retain water in low-humidity environment. We use hydrogels to
mimic the function of axons, transmitting electrical signals over long distances, at high speeds. We make a
high-speed ionic cable transmit signals with a diffusivity 16 orders of magnitude higher than the diffusivity of
ions in water. We make a loudspeaker play music over entire audible range, and transmit light of all colors.
We demonstrate an ionic skin—a stretchable, transparent, large-area sheet of distributed sensors. We use
hydrogel as transparent electrodes to enable electroluminescence of giant stretchability. We show that hydrogels outperform existing fire-retarding materials. This talk describes the mechanics and chemistry of these
materials and devices.
1. Jeong-Yun Sun, Xuanhe Zhao, Widusha R.K. Illeperuma, Kyu Hwan Oh, David J. Mooney, Joost J.
Vlassak, Zhigang Suo. Highly stretchable and tough hydrogels. Nature 489, 133-136 (2012).
2. Christoph Keplinger, Jeong-Yun Sun, Choon Chiang Foo, Philipp Rothemund, George M. Whitesides,
Zhigang Suo. Stretchable, transparent, ionic conductors. Science 341, 984-987 (2013).
3. Y. Bai, B. Chen, F. Xiang, J. Zhou, H. Wang, Z.G. Suo. Transparent hydrogel with enhanced water
retention capacity by introducing highly hydratable salt. Applied Physics Letters 105, 191903 (2014).
4. Jeong-Yun Sun, Christoph Keplinger, George M. Whitesides, Zhigang Suo. Ionic skin. Advanced Materials 26, 7608-7814 (2014).
5. Jianyu Li, Zhigang Suo, Joost J. Vlassak. Stiff, strong, and tough hydrogels with good chemical stability. Journal of Materials Chemistry B 2, 6708-6713 (2014).
6. W.R.K. Illeperuma, P. Rothemund, Z.G. Suo, J.J. Vlassak. Fire-resistant hydrogel-fabric laminates: a
simple concept that may save lives. ACS Applied Materials & Interfaces 8, 2071-2077 (2016).
7. C.H. Yang, B. Chen, J. Zhou, Y.M. Chen, Z.G. Suo. Electroluminescence of giant stretchability. Advanced Materials 2015. DOI: 10.1002/adma.201504031
39
Keynote Speakers
Filip Du Prez
“New Generation of Vitrimers: Permanent Polymeric Networks with
Glass-like Fluidity”
Ghent University, Belgium
Juergen Groll
“Dynamic Polymer Networks for Biofabrication: General
Strategies and Specific Examples”
University of Würzburg
Anne Ladegaard Skov
“Interpenetrating Networks Based on Covalent and Ionic
Networks Facilitating Self-healing “
Technical University of Denmark DTU, Denmark
Kazunari Akiyoshi
“Self-Assembled Nanogel Tectonics for Advanced Biomaterials”
Kyoto University, Kyoto, Japan
Alexander Zelikin
“Poly(vinyl alcohol) physical gels: New vista on a long serving
biomaterial”
Aarhus University, Aarhus, Denmark
Jacqueline Forcada
“Multi-stimuli-responsive Nanogels for Bio-applications”
University of the Basque Country, San Sebastian, Spain
Marco Sangermano
“Cationically UV-cured Functional Polymeric Networks”
Politecnico di Torino, Turin, Italy
Berit Løkensgard Strand
“Tailoring alginates for tissue engineering applications by chemoenzymatic modification”
Norwegian University of Science and Technology, Norway
40
Keynote
K-1
New Generation of Vitrimers:
Permanent Polymeric Networks with Glass-like Fluidity
Filip Du Prez, Wim Denissen, Johan Winne
Department of Organic and Macromolecular Chemistry, Polymer Chemistry Research Group, Ghent
University, Krijgslaan 281 S4bis, 9000 Ghent, Belgium
Email: [email protected]
Most covalent adaptable networks give highly interesting properties for material processing such as reshaping,
recycling and repairing. Classical thermally reversible chemical cross-links allow for a heat- triggered switch
between materials that behave as insoluble cured resins, and liquid
thermoplastic materials, through a fully reversible sol–gel transition.
In 2011, a new class of materials, coined vitrimers1,2, was introduced,
which extended the realm of adaptable organic polymer networks.
Such materials have the remarkable property that they can be thermally processed in a liquid state without losing network integrity. This
feature renders the materials processable like vitreous glass, without
the need of molds or precise temperature control. In this research3,
we developed vitrimers based on transamination of vinylogous urethanes. These urethane-like chemical moieties emerge as interesting bonds for building vitrimers as they combine chemical robustness
with rapid exchange kinetics. We show on model compounds that the
exchange reactions is swift in a favorable temperature window and
can even be fine-tuned by the presence of simple acids or base additives. Next, different kind of cross-linked materials, ranging from flexible elastomers to rigid thermosets, were made from bulk chemicals.
These materials behave at room temperature as classical thermosets
but become processable when heated as evidenced by stress-relaxation experiments. In addition, the networks are recyclable up to four
times by consecutive grinding/compression molding cycles without
significant mechanical or chemical degradation.
(1) Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Science 2011, 334, 965.
(2) Denissen, W.; Winne, J. M.; Du Prez, F. E. Chem. Sci 2016, 7, 30.
(3) Denissen, W.; Rivero, G.; Nicolaÿ, R.; Leibler, L.; Winne, J. M.; Du Prez, F. E. Adv. Funct. Mater. 2015, 25, 2451.
41
Keynote
K-2
Dynamic Polymer Networks for Biofabrication: General Strategies and
Specific Examples
Jürgen Groll1, Tomasz Jüngst1, Willi Smolan1, Simone Stichler1, Kristin Schacht2, Thomas Scheibel2, Jörg
Teßmar1
1) Chair for Functional Materials in Medicine and Dentistry, University of Würzburg, Pleicherwall 2, 97070
Würzburg, Germany
2) Chair of Biomaterials, Faculty of Engineering Science, University of Bayreuth, Universitätsstrasse 30,
95447 Bayreuth, Germany
[email protected]
Biofabrication is a young and dynamically evolving field of research [1]. It aims at the automated generation
of tissues from cells and materials through Bioprinting or Bioassembly. One of the major challenges in the
field is the lack of variety in printable hydrogel systems [2]. In order to be suitable for Biofabrication, hydrogels
have to comply with a number of prerequisites with regards to rheological behavior and especially stabilization of the printed structure instantly after printing, while at the same time allowing the cells to proliferate.
This lecture will briefly introduce the field and the major printing techniques, as well as the most important
material demands. It will then introduce thiol-ene cross-linking of poly(glycidyl-co-allylglycidylether) based
3D plotted hydrogels as alternative to the often used free radical polymerization to stabilize printed hydrogel structures with high resolution and reproducibility. Furthermore, a purely physically cross-linked system
based on recombinant spider silk proteins will be introduced [3], in which beta-sheet interactions facilitate
good printability and stability of the constructs.
Literature
[1] J. Groll, T. Boland, T. Blunk, J.A. Burdick, D.-W. Cho, P.D. Dalton, B. Derby, G. Forgacs, Q. Li, V.A. Mironov, L. Moroni, M. Nakamura, W. Shu, S. Takeuchi, G. Vozzi, T.B.F. Woodfield, T. Xu, J.J. Yoo, J. Malda: Biofabrication: Reappraising the definition of an evolving field. Biofabrication 2016, 8, 013001.
[2] T. Jüngst, W. Smolan, K. Schacht, T. Scheibel, J. Groll: Strategies and Molecular Design Criteria for 3D
Printable Hydrogels. Chemical Reviews, 2016, 116 (3), 1496.
[3] K. Schacht, T. Jüngst, M. Schweinlin, A. Ewald, J. Groll, T. Scheibel: Biofabrication of Cell-loaded, 3D Recombinant Spider Silk Constructs. Angewandte Chemie International Edition 2015, 54 (9), 2816.
42
Keynote
K-3
Interpenetrating networks based on covalent and ionic networks
facilitating self-healing
Anne Ladegaard Skov, Frederikke Bahrt Madsen and Liyun Yu
Danish Polymer Centre, Department of Chemical and Biochemical Engineering, Technical University of
Denmark, DTU, Søltofts Plads, Building 227, 2800 Kgs. Lyngby, Denmark
e-mail: [email protected]
Currently used dielectric elastomers do not have the ability to self-heal after detrimental events such as
tearing or electrical breakdown, which are critical issues in relation to product reliability and lifetime.[1] In this
work we present a self-healing dielectric elastomer which additionally possesses high dielectric permittivity
and consists of an interpenetrating polymer network (IPN) of silicone elastomer and ionic silicone species
which are cross-linked through the protonation of amines and acids.[2] The ionically cross-linked silicone
provides self-healing properties after electrical breakdown or cuts made directly to the material, due to the
reassembly of the ionic bonds that are broken during damage, as shown in Figure 1. The dielectric elastomers presented in this paper pave the way to increased lifetimes and the ability of dielectric elastomers to
survive millions of cycles in high-voltage conditions.
Figure 1: (a) Chemistry of the prepared IPNs and their self-healing abilities. (b) SEM images of a sample
that has been subjected to dielectric breakdown before and after self-healing. (c) Cylinder (here illustrated
by one piece coloured in green) and rectangle samples before and after self-healing.
References
[1] F. B. Madsen, A. E. Daugaard, S. Hvilsted, A. L. Skov. The Current State of Silicone-Based Dielectric
Elastomer Transducers. Macromolecular Rapid Communications 2016, 37(5): 378-413.
[2] L. Yu, F. B. Madsen, S. Hvilsted, A. L. Skov. Dielectric elastomers, with very high dielectric permittivity,
based on silicone and ionic interpenetrating networks. RSC Advances 2015, 5(61): 49739-49747.
43
Keynote
K-4
Self-Assembled Nanogel Tectonics for Advanced Biomaterials
Kazunari Akiyoshi
Department of Polymer Chemistry, Kyoto University, JST ERATO
Kyotodaigaku Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan [email protected]
Nanogels can be used as a new biologics DDS by efficiently trapping biomacromolecules such as DNA,
siRNA, peptides and proteins. We first reported physically cross-linked nanogels by self-assembly of hydrophobized polysaccharides (self-Nanogel). The proteins are trapped inside of the amphiphilic nanogel polymer
network without aggregation and are able to be released in the native form by various stimuli (chaperon function) 1. Polysaccharide nanogels act as a universal protein-based antigen delivery vehicle for efficient cancer
vaccine system and for intranasal vaccination. Recently, a new method, termed nanogel tectonics, was proposed to construct hydrogel materials with a hierarchical structure for advanced gel biomedical. Nanogels are
used as individual components for building nano-integrated functional hydrogel systems2.
Nanogel-crosslinked (NanoClik) microspheres have been developed via the emulsion-mediated crosslinking of self-Nanogels for the production of new injectable hydrogel particles3. The microspheres released
“drug-loaded nanogels” after hydrolysis, resulting in successful sustained drug delivery in vivo. A variety of
other microspheres with two-layered structure and lipid- or liposome- modified structures were also prepared
by nanogel tectonic method. Recently, we developed nanogel-crosslinked porous (NanoCliP) gels that can
trap proteins, liposomes, and cells4. Two-photon excitation deep imaging revealed that the NanoCliP gel comprises interconnected pores of several hundred micrometers in diameter. The NanoCliP gel enhanced cell
infiltration, tissue ingrowth, and neovascularization without requiring exogenous growth factors The NanoCliP
gel is a new universal platform suitable for use as a scaffold in tissue engineering.
Figure1. Nanogel tectonic materials
References
1. Y. Sasaki, K. Akiyoshi, The Chemical Record 2011, 10, 366-376.
2. Y.Sasaki, K. Akiyoshi, Chem. Lett. Highlight review 2012, 41, 202-208.
3. Y. Tahara, S. Mukai, S. Sawada, Y. Sasaki, K. Akiyoshi, Adv. Mater., 2015, 27, 5080-5088.
4. Y. Hashimoto, S. Mukai, S. Sawada, Y. Sasaki, K. Akiyoshi, Biomaterials 2015, 37, 107-115.
44
Keynote
K-5
Poly(vinyl alcohol) physical hydrogels:
New Vista on a Long Serving Biomaterial
Alexander N. Zelikin
Department of Chemistry, Aarhus University, Aarhus, Denmark
Email : [email protected]
Poly(vinyl alcohol) physical hydrogels are biomaterials with a long and a successful history of biomedical
applications. However, historically, these matrices have been prepared as non-degradable, permanent implants and most often as highly porous materials (via cryogelation). While beneficial for some applications,
these characteristics significantly limited the scope and utility of PVA gels in biomedicine.
Over the past few years, we have paid much attention to re-designing PVA physical hydrogels, specifically
to obtain these biomaterials as spontaneously eroding matrices with facile tools for bioconjugation and drug
delivery. Key to controlling the biodegradation kinetics of the gels was in the synthesis of polymer samples
with controlled molar mass and narrow dispersity. 1 Synthesized via RAFT polymerization, polymer chains
were also equipped with specific terminal groups for bioconjugation with diverse solutes, including peptides,
2
globular proteins and growth factors 3 – all performed at physiological conditions. Non-cryogenic methods of polymer gelation were developed to produce biomaterials with sub-micrometer control over surface
topography. 4, 5 Thus re-designed PVA biomaterials provided both, biophysical and biochemical cues for
controlled proliferation of the adhering cells.
For site-specific drug delivery, we developed an approach for a localized synthesis of drug molecules via
the Enzyme-Prodrug Therapy. 6-9 PVA hydrogels containing enzymes were effective in converting externally administered prodrugs. 8, 9 These biocatalytic hydrogel matrices produced drugs on demand, in the
quantity fine-tuned for a particular application, and at the time required. 9 Multiple drugs could be produced
with independent kinetics and overall content towards a facile sequential administration of therapeutics and
combination therapy. We are now investigating hydrogel biomaterials equipped with the tools for the enzyme prodrug therapy in diverse biomedical applications.
1.
Smith, A. A. A. et al. Polym. Chem. 2012, 3, 85-88.
2.
Chong, S.-F. et al. Small 2013, 9, 942-950.
3.
Jensen, B. E. B. et al. Biomaterials 2015, 49, 113-124.
4.
Jensen, B. E. B. et al. Nanoscale 2013, 5, 6758-6766.
5.
Jensen, B. E. B. et al. Langmuir 2011, 27, 10216-10223.
6.
Andreasen, S. O. et al. Nanoscale 2014, 6, 4131-4140.
7.
Fejerskov, B. et al. Small 2014, 10, 1314-1324.
8.
Fejerskov, B. et al. PLOS One 2012, 7, e49619.
9.
Mendes, A. C. et al. Advanced Functional Materials 2014, 24, 5202-5210.
45
Keynote
K-6
Multi-stimuli-responsive nanogels for bio-applications
Jacqueline Forcada
Bionanoparticles Group. Department of Applied Chemistry. Faculty of Chemistry. University of the Basque
Country UPV/EHU. Donostia-San Sebastián, Spain
[email protected]
Advanced nanoscale carriers for drug delivery are receiving tremendous attention in biomedicine. The need
for drug nanocarriers that efficiently target diseased areas in the body arises because drug efficacy is often
altered by nonspecific cell and tissue biodistribution, and because some drugs are rapidly metabolized
or excreted from the body. Much attention has been directed to stimuli-responsive crosslinked colloidal
particles, known as nanogels, considering their unique property to swell in a thermodynamically good solvent,
responding to external stimuli such as temperature, ionic strength, magnetic field, biomolecules, or pH, among
others. Furthermore, their small size allows them to overcome various biological barriers and achieve passive
and active targeting, reducing adverse reactions in tumor therapy. In addition, due to their porous structure
they are able to contain small molecules inside and release them by changing their volume. These properties
make them interesting and suitable materials to be used as nanocarriers in drug/gene delivery.1,2
During the last few years, our interest has been focused on the design of multi-responsive nanogels able
to combine multiple stimuli for advanced bio-applications.3-5 In this talk, our most recent approaches will be
presented showing special interest in the synthesis strategies, and also in the colloidal characterization of the
nanogels. Some preliminary bio-applications using these nanogels will be also presented.
1.
2.
3.
4.
5.
J. Ramos, J. Forcada, R. Hidalgo-Alvarez, Chem. Rev. 2014, 114, 367.
J. Ramos, A. Imaz, J. Forcada, Polym. Chem. 2012, 3, 852.
J. Ramos, R. Hidalgo-Alvarez, J. Forcada, Soft Matter 2013, 9, 8415.
G. Aguirre, J. Ramos, J. Forcada, Soft Matter 2013, 9, 261.
A. Pikabea, J. Ramos, N. Papachristos, D. Stamopoulos, J. Forcada, J. Polym. Sci. Part A. Polym.
Chem. DOI: 10.1002/pola.27996
46
Keynote
K-7
CATIONICALLY UV-CURED FUNCTIONAL POLYMERIC NETWORKS
Marco Sangermano
Politecnico di Torino, Dipartimento di Scienza Applicata e Tecnologia, Torino, Italy
[email protected]
UV-induced polymerization of multifunctional monomers has found a large number of industrial applications,
mainly in the production of films, inks and coatings on a variety of substrates including paper, metal and wood
[1]. The UV-Curing process could follow either a radical or a cationic chain grown polymerization mechanism.
Cationic UV-curing process presents additional benefits with respect to radical one, including; the absence
of air inhibition, inherent low levels of toxicity and irritation characteristics of the monomers employed, and a
lower volume shrinkage during photopolymerization [2].
The crosslinked process is started by diaryliodonium and triarylsulfonium salts, which may be viewed as
photoacid generators capable of producing acids of whatever strength desired depending on the starting
anion. The range of monomers polymerizable by a cationic mechanism is broad.
Cationic UV-Curing process can be used to tailor specific properties of the polymeric networks, simply
modifying the starting UV-Curable formulation.
It is reported different strategies to achieve multifunctionality facing different goals from conductive to
photoluminescent UV-cured films, which can find important sensor applications [3], to hybrid coatings
containing graphene which imparts specific properties to the crosslinked material [4].
Good conductivity was achieved by the in situ metal nanoparticles formation through a photo-reduction process
[5]. Photo-luminescent UV-cured films were prepared by embedding Gd2O3:Eu3+ nano-rods in different epoxy
matrices obtained through cationic UV-curing [6] or via a click-reaction using photoluminescent dies [7].
Graphene-epoxy polymers were studied to modify mechanical, electrical and thermal properties [8].
References:
1. Y. Yagci, Macromol. Symp., 240, 93-108, 2006.
2. M. Sangermano, “Advances in Cationic Photopolymerization”, Pure Appl. Chem., 84, 2089, 2012.
3. M. Martin-Gallego,, M.A. Lopez-Manchado, M. Sangermano, P. Calza, I. Roppolo, M. Sangemrano,
J. Mat. Sci., 50, 605-610, 2015
4. M. Sangermano, A. Chiolerio, G.P. Veronese, L. Ortolani, R. Rizzoli, V. Morandi, Macromol. Rap.
Comm., 35, 355-360, 2014
5. W. D. Cook, Q. Dat Nghiem, Q. Chen, F. Chen, M. Sangermano, Macromolecules, 44, 4065-4071,
2011
6. I. Roppolo, M.L. Debasu, R.A.S. Ferreira, L.D. Carlos, M. Sangermano, Macromol. Mat. Eng., 298,
181-188, 2013
7. S. Medel, P. Bosch, M. Sangermano, Polymer International, 63, 1018-1024, 2014.
8. M. Sangermano, L. Calvara, E. Chiavazzo, L. Ventola, P. Asinari, V. Mittal, R. Rizzoli, L. Ortolani, V.
Morandi, Prog. Organ. Coat., 86, 143-146, 2015.
47
K-8
Keynote
Tailoring alginates for tissue engineering applications by chemoenzymatic
modification
Berit L. Strand*, Marianne Ø. Dalheim, Øystein Arlov, Finn L. Aachmann, and Bjørn E. Christensen,
Gudmund Skjåk-Bræk
NOBIPOL, Dept of Biotechnology, NTNU Norwegian University of Science and Technology,
N-7491 Trondheim, Norway
[email protected]
Alginate hydrogels are attractive for tissue engineering applications as they have a low toxicity and
immunogenicity profile and as cells can be entrapped in the gel at physiological conditions ensuring good
viability and function of the cells. Alginates are linear polysaccharides from brown algae and some few bacteria
consisting of 1->4 linked β-D-Mannuronic acid (M) and its C5 epimer α-L-Guluronic acid (G). G-blocks are
main contributor to the binding of divalent ions in the gel and determine to a great extent the mechanical
properties of an alginate gel. Alginates are in general not known to promote specific cell interaction. Chemical
modification of alginate allows the introduction of biological activity but weaken the mechanical properties of
the alginate gels as the G-blocks are disrupted. By chemical modification of mannuronan and subsequent
enzymatic modification by mannuronan C5 epimerases, the chemical modifications are exclusively on the
M and the mechanical properties of the alginate are maintained. Here, we will discuss chemo-enzymatic
methods for the production of peptide grafted alginates1. Grafting of alginates using carbodiimide chemistry
with substitution on the carboxylic group will be discussed in comparison to partial periodate oxidation
followed by reductive amination2. Both material characterization and biological response will be discussed.
Further, sulfated alginates are attractive candidate as heparan sulfate analogue. Also here, chemo-enzymatic
modification enable the tailoring of molecule structures that together with the molecular weight determine
biological activity3,4.
(1)
Sandvig, I.; Karstensen K. Rokstad, A. M.; Aachmann, F. L.; Formo, K.; Sandvig, A.; SkjakBraek, G.; Strand, B. L.; J Biomed Mater Res Part A 2015, 103, 896.
(2)
Dalheim, M. Ø.; Vanacker, J.; Aachmann, F. L.; Strand, B. L.; Christensen, B. E. Biomaterials
2016, 80:146.
(3)
Arlov, O.; Aachmann F. L.; Feyzi E et al. The Impact of Chain Length and Flexibility in the
Interaction between Sulfated Alginates and HGF and FGF-2. Biomacromol 2015;16:3417.
(4)
Arlov, O.; Aachmann, F.L.; Sundan, A.; et al. Heparin-like properties of sulfated alginates with
defined sequences and sulfation degrees. Biomacromol 2014;15:2744.
.
48
Oral presentations
49
Oral
O-1
Particulate β-Sheet Nanocrystal-Reinforced Supramolecular Elastomers
Li Jia
The University of Akron, Department of Polymer Science
Akon, Ohio 44325, USA
Many synthetic supramolecular thermoplastic elastomers (TPEs) are analogs of natural silks in the sense
that both types of materials contain β-sheet crystalline domains that serve to crosslink and reinforce the elastic network. However, one of the key differences between the synthetic and natural analogs is the aspect ratio
of β-sheet crystals. The nanocrystals in silks are particulate, with the sizes in all three dimensions less than
10 nanometers (e.g., 2.1x2.7x6.5 nm3 in spider dragline), while the crystalline domains in synthetic supramolecular TPE display fibrous morphology with the longest dimension ranging from hundreds of nanometers to
micrometers (Figure 1).
a
a
amorphous
continuous
phase
β-sheet
crystalline
domain
b
c
c
b
VS
B
A
Figure 1. Schematic illustration of β-sheet nanocrystallites (A) and fibrous crystalline domains (B) dispersed
in an amorphous phase. The a, b, and c axes correspond to the direction of covalent bonding, hydrogen-bonding, and β-sheet stacking, respectively.
To provide reinforcement, these crystalline domains must be strong and stiff. In order to attain the strength
and stiffness at such a small length scale, it is necessary to use strongly associating molecular motifs. Thus,
those capable of forming multiple cooperative hydrogen bonds are adopted by both nature and man. However, the strong association also provides a thermodynamic incentive for a high degree of association that
exceeds the aforementioned nanometer scale. In silk, the size of the crystallites is generally believed to be
attributable to their specific amino acid sequences. In the absence of specific amino acid sequences, how to
achieve the nanometer size is an interesting challenge for synthetic TPEs.
In this presentation, I will first show that particulate β-sheet nanocrystals with the longest dimension well-below 100 nm can be attained without an elaborate amino acid sequence. The small size is attributed to the
grafting topology. The topology renders a rapid increase of entropic loss as the degree of association increases to stop the growth of the β-sheet. Second, I will show that the particulate nanocrystals display a remarkable ability to simultaneously provide stiffness, extensibility, and strength to the synthetic elastic network
and do so highly efficiently at a low volume fraction of the material. The herein studied butyl rubber-based
thermoplastic elastomers containing 3.6 volume % of β-sheet nanocrystals are stiffer, stronger, and more
extensible than vulcanized butyl rubber reinforced by 20 volume % of carbon black and poly(styrene-b-isobutylene-b-styrene) reinforced by >33 volume % of polystyrene domains. The high reinforcing efficacy of the
β-sheet crystals is attributable to two phenomena associated with their small sizes, a stick-slip mechanism for
energy dissipation and an auxiliary layer of polymer brush that contributes to increasing the modulus.
50
Oral
O-2
Thiol-ene thermosets exploiting surface reactivity for layer-by-layer structures
and control of penetration depth for selective surface reactivity.
Anders E. Daugaard, Andreas Westh, Ines P. Rosinha, Ulrich Krühne and Christian Hoffmann
Danish Polymer Centre, Department of Chemical and Biochemical Engineering, Technical University of
Denmark, Søltofts plads bygning 227, DK2800 Kgs. Lyngby, Denmark
Thiol-ene thermosets have been shown to be an efficient platform for preparation of functional polymer
surfaces. Especially the effectiveness and versatility of the system has enabled a large variety of network
properties to be obtained in a simple and straight-forward way. Due to its selectivity, various thiols and allyl
or other vinyl reactants can be used to obtain either soft and flexible1 or more rigid functional thermosets2.
The methodology permits use of etiher thermal or photochemical conditions both for matrix preparation as
well as for surface functionalization. Due to excess reactive groups in the surface of thiol-ene thermosets,
it is possible to prepare surface functional thermosets or to exploit the reactive groups for modular construction and subsequent chemical bonding. Here a different approach preparing monolithic layer-by-layer
structures with controlled mechanical properties across freestanding samples is presented. The appraoch is
further exploited for preparation of surface structures down to features of 25 mm scale by use of an absorber and simple masking.
The combination of masking and absorbers were similarly used to prepare a reactor with controlled surface properties as shown in Figure 1. Here fully sealed reactors (Figure 1a) were prepared modularly by a
combination of thiol-ene and thiol-epoxy curing reactions. The reactors were functionalized in different patterns on the top side of the assembled reactor, illustrating the effectiveness of absorbers in controlling the
penetration depth and surface grafting. The methodology was used for surface immobilization of enzymes
providing a direct link between the distribution of enzymes on the surface and the activity of the reactor.
Figure 1: Surface functionalization inside a flow reactor with an allyl-disperse red, taking place only on the
top face of the reactor; a) Assembled reactor during surface functionalization; b) Reactor after surface functionalization; c) Opened reactor showing top and bottom of the reactor, where only the top has been reacted (eventhough both sides have reactive thiols).
References
(1) Goswami, K.; Skov, A. L.; Daugaard, A. E. Chem. - A Eur. J. 2014, 20, 9230–9233.
(2) Mazurek, P.; Daugaard, A. E.; Skolimowski, M.; Hvilsted, S.; Skov, A. L. RSC Adv. 2015, 5, 15379–
15386.
(3) Goswami, K.; Daugaard, A. E.; Skov, A. L. RSC Adv. 2015, 5, 12792–12799.
51
Oral
O-3
Polymer Networks from Nanosized Multifunctional Precursors
Karel Dušek and Miroslava Dušková-Smrčková
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Prague 162 00
[email protected], [email protected]
The large majority of cross-linked materials of application importance (coatings, thermosets, bio-inspired and
bio-active gels, etc.) are fabricated from pre-prepared multifunctional precursors. Their typical size varies
between 1 and 10 nm and they are characteristic by distributions of molecular weights, number and type of
functional groups, and arrangement of building units in the precursor molecules. Precursors are prepared in
order to adjust the group reactivity, processing properties like build-up of viscosity and pot life, and application
properties or to introduce specific chemical environment into the product. Not less important is a reduction of
health hazards by lowering the volatility and penetration ability of larger molecules. Functional copolymers,
hyperbranched polymers, off-stoichiometric highly branched copolyadducts, chain–extended systems, and
networks prepared in several stages are typical examples of such systems. To describe and predict development of network structure and properties theoretically, one has to deal with a relatively complicated initial
system cross-linked with a simpler (but not necessarily) cross-linker. One can proceed in two ways. One way
is a strictly two-stage method: The distributions of the precursor molecules bearing functional groups that are
active in the second stage, are generated in the first stage and the output is used, after transformation, as
input in the second, cross-linking stage. The transformation involves passage from the second moment to
first moment distributions. The second way is formally simpler in which the unreacted groups are specially
labelled (by special variables of the generating function) and those remaining unreacted after the first stage
are allowed to react in the second stage. The bonds even between the chemically same groups formed in the
first and second stages must be strictly distinguished. The generation methods can be kinetic or statistical, or
they are combined; in the latter case, first-order Markovian statistics is sufficient. The precursors contain as a
rule branch points and with respect to cross-link density these branch points are inactive.at low network connectivity. The whole unit is first dangling, then it becomes a part of elastically active network chain (EANCs),
and later more and more branch points start contributing to the number of EANCs. This is called activation
of branch point and can be well theoretically described based on probabilities of finite or infinite continuation
of sequences of bonds. Comparison of experimental and theoretical results will be demonstrated using the
example of cross-linking of chain-extended stars and simple and chain-extended hyperbranched polymers.
Cyclization reactions during cross-linking in these kinds of precursors are not negligible but their extent is
not easy to be predicted. Therefore, at present we prefer their characterization by the shift of the gel point
conversion with dilution of the system. The design of binders in organic coatings based on such precursors
and their effect on coating film formation and properties are discussed.
52
Oral
O-4
Dynamics of nano-particles in polymer networks near gelation point
Xiang Li1, Nobuyuki Watanabe1, Mitsuhiro Shibayama1
1
ISSP, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwashi, Chiba, 277-0882, Japan
Email: [email protected]
Diffusion process of nanoparticles in polymer solutions and
gels is of great interest in chromatography, drug release, molecular biology and many other fields. One of the most powerful techniques to measure particles diffusion is dynamic
light scattering (DLS), which can estimate the diffusion coefficient by evaluating the time-correlation of scattered light
intensity from the samples. 1,2 However, generally the light is
not just scattered from the particles but also from the polyFig 1. Illustration of index matched DLS system
mers. Thus, it was difficult to simply extract the information
of particle dynamics near and after gelation point. In this study, we applied the contrast matching method, which
is often used in neutron scattering, to DLS by matching the refractive index of polymers and solvent. In an index-matched system, only scattered light from probe-particles can be detected. In this system, we conducted a
series of diffusion experiments with various sized probe particles in a well controlled PEG gelation system (Fig 1).
Tetra-armed PEG polymers with mutual reactive end groups (Mw
20k, conc. 60 g/L) and gold nano-particles (diameter 10-100 nm,
conc. < 0.005 g/L) were dissolved in dehydrated dimethyl sulfoxide
(DMSO). Dynamic light scattering measurements were performed for
all samples at 298.3±0.3 K with ALV 5022F. The reaction rates were
determined by measuring UV absorption change of the end groups
of unreacted tetra-arm PEG polymers. Fig 2. shows correlation functions of gold nanoparticles in a polymer solution. As the gelation reaction proceeded, the correlation function changed. We employed
stretched exponential function to analyze the correlation function.
g(2)(τ)-1=A2 exp(-(τ⁄τs )2β)
Fig 2. Correlation functions of gold
(1)
nanoparticle in PEG gelation system
The obtained parameters, A, β, τs were shown in Fig 3. All
parameters changed drastically near the gelation point.
Further discussion will be given in the presentation.
(1) Shibayama, M. et al., Macromolecules 1999, 32 (21),
7086–7092.
(2)
Fadda, G. C. et al., Phys Rev E 2001, 63 (6), 061405–
061409.
Fig 3. Fitting parameters α, β, τs vs. reaction rate of PEG polymers
53
O-5
Oral
Gel-like Properties of Cartilage Proteoglycans
Ferenc Horkay
Section on Quantitative Imaging and Tissue Sciences, National Institutes of Health, Bldg. 13, Room 3W16,
13 South Drive, Bethesda, MD 20892, USA,
[email protected]
Cartilage extracellular matrix (ECM) can be considered a network of large molecules that provides structural
strength to the tissue by maintaining a complex hierarchical architecture. ECM is composed of two main components that define its biomechanical properties: proteoglycan assemblies, which give articular cartilage its
ability to resist compressive loads, and a collagenous network, which is responsible for the tensile strength of
the tissue. The most abundant proteoglycan is aggrecan, a bottlebrush shaped molecule that possesses over
100 sulfated glycosaminoglycan (chondroitin sulfate and keratan sulfate) chains. The side-chains are long,
linear carbohydrate polymers that are negatively charged under physiological conditions. Aggrecan interacts
with hyaluronic acid (HA) to form large aggregates. The aggregation between aggrecan and hyaluronic acid
is essential for the biomechanical function of cartilage. The negatively charged aggrecan/HA complexes interspersed in the collagen matrix provide a high osmotic pressure that defines the compressive resistance
of the tissue. The other proteoglycans (decorin, fibromodulin, etc.) are much smaller than aggrecan. They
interact with collagen and help maintain the structural integrity. The collagen matrix counterbalances the
osmotic swelling pressure of the embedded proteoglycan assemblies. The biomechanical properties of cartilage strongly vary with age, injury and disease.
Bone formation, i.e., the conversion of cartilage into bone requires several processes that involve different
ECM components and ions, particularly divalent calcium ions. In charged polyelectrolyte systems [e.g.,
poly(acrylic acid), DNA] higher valence counter-ions often results in phase separation. It is unlikely that the
aggrecan/HA assemblies could fulfill their biological functions if they exhibit similar ionic sensitivity.
Our objectives are to:
(i)
determine the effect of complex formation between aggrecan and HA molecules on the osmotic
pressure at different ratios of aggrecan to HA;
(ii)
identify important differences between the static and dynamic properties of aggrecan and chondroitin sulfate solutions;
(iii)
quantify the effect of calcium ions on the supramolecular organization and dynamic behavior of
aggrecan assemblies.
Experimental results obtained by complementary techniques (small angle neutron and X-ray scattering,
neutron spin echo, static and dynamic light scattering, osmotic pressure measurements) probing the structure and dynamics over a broad range of length and time scales will be discussed.
ACKNOWLEDGEMENT This research was supported by the Intramural Research Program of the NICHD, NIH.
54
Oral
O-6
A new strategy for ionotropic alginate gelation applied in microfluidic assisted
homogeneous bead synthesis and cell immobilization.
Armend G. Håti, David C. Bassett, Jonas M. Ribe, Pawel Sikorski and Bjørn T. Stokke
Biophysics and Medical Technology, Dept. of Physics, NTNU Norwegian University of Science and
Technology, NO-7491 Trondheim, Norway.
Alginates are a family of structural polysaccharides derived from seaweeds or certain bacteria. They
readily form ionotropically induced physical gels under aqueous conditions in the presence of multivalent
cations, driven by lateral association of chain segments thus making a junction zone. In particular, the gel
formation of alginates in aqueous Ca2+ containing solutions is of significant interest due to mild and non-toxic
reaction conditions making biological and biomedical applications feasible. Due to the ease of the ionotropic,
e.g., Ca2+, induced gelation and the biocompatible nature of the polysaccharide, alginates have found widespread use as both eukaryotic and prokaryotic cellular encapsulation materials. Typically, cells are immobilized in sub-millimeter spherical beads by passing a Na-alginate solution containing the cells through a fine
needle into an aqueous Ca2+ solution, the laminar injection flow passes through an air space and is broken
into small droplets using a static electric field or mechanical (sound) vibration. These processes take advantage of the rapid Ca2+ induced alginate gelation, however the size of the resulting gel beads is dependent
on the geometry of the injection needle and is limited to the range above approximately 250 µm (diameter);
additionally size heterogeneity is particularly difficult to control. Microfluidics is a rapidly evolving discipline
focusing on the precise control and manipulation of fluids that are geometrically constrained in microscale
channels. Microfluidics therefore offers an attractive route to create homogeneous microscale beads of alginate and was explored for this purpose and to encapsulate cells in beads in the size range below 250 µm.
While droplet microfluidics potentially offers good control of gel bead size, e.g., below 100 µm, its compatibility with conventional methods for Ca2+ induced gelation of alginate is poor. Microchannel clogging due to rapid
gelation of alginate in contact with a Ca2+ containing aqueous stream or due to the use of a solid, particulate
source of Ca within the gel solution is a substantial hurdle. Current strategies using chelated forms of Ca2+
have significant shortcomings in terms of insufficient control of release kinetics or poor biocompatibility.
In this presentation, we describe a novel approach for inducing ionotropic alginate gels within microscale alginate droplets prepared using microfluidic emulsification of alginate solutions. The approach is
based on the reaction of two alginate solutions, one of which contains a soluble form of Ca2+, which upon
mixing is rendered free to crosslink both alginate solutions. The microfluidic devices were designed with two
inlets for the two alginate solutions which are mixed before being emulsified using a fluorinated oil and a
biocompatible surfactant. The size of the beads is dependent on channel geometry and can be fine-tuned
by modifying the fluid flow rates. Highly monodisperse populations of gelled alginate microbeads with mean
diameters in the range 10 to 50 μm can readily be obtained and microfluidic devices were operated without
issue for several hours. Both eukaryotic and prokaryotic cells immobilized using this technique displayed excellent viability post encapsulation and up to 28 days in culture. We believe this method represents a highly
significant advance in alginate gelation technology and is highly attractive for cell encapsulation applications,
for both microfluidic and conventional techniques.
55
Oral
O-7
INSECTCHITIN-BINDING PROTEINS INDUCED BIOMACROMOLECULAR
MICROPRAARTICLE FORMATION IN BIOMACROMOLECULE SOLUTIONS:
INSPIRATIONS FROM INSECT CUTICLE FOR HEIIERARCHICAL
SELF-ASSEMBLY USING COMPONENTS OF THE INSECT CUTICLE SYSTEM
Stevin H. Gehrke1, M. Coleman Vaclaw, 1 Patricia A. Sprouse, 1 Neal T. Dittmer,2 Michael R. Kanost,2 and
Prajnaparamita Dhar1
1
Dept. of Chemical & Petroleum Engineering, University of Kansas, Lawrence, KS 66045 USA; 2 Dept. of
Biochemistry, Kansas State University, Manhattan, KS 66056 USA
email: [email protected]
Insect cuticle, the primary component of the exoskeleton, is one of the most widespread materials in nature. It
is a valuable model for the development of biomimetic materials because its moduli can vary by six orders of
magnitude or more. The exceptional properties of insect cuticle are hypothesized to arise from a combination
of covalent and non-covalent interactions among proteins, catechols, chitosan and chitin nanofibers,
including protein-catechol crosslinking, generation of catechol-derived microparticles and protein-metal ion
interactions. Here we examine the interactions between novel structural proteins that we have identified in
the beetle Tribolium castaneum and their interactions with chitin, chitosan and metal ions. The goal of this
work extends from understanding the in vivo roles of specific interactions to development of new biomaterial
design motifs.1
Two abundant cuticle proteins in the elytra of T. castaneum that we named CPR27 and CP30 were the foci
of this study. CPR27 has a conserved sequence of amino acids first hypothesized by Rebers and Riddiford
to bind chitin. In this work, we establish direct evidence of this protein-chitin binding by using an active
microrheology technique, coupled with fluorescence and bright-field microscopy. While our results from
active microrheology showed that addition of CPR27 to aqueous chitosan solutions caused a 2-fold decrease
in viscosity, simultaneous visualization of the solution microstructure shows the formation of micron-sized
particles. Together these results indicated that CPR27 complexed with chitosan as hypothesized to form
micron-scale structures. Furthermore, by using fluorescently-labeled chitosan, our simultaneous fluorescence
images confirm the presence of clusters of chitosan, suggesting that the protein CPR-27 serves as a
nucleation agent to induce the complexation of the polyelectrolyte. However, varying the concentration of the
protein over several orders of magnitude does not alter the viscosity drop, suggesting that the RR interactions
are the first step in inducing complexation of chitosan, but particle formation doesn’t follow Einstein’s law of
viscosity for colloidal suspensions. In contrast, CP30, which does not contain the chitin-binding sequence,
displayed no evidence of complexation. The role of quinone-crosslinking of both proteins with the catechol
N-b-alanyldopamine (similar to that observed in mussel adhesion) was also examined. Microparticle formation
was observed in solutions containing protein, catechol and the oxidative enzyme laccase. Understanding
the interactions involving these cuticle proteins suggest new motifs that could be used in the design of new
composite materials. The rational design of recombinant proteins following these principles, with specific
covalent and non-covalent interactions with polysaccharides or ions, inspired by insect cuticle, may lead to
biomaterials with enhanced mechanical properties.
REFERENCES
[1] Lomakin, J.; Huber, P.A.; Eichler, C.; Arakane, Y.; Kramer, K.J.; Beeman, R.W.; Kanost, M.R.; Gehrke,
S.H. Biomacromolecules (2011) 12, 321.
56
Oral
O-8
Structural formation and gelation of neutral polysaccharides as observed by
small angle X-ray scattering
Yoshiaki Yuguchi1, Kyoko Yamamoto1, Shiho Suzuki2 and Shinichi Kitmura2
1
Faculty of Engineering, Osaka Electro-Communication University, Japan
2
Osaka Prefecture University, Japan
We have some neutral polysaccharides as starch and cellulose, which are insoluble in water due to strong association between saccharide chains including crystal structure with hydrogen bonding. Amylose is one component of starch and it is linear polymer constructed of α-1,4 linked D-glucose. On the other hand schizophyllan, which is water soluble polysaccharide, is also linear β-1,3 linked D-glucose. They build helical structure
with hydrogen bonding. These polysaccharides can be dissolved in alkaline aqueous solutions by breaking
association between chains. And they can yield homogeneous gels as proceeding and controlling structural
formation by in situ neutralization method1. This slow process allow us to use time-resolved small angle X-ray
scattering technique (tr-SAXS). In this study we report the results of structural observation for amylose and
schizophyllan.
Polysaccharide samples are dissolved by 0.5 or 1M NaOH aqueous solutions. Formamide was used as neutralization reagent. SAXS measurements were carried out at SPring-8, synchrotron radiation facility in Japan.
Time course of SAXS profiles were detected during neutralization and gelation of amylose and schizophyllan solutions, and these time dependences indicated the structural formation of polysaccharide chains at
nano-scale. The scattering intensity in smaller angle region gradually increased due to the aggregation of
amylose chains, accompanying with crystal growth as observing diffraction peaks in wider angle region.
1)Aasprong, E.; Smidsrød, O.; Stokke, B. T. Biomacromolecules 2003, 4, 914
57
O-9
Oral
Interpenetrating Network Hydrogels:
Roles and Fates of Network 1 and Network 2
Miroslava Dušková-Smrčková, Zhansaya Sadakbayeva, Miloš Steinhart and Karel Dušek
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic
Prague 162 00
[email protected]
Sequential interpenetrating polymer networks of 2-hydroxyethyl methacrylate (HEMA) and glycerol methacrylate (GMA) cross-linked with ethylene dimethacrylate (EDMA) in which the first network was homogeneous
or macroporous (phase-separated or cryogel types), were prepared and characterized by swelling, tensile
and oscillatory shear mechanical measurements and various microscopic techniques. The polyHEMA is less
hydrophilic than polyGMA. Hydrophobic associations between PHEMA segments in aqueous medium exist
and were detected by wide-angle X-ray scattering (WAXS) in the nanometer range and their changes were
characterized during and after network formation. In the majority of cases, the role of network 2 was to generate expansion of chains of network 1. The effect of network 2 was larger when it acted as separate phase
in the pores of macroporous network 1. The pores walls could be expanded by a factor up to 4. The tensile
strain caused the hydrophobic associates of polyHEMA to unfold which was manifested by weakening and
disappearing of a prolonged maximum of the intensity of WAXS in the 1-2 nm region. Replacement of water
for a better solvent (structure breaking additive) had a similar effect on the WAXS intensity.
When the concentration of cross-linker in network 2 increases, one would expect the elastic modulus of the
IPN also increases. However, the outcome of experiments was very surprising and at variance with expectations and theoretical predictions based on conventional interpenetrating network models: The shear and
tensile moduli sharply decreased with increasing concentration of cross-linker in network 2 while the degree
of swelling changed only little! It was found that this unexpected behavior was due to reaction induced phase
separation of branched and partly cyclized polymer 2 prior gelation within the large mesh of network 1.
During free swelling in water, the chains of network 1 take the more water the tighter is the phase separated
polymer 2. The tightness of structure of phase separated polymer 2 is supported by not only by its increased
degree of branching but also by the cyclization induced and progressively increasing microgelation tendency
of the free-radical cross-linking polymerization.
58
Oral
O-10
Anomalous Self-Diffusion in Physical Polymer Gels
Bradley D. Olsen, Shengchang Tang, Jorge Ramirez, Thomas Dursch, and Muzhou Wang
Massachusetts Institute of Technology Room 66-558a
77 Massachusetts Ave., Cambridge, MA 02139, USA
[email protected]
Physical polymer gels and associating polymers are of widespread interest for applications as diverse as
rheology modifiers, food science, tissue engineering, and responsive materials. While a great deal of effort
has gone into understanding their mechanical response, there have been significantly fewer investigations
of diffusion within the materials. Using forced Rayleigh scattering (FRS), we have probed self-diffusion in a
model associating gel made from artificially engineered protein polymers, using the resulting measurements
to provide insight into mechanical behavior. Below a certain length scale, Fickian diffusion transitions to
a super diffusive regime that occurs due to the interplay between chain association/dissociation with the
network and chain diffusivity. This super-diffusive behavior can be quantitatively modeled using a simple
two state model for the dynamic equilibrium between a fast diffusing dissociated species and a slow diffusing
associated species. Using the kinetic constant for dissociation extracted from diffusion measurement, timetemperature-concentration superposition can be achieved.
Further studies of synthetic hydrogels using metal coordinate bonds show that this behavior is common
across different categories of associating polymers. Comparison of molecular exchange rates, rheology
crossover times (mechanical measurement of bond lifetime), and diffusive measurements of bond lifetime
suggest that they are all governed by similar processes, but quantitative differences and structure-lifetime
relationships present in macromolecular systems point to important differences between the different
processes. We are also developing coarse-grained molecular approaches to computing diffusivities using
the Langevin formalism, where simulations provide insight into how molecular processes translate into the
observed phenomenological models of transport.
59
O-11
Oral
Mechanical and thermoresponsive properties of PNIPA - graphene-oxide composite gels
Barbara Berke1,2, Orsolya Czakkel*2, Lionel Porcar2, Erik Geissler3, Krisztina László1
1
Department of Physical Chemistry and Material Science, Budapest University of Technology and
Economics, 1521 Budapest, Hungary
2
3
Institut Laue-Langevin, CS 20156, F – 38042 Grenoble Cedex 9, France
Laboratoire Interdisciplinaire de Physique, CNRS and Université Grenoble Alpes, 38000 Grenoble, France
* Corresponding author: [email protected]
Thermoresponsive hydrogels have enormous potential as e.g., sensors, actuators, pollution control remedies
or in drug delivery systems. However their application is often restricted by physical limitations (e.g., poor
mechanical strength, uncontrolled thermal response). These challenges can be conceivably overcome by
preparing composite hydrogels [1, 2]. Carbon nanoparticles are among the most common fillers, however
nowadays nanocomposites containing members of the graphene family, especially graphene oxide (GO), are
in the focus of interest. As GO is considered to be non-toxic and highly biocompatible favours the use of its
nanocomposites in biomedical applications. Furthermore the incorporation of GO gives visible or near infrared light sensitivity to the systems, which enhances their potential e.g. as NIR controlled microvalves, artificial
muscles or actuators. Potential applications are numerous, but the detailed properties of graphene-based
composites remain to be explored, especially on the microscopic lengthscale.
Here we present a systematic study of the structure and dynamics of GO - poly(N-isopropyl acrylamide) (PNIPA) composite systems.. Combination of macroscopic (stress-strain and swelling measurements, temperature sensitivity) and microscopic (differential scanning microcalorimetry, small angle neutron scattering and
neutron spin-echo spectroscopy) investigations reveal that incorporation of GO changes the architecture of
the polymer gel resulting from the build up of an interpenetrating GO network in which the polymer network is
attached through chain nucleation at the surface of the GO. Our results show as well that whereas the mobility of the polymer chains in the swollen state is practically unaffected, the macroscopic deswelling properties
of the composites are strongly modified by the GO, and gives rise to controlling the thermal response of the
composites by the GO content [3].
[1] P. Schexnailder and G. Schmidt, Colloid Polym. Sci., 287, 1–11 (2009)
[2] K. Haraguchi, Curr. Opin. Solid State Mater. Sci., 11, 47–54 (2007)
[3] B. Berke, O. Czakkel, L. Porcar, E. Geissler, K. László: Static and dynamic behaviour of responsive
graphene oxide - poly (N-isopropyl acrylamide) composite gels. Submitted
60
Oral
O-12
Crosslinker Effects on Properties of Hydroxyethylacryl Chitosan/
Sodium Alginate Hydrogel Films
Pitchaya Treenate and Pathavuth Monvisade
Polymer Synthesis and Functional Materials Research Unit, Department of Chemistry, Faculty of Science,
King Mongkut’s Institute of Technology Ladkrabang, Bangkok, Thailand
The aim of this research is to investigate the effects of Ca2+ and Zn2+ on the swelling behaviors and antibacterial properties of crosslinked hydroxyethylacryl chitosan (HC)/ sodium alginate (SA) films. The hydrogel
films composed of HC and SA in different proportions (75:25, 50:50, 25:75 and 0:100 w/w) were prepared by
using calcium chloride as a single crosslinking agent and both calcium chloride and zinc sulfate as a couple
crosslinking agent. The structures of the films were characterized by infrared spectroscopy (FT-IR). It was
found that Ca2+ ions can only crosslink with SA via ionic bonding while Zn2+ ions can crosslink both HC and SA
via mainly coordinate bonding. The swelling behaviors of the films in phosphate buffer solution (PBS) were
investigated. The results showed relatively high stability for the crosslinked films with the couple crosslinking
agent. The calcium-zinc crosslinked films evidenced antibacterial properties to Escherichia coli. In addition,
the hydrogel films exhibited no cytotoxicity for Vero cells. The comprehensive results suggest their potential
as a wound dressing material.
61
Oral
O-13
Mesoscopic structural order in hydrogen bonding liquid
Nobuyuki Takahashi1, 2, Wolfgang Paul2 and Do Y. Yoon3
1
2
Hokkaido University of Education, Hakodate, 1-2 Hachimancho, Hakodate 040-8567, Japan
Institut fur Physik, Martin-Luther-Universitat Halle-Wittenberg, 06099 Halle (Saale), Germany
3
Stanford University, Stanford, California 94305, USA
A thermally persistent heterogeneous orientational order in a liquid state of the meso-2,4-pentanediol, a
dimer of poly(vinyl alcohol) (PVA), was simulated by the molecular dynamics method in a temperature range
between 240 K and 420 K for nanoscale fibers and for the bulk system. The calculated X-ray diffraction profile
shows essentially the same structure in both the nanoscale fibers and the bulk, with the orientational order
that is stable in the fiber and fluctuating in the bulk. The dynamic heterogeneity was also analyzed for the
ordered domain structure. Experimental diffraction profiles were discussed based on the simulation.
62
Oral
O-14
Soft Sensitive Matter: Structure, Dynamics, and Function of Supramolecular
Polymer Gels
Sebastian Seiffert
Freie Universität Berlin, Institute of Chemistry and Biochemistry, Takustr. 3, D-14195 Berlin, Germany.
Supramolecular polymer gels consist of polymer chains connected by non-covalent interactions [1]. These
materials are promising for a plethora of applications, ranging from adaptive and self-healing scaffolds [2]
to designed extracellular matrixes [3]. To truly exploit the utility of these gels, it is necessary to understand
the interplay between their structure, dynamics, and properties [1]. We address this challenge on the
basis of macromolecular toolboxes derived from the same precursor polymer but functionalized with
different crosslinkable motifs, thereby exhibiting greatly varying strength of association without perceptible
alteration of other parameters [4, 5]. We find that a prime factor of impact on the mechanics and responsive
performance of the resulting supramolecular gels is their nanometer-scale polymer-network architecture. To
specifically account for this circumstance, we prepare our sample platforms such to either exhibit irregular,
heterogeneous distributions of their supramolecular crosslinking nodes [4] or model-type, homogeneous and
regular supramolecular chain interconnection [5]. These different gels are then further studied to correlate their
macroscopic properties to their supramolecular binding–unbinding equilibria [4–6], nano- and mesoscopic
polymer-network topologies [4, 5], and chain+junction dynamics [7, 8] on multiple scales of length and time
[9].
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
S. Seiffert, J. Sprakel, Chem. Soc. Rev. 2012, 41, 909.
F. Herbst, S. Seiffert, W. H. Binder, Polymer Chem. 2012, 3, 3084.
T. Rossow, S. Bayer, R. Albrecht, C. C. Tzschucke, S. Seiffert, Macromol. Rapid Commun. 2013, 34,
1401.
T. Rossow, S. Hackelbusch, P. Van Assenbergh, S. Seiffert, Polymer Chem. 2013, 4, 2515.
T. Rossow, S. Seiffert, Polymer Chem. 2014, 5, 3018.
S. Hackelbusch, T. Rossow, H. Becker, S. Seiffert, Macromolecules 2014, 47, 4028.
S. Hackelbusch, T. Rossow, P. Van Assenbergh, S. Seiffert, Macromolecules 2013, 46, 6273.
T. Rossow, A. Habicht, S. Seiffert, Macromolecules 2014, 47, 6473.
S. Seiffert, Macromol. Rapid Commun. 2016, DOI: 10.1002/marc.201500605.
63
Oral
O-15
Advantages to do in-situ measurements by Raman spectroscopy and coupling
with other techniques for the determination of physico-chemical properties of
polymers
Patrice Bourson1, Marie Veitmann1, Elise Dropsit1, David Chapron1, Aurélie Filliung1, Alain Durand2,
Sandrine Hoppe3, Jean Guilment4, Stephane Bizet4, Samuel Devismes4
LMOPS, University of Lorraine – Supelec, 2 rue E. Belin 57070 Metz, France
LCPM University of Lorraine- CNRS, ENSIC, 1 rue Grandville 54000 Nancy, France
3
LRGP University of Lorraine- CNRS,ENSIC 1 rue Grandville 54000 Nancy, France
4
ARKEMA - Research Center CRDE BP 61005 - 57501 Saint-Avold Cedex, France
1
2
[email protected]
Raman spectroscopy is a technique particularly rapidly evolving in spectral qualities, quality of instruments
and transportability of new equipments.
This allows uses in-situ or real time using of these equipments and permit to control or optimize the properties of polymer and for example, the possibility of their use for monitoring the industrial flows directly into the
plant or reactor.
We show, in this presentation, two examples of real-time monitoring of the physico-chemical properties of
polymers by Raman spectroscopy and coupling experiments. The first example showing interest to make
in-situ measurements for measuring the mechanical properties of polymers, and so to establish an original
coupling (Raman spectroscopy /Video extensometer) for characterizing in real time the microstructure of a
polymer during the mechanical deformation. The second example consists the control in real time of industrial
flows using Raman spectroscopy combined with a chemometrics study to monitor very effectively an industrial production of a polymer.
64
Oral
O-16
Chemically modified hybrid thermosets: elastic behavior in the plateau regime
of polyaminosiloxane-nitrile-DGEBA
Antonio González-Jiménez1, Artemia Loayza,2 Juan L. Valentín1, Juan Baselga2, Juan C. Cabanelas2,
María González2,
1
2
Instituto de Ciencia y Tecnología de Polímeros, CSIC, C/ Juan de la Cierva 3, 28006 Madrid.
Universidad Carlos III de Madrid, Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química, Av.
Universidad 30, 28911 Leganés, Madrid
The structure and properties of epoxy / siloxane reactive blends is currently an open question in the field
of advanced thermosetting materials. Both components are immiscible and phase segregation limits the
morphology and phase composition, size and distribution. Among the different approaches to improve compatibility we used poly(3-aminopropylmethyl siloxane) (PAMS) as a reactive crosslinker1-5. The most interesting feature of these systems is probably concerned with their high functionality which, at the same time,
increases the Young’s modulus in the rubbery state, increases hydrophobicity and switches gelation towards
lower conversion fixing the final morphology well before limiting conversion. This high functionality can be
tuned reacting some of the pendant amino groups with molecules that may impart specific properties while
the remaining provide enough crosslinking density to give high performance thermosets. In a recent report6
we presented the structure and the low and high temperature relaxations of these systems using adducts
with acrylonitrile. We have been able to identify two subnetworks associated
to the two different crosslinking sites as depicted in the figure, whose contribution depends on the extent of acrylonitrile modification. In this communication
we present the elastic behavior in the rubbery plateau using two techniques:
Time-domain solid-state NMR spectroscopy7 (proton double-quantum NMR)
and DMTA. Results are discussed in terms of the presence of inhomogeneities
and the non-gaussian character of the chains.
1. Cabanelas, J. C.; Serrano, B.; Gonzalez-Benito, J.; Bravo, J.; Baselga, J. Macromol. Rapid Commun.2001, 22, 694–699.
2. Cabanelas, J.C.; Serrano, B; González, M.G.; Baselga, J. Polymer 2005, 46, 6633-6639.
3. Cabanelas, J.C.; Serrano, B.; Baselga, J. Macromolecules 2005, 38, 961-970.
4. Cabanelas, J. C.; Prolongo, S.G.; Serrano, B.; Bravo, J.; Baselga, J. J. Mat. Proc. Tech., 2003, 143-144,
311–315.
5. Prolongo, S.G.; Cabanelas, J.C.; Baselga, J. Macromol. Symp. 2003, 198, 283-293.
6. Loayza, A.; Cabanelas, J.C.; González, M.; Baselga, J. Polymer 2015, 69, 178-185
7. Martin-Gallego, M.; González-Jiménez, A.; Verdejo, R.; Lopez-Manchado, M.A.; Valentin, J.L. J. Polym.
Sci. B. Polym Phys. 2015, 53, 1324-1332
65
Oral
O-17
Enhanced mechanical properties in multiple network elastomers
Pierre Millereaua, Etienne Ducrota, Meredith Wiseman-Mb, Markus Bultersb and Costantino Cretona
a
SIMM, ESPCI ParisTech-UPMC-CNRS, 10 Rue Vauquelin, 75231 Paris Cédex 05
b
DSM Research, P.O. Box 18, 6160 MD Geleen, The Netherlands
email : [email protected]
Elastomers are widely used in the aeronautic and automobile industries. They are often subjected to many
mechanical stresses hence the desire to study and improve their mechanical properties. Nowadays, elastomers are commonly reinforced with fillers to improve both stiffness and toughness. On the contrary, unfilled
elastomers are known to present very poor mechanical properties. With the goal of using pure polymers in
order to maintain specific properties, such as low density and reversible elastic deformation to large strain,
and better retention of mechanical properties with increasing temperature, we developed a generic method
to reinforce weak elastomers.
In the past decade, Gong et al. have synthesized hydrogels formed with two interpenetrating networks with
very different levels of crosslinking. Those double networks show a significantly enhanced fracture toughness
compared to a single networks [1][2][3]. This improvement in toughness is due to the breaking of the bonds of
the more crosslinked and highly stretched minority network while avoiding crack propagation through the less
crosslinked and unstretched majority network. This method has been adapted to acrylic elastomers resulting
in reinforced double and triple networks obtained with sequential swelling/polymerization steps.
Figure 1: Stress/strain curves of different multiple Ethyl Acrylate networks showing the different
behaviors that can be obtained by changing the prestretching λ0 : brittle fracture (red); hardening
(blue); hardening followed by a softening (green); yielding and necking phenomenon (black).
Here we propose to focus on the different mechanical properties that can be obtained with these elastomers. Studies systematically varying the prestretching λ0 of the first network highlight the importance of the
this parameter on the properties of the multiple network elastomers as can be seen in Figure 1. The influence of this parameter on the dissipation will also be discussed as well as the fracture properties of this set
of multiple network materials.
[1] Gong, J. P.; et al, Y. Adv. Mater. 2003, 15, 1155-1158.
[2] Tanaka, Y.; et al J. of Physical Chemistry B 2005, 109, 11559-11562.
[3] Gong, J. P. Soft Matter 2010, 6, 2583.
[4] Chen, Y. ; et al, Nature Chemistry 2012, 4, 559-562
[5] Ducrot, E. ; et al, Science 2014, 40, 186-189.
66
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O-18
Gel networks as confined microenvironments for photochemical reactions
that are inaccessible in solution under mild conditions
David Díaz Díaz
Universität Regensburg, Fakultät für Chemie und Pharmazie, Institut für Organische Chemie,
Universitätsstr. 31, D-93053 Regensburg, Germany
e-Mail: [email protected]
Through millions of years of evolution, nature has used confinement and compartmentalization to access
otherwise slow or forbidden pathways and achieve high selectivity under mild conditions.1 This has inspired
scientists all over the world to study the effects of reactant confinement in non-conventional media on their
chemical properties and reactivity.2 The fields of photochemistry and photocatalysis, among others, have
also capitalized on the benefits of spatial confinement,3 which are related to changes in key properties such
as light absorption, formation of redox intermediates, lifetime of excited species, thermodynamics of reacting
mixtures, kinetics of competitive steps and adsorption/desorption of chemical species.
Herein, the first proof of concept for the application of intragel green-to-blue photon upconversion to a chemical
reaction will be discussed (Figure 1). The developed method allows the photoreduction of aryl halides at
room temperature and under aerobic conditions.4 These results open the door for future work involving bond
activation pathways that are inaccessible in solution under very mild conditions.
Figure 1. General concept of this work: Two photons process based on TTA-UC produces one photon of
higher energy that can be used in chemical reactions. This event can be achieved using visible light at room
temperature and in air when confined into a gel doped with a donor/acceptor pair. R = reactant; P = product.
(Endnotes)
1 . 2 . 3 . 4.
Prescher, J. A.; Bertozzi, C. R. Nat. Chem. Biol., 2005, 1, 13-21.
Todres, Z. V. in Organic Chemistry in Confined Media. Springer, Switzerland, 2013.
Palmisano, G.; Augugliaro, V.; Pagliaro, M.; Palmisano, L. Chem. Commun., 2007, 3425-3437.
Häring, M.; Pérez-Ruiz, R.; von Wangelin, A. J.; Díaz, D. D. Chem.Commun. 2015, 51, 16848-16851.
67
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O-19
Linear-Dendritic Macromolecules as components in Biomedical Soft Tissue
Adhesives
Viktor Granskog, Oliver C. J. Andrén, Yanling K Cai, Marcela Gonzalez-Granillo, Li Fellander-Tsai,
Hans von Holst, Lars-Arne Haldosen, Michael Malkoch
KTH – Royal Institute of Technology, School of Chemical Science and Engineering,
Dept. of Fiber and Polymer Technology, Teknikringen 56, SE-100 44, Sweden
[email protected]
There is a large interest in dendritic polymers due to their different properties compared to linear polymers.
Their decreased entanglement and large amount of peripheral end-groups that are readily available for further functionalization open up great possibilities in material design and applications[1,2]. Dendritic molecules
are i.e. used in medical applications such as drug delivery systems and tissue engineering[3-5]. The dendritic
structures have also taken the step into soft tissue sealants, where Grinstaff’s group has introduced dendron-structures to as sealants in ophthalmic surgery[6,7].
In this study, dendritic-linear-dendritic (DLD) hybrids of poly(ethylene glycol) (PEG) and 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) were synthesized and functionalized to attain allyl-functional end-groups. The
DLDs were designed in order to achieve biocompatible adhesive components with biodegradable ester-bonds
and to attain suitable resin viscosity without addition of a co-solvent. DLDs with pseudo-generations of 3 to
6 (G3-G6) were created and evaluated to acquire a view of their potential as components in biomedical adhesives. The DLDs were used in soft tissue adhesive patches (STAPs) together with tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate (TEMPIC) as crosslinker and a surgical mesh for structural support. By using
high-energy visible (HEV) light initiated thiol–ene coupling (TEC) chemistry, STAPs were cured in only 30
seconds and displayed good adhesion to wet soft tissue and also encouraging results in cytotoxicity tests[8].
[1] F.Vögtle, G. Richardt, N. Werner and A. J. Rackstraw, Dendrimer Chemistry: Concepts, Syntheses, Properties,
Applications, Wiley-VCH, Weinheim, 2009.
[2] J. M. J. Frechet and D. A. Tomalia, Dendrimers and Other Dendritic Polymers, Wiley, Chichester, 2001.
[3] Zhang HB, Patel A, Gaharwar AK, Mihaila SM, Iviglia G, Mukundan S, et al. Hyperbranched Polyester Hydrogels
with Controlled Drug Release and Cell Adhesion Properties. Biomacromolecules. 2013;14(5):1299-310.
[4] Oudshoorn MHM, Rissmann R, Bouwstra JA, Hennink WE. Synthesis and characterization of hyperbranched polyglycerol hydrogels. Biomaterials. 2006;27(32):5471-9.
[5] Altin H, Kosif I, Sanyal R. Fabrication of “Clickable” Hydrogels via Dendron-Polymer Conjugates. Macromolecules.
2010;43(8):3801-8.
[6] Velazquez AJ, Carnahan MA, Kristinsson J, Stinnett S, Grinstaff MW, Kim T. New dendritic adhesives for sutureless
ophthalmic surgical procedures - In vityo studies of corneal laceration repair. Arch Ophthalmol-Chic. 2004;122(6):86770.
[7] Oelker AM, Berlin JA, Wathier M, Grinstaff MW. Synthesis and Characterization of Dendron Cross-Linked PEG
Hydrogels as Corneal Adhesives. Biomacromolecules. 2011;12(5):1658-65.
[8] Granskog V, Andren OCJ, Cai YK, Gonzalez-Granillo M, Fellander-Tsai L, von Holst H, Malkoch M. Linear Dendritic Block Copolymers as Promising Biomaterials for the Manufacturing of Soft Tissue Adhesive Patches Using Visible
Light Initiated Thiol-Ene Coupling Chemistry. Adv Funct Mater. 2015;25(42):6596-605.
68
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O-20
Hydrogels as hosts for Substrate Mediated Enzyme Prodrug Therapy
Molly M. Stevens c, Frederik Dagnæs-Hansen d and Alexander N. Zelikin a, b
a
b
Department of Chemistry, Aarhus University, Denmark
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Denmark
Department of Materials, Department of Bioengineering, and Institute of Biomedical Engineering, Imperial
College London, UK
c
d
Department of Biomedicine, Aarhus University, Denmark
Abstract: With 8.2 million cancer deaths worldwide in 2012 (1), cancers impose a major health threat to the
human population, whilst prompting a significant biomedical challenge to the scientific community. Conventional anti-cancer therapies often imply high risks of severe adverse events due to low targeting specificity
of highly potent chemotherapeutic agents. Furthermore, first generation targeting biomedical devices, such
as, drug eluting beads (DEB) utilized clinically for transarterial chemoembolization (TACE), entails a low degree of flexibility once implanted. In the presented work, we introduce an implantable biocatalytic platform
facilitating on-site activation of inactive prodrugs, thus increasing the therapeutic flexibility while lowering
the risk of potentially lethal side effects. To expedite clinical translation, we investigate hydrogels comprised
of FDA approved polymers and prodrug-specific enzymes, as hosts for substrate mediated enzyme prodrug
therapy (SMEPT; refer to figure) (2, 3). By utilizing different formats of these hydrogels, they can be adapted to different clinical applications. One such format is macro-sized biocatalytic hydrogel beads (BHB),
which can be fine-tuned in size and enzyme composition, allowing precise implantation into specific blood
vessels using clinically established TACE techniques. Furthermore, also replacement of an administered
drug, drug dose and implementation of combination therapy, etc., during an ongoing treatment regimen,
can be achieved. Another hydrogel format is electrospun polymer fibers. To increase the enzymatic stability,
liposome encapsulated enzymes have been employed and embedded into electrospun poly(vinyl alcohol)
(PVA) fibers, that have proven effective for anti-proliferative SMEPT applications, in vitro. The small size of
the biocatalytic components of the presented SMEPT-based platform, the enzymes, and the plasticity of the
substrates, the hydrogels, allows fine-tuned engineering of the size (from nano to micro and macro), shape
and appearance of such biomedical devices, potentially making it suitable for delivery to any desired tissue.
1.
World Health Organization, Feb. 2016, http://globocan.iarc.fr/Pages/fact_sheets_cancer.aspx
2.
Mendes, A.C. and A.N. Zelikin, Enzyme Prodrug Therapy Engineered into Biomaterials. Advanced
Functional Materials, 2014. 24(33): p. 5202-5210.
3.
Fejerskov, B., et al., Biocatalytic Polymer Coatings: On-Demand Drug Synthesis and Localized
Therapeutic Effect under Dynamic Cell Culture Conditions. Small, 2014. 10(7): p. 1314-1324.
69
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O-21
Interface Design using Block Copolymers: Crosslinking and
Interpolyelectrolyte Complexation
F. H. Schacher
Friedrich-Schiller-University Jena, Laboratory of Organic and Macromolecular Chemistry, D-07743 Jena,
Germany
Jena Center for Soft Matter (JCSM), Philosophenweg 7, D-07743 Jena, Germany
[email protected]
Block copolymers represent a unique class of materials for the generation of nanostructured materials in
different environments – mainly driven by the inherent immiscibility of unlike building blocks.[1] Together
with the use of monomers featuring unreacted functional groups in the side chain, this allows for straightforward modifications reactions or (reversible) crosslinking of nanostructured materials.[2, 3]
Here, our focus is put on (intra-micellar) interpolyelectrolyte complexation as driving force to create materials
for biomedical applications. By adjusting monomer structure, block length ratios, and sequence, precise control over charge and charge density in nanostructured materials can be achieved. Examples are multicompartment micelles from apmpholytic ABC triblock terpolymers featuring a discontinuous (patchy) shell, which
represent highly interesting vehicles for non-viral gene delivery into
adherent and suspension cells.[4] Further, we designed a small library
of ABC triblock terpolymers based on polyethers where blocks A and
C are identical. Only block B differs regarding side chain functionality,
charge, or solubility. With these materials at hand, we start exploring
possibilities for co-assembly strategies towards core-shell-corona micelles where charge, charge density, and composition of the shell can
be purposefully varied.[5] Finally, iron oxide nanoparticles have been
coated with polyelectrolytes of varying charge and charge density
and effects on subsequent protein adsorption were investigated.[6, 7]
Figure 1: Schematic depiction of an ampholytic ABC triblock terpolymer undergoing intra-chain interpolyelectrolyte complexation.
References:
[1] Schacher, FH; Rupar, PA; Manners, I; Angew. Chem. Int. Ed. 2012, 51, 7898-7921; [2] Hörenz, C; Rudolph, T; Barthel, MJ; Günther, U; Schacher, FH; Polym. Chem. 2015, 6, 5633-5642; [3] Rudolph, T; Espeel,
P; DuPrez, FE; Schacher, FH; Polym. Chem. 2015, 6, 4240-4251; [4] Rinkenauer, AC et al.; ACS Nano
2013, 7, 9621-9631; [5] Barthel, MJ et al.; Biomacromolecules 2014, 15, 2426-2439; [6] vdLühe, M et al.;
RSC Advances 2015, 5, 31920-31929; [7] Weidner, A et at.; Nanoscale Res. Lett. 2015, 10, 282;
70
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O-22
Rheological Behavior of Dense Suspensions of Thermo-Responsive Microgels
Kenji Urayama1, Sarori Minami1, Shota Uratani1, Taku Saeki2, Shen Cong2, Toshikazu Takigawa2, Takumi
Watanabe3, Masaki Murai3, Daisuke Suzuki3
1
Kyoto Institute of Technology, Department of Macromolecular Science & Engineering, Kyoto, Japan
2
Kyoto University, Department of Materials Chemistry, Kyoto, Japan
3
Shinshu University, Department of Textile Science & Engineering, Japan
We study the rheological behavior of the dense suspensions of soft microgels. In contrast to suspensions
of hard particles, suspensions of soft microgels can be concentrated beyond a critical volume fraction for
dense close packing, because they can undergo deformation, interpenetration and deswelling. Such dense
suspensions of soft microgels behave like elastic solids at sufficiently low stresses or strains below a critical
stress or stain, while they flow at high stresses or strains beyond a critical stress (strain). This yielding
behavior for soft microgel pastes has long been known, but it still remains to be fully understood what kind of
characteristic of microgel suspension governs the critical stress (or strain). We systematically investigate the
yield stress and strain for the dense suspensions as a function of particle concentration, particle size, particle
size-distribution, and the kind of constituent polymer using the well-characterized specimens. We discuss the
physical origin of the yielding of dense microgel pastes on the basis of these data.[1]
We also investigate the temperature dependence of the linear viscoelasticity for the suspensions of poly(Nisopropylacryamide) (PNIPA) microgels. The PNIPA microgels undergo volume transition at a critical
temperature (Tc) between the swollen and shrunken states. The heating across Tc not only reduces the
volume fraction of microgels in the suspensions but changes the interparticle interaction from repulsive to
attractive one. In the collapsed state with attractive interparticle interaction, the moderately concentrated
suspensions become viscoelastic liquids with high viscosities and long terminal relaxation times due to the
formation of a network-like aggregation of particles. The network-like aggregation of particles is so fragile that
it can be broken by very small stress of several Pascal.
[1] Urayama, K., Saeki, T., Chen, S., Uratani, S., Takigawa, T., Murai, M., Suzuki, D., Soft Matter, 10, 9486
(2014).
71
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O-23
Hydrogels of cellulose nanofibrils and thermoresponsive cationic block
copolymers
Tobias Ingverud,1,3 Emma Larsson,1,2 Guillaume Hemmer,1 Ramiro Rojas,1,3 Michael Malkoch,1
Anna Carlmark1,2,3
1
KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Fibre and
Polymer Technology, Teknikringen 56, SE-100 44, Stockholm, Sweden
2
KTH Royal Institute of Technology, BiMaC Innovation, Teknikringen 8(D), SE-100 44, Stockholm, Sweden
3
KTH Royal Institute of Technology Wallenberg Wood Science Center, Teknikringen 56-58, SE-100 44,
Stockholm, Sweden
Figure 1. Schematic representation of electrostatic crosslinking of TEMPO oxidized CNF and cationic star block copolymer
Atom transfer radical polymerization (ATRP) has been utilized to synthesize triblock and star-block copolymers of poly(di(ethylene glycol) methyl ether methacrylate) (PDEGMA) and quaternized poly(2-(dimethylamino)ethyl methacrylate) (qPDMAEMA). The block copolymers, that all contained a minimum of two cationically
charged blocks, were sequentially used for ionic crosslinking to a dilute dispersion of anionic TEMPO-oxidated cellulose nanofibrils (CNF, 0.3 wt%), forming free-standing hydrogels through electrostatic crosslinking,
with a storage modulus up to 2.9 kPa. The ability of the block copolymers to adsorb to CNF was confirmed
by quartz crystal microbalance with dissipation monitoring (QCM-D) and FT-IR, and the thermoresponsive
properties of the hydrogels were investigated by rheological stress and frequency sweep, and gravimetric
measurements.
72
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O-24
Biobased hydrogels for metal ion waste water treatment
Geng Hua and Karin Odelius
Department of Fiber and Polymer Technology, KTH Royal Institute of Technology, SE-100 44 Stockholm,
Sweden
Correspond to: [email protected]
The demand for waste water treatment has been inclining over the years, especially in the developing countries where pollution-generating industries are heavily located. The issue of heavy metal water waste treatment is highly important since the substances are high toxicity and accumulate in the human body, where
absorption using absorbents is a generally applied means. Existing examples of absorbents include active
carbon, modified silica gel, crosslinked polystyrene sulfonate and crosslinked cellulose. We here show a new
pathway to a lactone based, heavy metal water waste absorbent. The hydrogel-type of absorbent is obtained
through the highly efficient aminolysis reaction in combination with hydroxyl-anhydride esterification crosslinking chemistry. Unlike the statistical information usually obtained from the bio-resourced precursors such
as cellulose and chitin, the precise structures presented here allow a well-tuned network formation. Not only
can the crosslinking density be adjusted, but also the hydrophilicity/hydrophobicity of the hydrogel can be
varied. The performance of the absorbent over a range of heavy metal ions was evaluated through various
techniques such as titration, SEM-EDS and TGA. The absorbent shows good metal chelating ability over the
complete range of investigated heavy metal ions. The relationship between the network structures and the
chelating performance is also revealed.
This financial support of this project comes from the Swedish Research Council, VR (grant ID: 621201356
25).
73
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O-25
Highly Flexible, Tough, and Self-Healable Supramolecular Polymeric Materials
Using Host–Guest Interaction
1
Masaki Nakahata1, Yoshinori Takashima2, and Akira Harada1,3
Graduate School of Science, Osaka University, 1-1 Machikaneyama-cho, Toyonaka, Osaka, 560-0043,
Japan. 2ImPACT, Cabinet Office, Japan.
<Introduction>
Flexible, tough, and self-healable polymeric materials are
promising to be a solution to the energy problem by substituting
for conventional materials. A fusion of supramolecular chemistry
and polymer chemistry is a powerful method to create such
intelligent materials. We previously developed self-healable
or highly elastic polymeric materials1,2 based on host-guest
interaction of cyclodextrins (CDs) and hydrophobic guest
molecules. Here we report a flexible, tough, and self-healable
polymeric material based on water-soluble polymers carrying
CD and guest residues.
<Results and discussion>
Terpolymerization of acrylamide (AAm) carrying βCD, AAm
carrying adamantane (Ad), and water soluble monomers
resulted in a transparent gel (βCD-Ad gel (x,y)). Here x and y
represent the mol% of βCD and Ad units. βCD-Ad gel exhibited
high flexibility and toughness. The gel also showed self-healing
properties when damaged (Figure 1). It is likely that reversible
complex formation between βCD and Ad gives the resultant gel
these properties. The self-healing property was observed not
only in a hydrogel state but also in a xerogel state. We utilized
the xerogel for a self-healable coating film which can self-heal
from injury on its surface by misting with a little amount of water
(Figure 2).3
<References>
1. Nakahata, M.; Takashima, Y.; Yamaguchi, H.; Harada, A. Nat.
Commun. 2011, 2, 511.
2. Kakuta, T.; Takashima, Y.; Nakahata, M.; Otsubo, M.;
Yamaguchi, H.; Harada, A. Adv. Mater. 2013, 25, 2849-2853.
3. Nakahata, M.; Takashima, Y.; Harada, A. Macromol. Rapid
Commun. 2016, 37, 86-92.
74
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O-26
A new microfluidic switch technique by controllably buckling
Stimuli-responsive polyelectrolyte hydrogel thin layer
Ben B. Xu,
Smart Materials and Surfaces Lab, Faculty of Engineering and Environment,
Northumbria University, Newcastle upon Tyne, NE1 8st, UK
Abstract:
Elastic mechanical instabilities in thin polymer films may present as different out-of-plane deformation modes
including wrinkling, creasing, buckling, folding, and delamination. Elastic transformation can achieve the
giant morphology change in very short time. Recent experimental and theoretical progress has provided a
fundamental understanding on these instabilities in gel systems (Phys. Rev. Lett. 105, 2010; Adv. Mater. 23,
2011; Soft Matter 8, 2012; Soft Matter 10, 2013). Some applications incorporate buckled thin film structures
into devices to fulfill certain purposes such as, to prevent device/structure failure during large deformations (Adv. Mater. 20, 2008), to relieve surface/
interfacial mechanical stress (Nature Nanotech.
1, 2006), to yield novel strain sensing structures (Adv. Mater. 26, 2014), or to improve the
efficiency of solar cells.(Nat. Photonics 6, 2012).
In recent work, we have shown fast actuation of
crease instability (< 1 sec) on the surfaces of thin
ionic hydrogel layers at low electric voltages of 2
– 4 V (Adv. Mater. 25, 2013) by constructing layer
system. In the current report, we describe the
reversible electrically actuated delamination and
buckling of a thermally responsive poly(N-isopropylacrylamide-co-sodium acrylate) (PNIPAM)
Fig.1 a) Stress state before buckling, b) buckling
polyelectrolyte gel layer on micro-patterned elecinduced delamination stripes patterns, c) Structure trode surfaces. Through a two-step mechanism
design and PNIPAM gel, d) Electro-actuated irregu- corresponding to electrochemically-triggered delar buckling blisters, and e) Euler buckling blisters, f) lamination at a first critical voltage, followed by
cross-sections of irregular buckling blister and Euler gas bubble formation at a second critical voltage,
we demonstrate that large out of plane displacebuckling.
ments (up to 8 times the initial gel thickness) can
be achieved, with rapid switching at modest triggering voltages (from – 3 to – 6 V). Using thermally triggered
deswelling of the gel, we show that it is possible to return the gel to its initially flat and adherent state, enabling
reproducible formation of buckled structures through multiple cycles of actuation. Our ambition is to investigate the actuated buckling instability and use it as passive valve for micro-fluidic application.
75
Oral
O-27
Synthesis of Rotaxane-Cross-Linked Polymers Using Macromolecular [2]
Rotaxane Having Hydrophilic Axle Component as a Vinylic cross-linker
Daisuke Aoki1, Daisuke Suzuki2, Toshikazu Takata1
Department of Chemical Science and Engineering, Tokyo Institute of Technology, 2-12-2 O-okayama,
Megro-ku, Tokyo 152-8552, Japan
2
Graduate School of Textile Science and Technology, Shinshu University, 3-15-1 Tokida, Ueda, Nagano
386-8567, Japan
1
Rotaxane cross-linked polymers (RCPs) are characterized by the high mobility of the polymer chains at the
cross-link points or the movable cross-link points due to the mechanically linked components. RCPs have
attracted great interest of polymer scientists from both scientific and practical viewpoints.1, 2 In this work, novel
rotaxane cross-linkers (RCs) having macromolecular [2]rotaxane structures, which consist of a hydrophilic
polymer as a axle component and a crown ether as a wheel component, were synthesized. RC having
poly(ethylene oxide) (PEO) axle was synthesized via the rotaxane-end cap method. RCP was obtained by the
radical polymerization of 2-ethylhexyl acrylate and N-isopropylacrylamide in the presence of RC. Meanwhile,
covalently cross-linked polymer (CCP) was prepared for comparison using a similar macromolecular
chemical cross-linker (CC). The properties of RCPs and CCPs were evaluated by DSC, swellability, tensile
strength, and phase transition behavior in water, demonstrating the prominent characteristics of the rotaxane
cross-linkers.
(1) Iijima, K.; Kohsaka, Y.; Koyama, Y.; Nakazono, K.; Uchida, S.; Asai, S.; Takata, T. Polym. J. 2014, 46,
67–72.
(2) Kato, K.; Ito, K. React. Funct. Polym. 2013, 73, 405–412.
76
Oral
O-28
Study on crosslinked structure and thermal properties of polymer networks
based on Tung oil and PVA with different catalytic systems
Apichaya Jianprasert1, Pathavuth Monvisade2 and Masayuki Yamaguchi3
1
2
College of Nanotechnology, King Mongkut’s Institute of Technology Ladkrabang, Thailand
Polymer Synthesis and Functional Materials Research Unit, Department of Chemistry, Faculty of Science,
King Mongkut’s Institute of Technology Ladkrabang, Thailand
3
School of Materials Science, Japan Advanced Institute of Science and Technology, Japan
This work is focused on the effect of the different catalytic systems on network structures and thermal properties of the polymer networks from poly(vinyl alcohol) (PVA) and Tung oil. The polymer networks based on
Tung oil and PVA using potassium persulfate (KPS) as a thermal catalyst or KPS and sodium thiosulfate as a
redox catalyst was performed at 60 ºC and 80 ºC. FTIR results of the polymer networks indicated crosslinking reaction at double bonds of Tung oil as confirmed by the lower intensity of the conjugated double bond at
992 and 965 cm−1. In addition, Tung oil could be crosslinked by both catalysts. Moreover, at 60 ºC, it can be
seen that the crosslinking reaction with the redox catalyst could occur better than with the thermal catalyst.
To prove the crosslinking reaction of PVA in the polymer networks, water resistance of the polymer networks
was also investigated by swelling in distilled water. It was found that the PVA was successfully crosslinked
by thermal catalyst but was not by redox catalyst. Besides, from this result, it could be suggested that, in the
redox system, structure of the polymer networks was mainly formed by Tung oil. Thermal properties of the
polymer networks were evaluated by DMA. Tg of PVA with the thermal catalyst is higher than that with the
redox catalyst because of the network formation of PVA in thermal catalytic system. While the Tg of Tung oil in
the polymer networks with the redox catalyst is higher than that with the thermal catalyst. This is reasonable
because the crosslinking reaction of Tung oil with the redox catalyst could easily occur better than with the
thermal catalyst. Altogether, crosslink structure of Tung oil exhibited major influence on properties of PVA/
Tung oil polymer network.
77
Oral
O-29
Photo stimuli responsive supramolecular and topological materials using
host-guest complexes
Yoshinori TAKASHIMA, Akira HARADA
Dept. Macromol. Sci., Grad. Sci. Osaka University, Toyonaka, Osaka, 560-0043 JAPAN
Various kinds of biological molecular motors, such as myosin, kinesin, and dynein, realize the conversion of
energy in ATP hydrolysis into mechanical work. These mechanical motions inspired supramolecular chemist
to realize polymeric materials with supramolecular materials. Two structural approaches may realize supramolecular actuators through host–guest interactions: a method with a linear main chain and one with a side
chain in the polymer structure. We have prepared photo responsive supramolecular actuators by integrating
host–guest interactions on the polymer side chains (Fig. 1a). The association and dissociation of inclusion
complexes as crosslinking units on the polymer side chains demonstrate contraction and expansion motions
due to changes in the crosslinking density. A plate-shaped actuator bent against the incident ultraviolet (UV)
light. Herein we report that topological hydrogel containing CD-based [c2]daisy chains as crosslinkers contract and expand through photoresponsive sliding motions of the [c2]daisy chain (Fig. 1b). The photogenerated topological hydrogel is reminiscent of contraction and expansion motions of skeletal muscle.
Figure 1. Stimuli responsive gel using cyclodextrin derivatives
and their photo responsive behavior.
References
1. Harada, A.; Takashima, Y.; Nakahata, M. Acc. Chem. Res. 2014, 47, 2128-2140.
2. Takashima, Y.; Hatanaka, S.; Otsubo, M.; Nakahata, M.; Kakuta, T.; Hashidzume, A.; Yamaguchi, H.;
Harada, A. Nat. Commun. 2012, 3, 1270.
3. Iwaso, K.; Takashima, Y.; Harada, A. Nat. Chem. 2016, accepted.
78
Oral
O-30
Studying processes leading to swelling of DNA-responsive hydrogels
Eleonóra Parelius Jonášová, Astrid Bjørkøy and Bjørn Torger Stokke
Biophysics and Medical Technology, Department of Physics, Norwegian University of Science and
Technology (NTNU), Trondheim, Norway
Responsive hydrogels – materials that adjust their properties in response to a stimulus – have gained great
interest in the biomedical field for their potential applications in sensing, targeted drug delivery and regenerative medicine. One reason for this is the tunable properties of these materials. In case of molecule-sensitive
hydrogels, exposure to a target molecule leads to a change in the gel’s swelling equilibrium. The swelling,
however, is only the last of the cascade of processes that take place after the addition of the target compound.
These processes, such as migration of the molecule within the network, its binding, and network relaxation,
affect each other and are also influenced by environmental variables (temperature, pH, etc.) and gel properties (pore size, etc.). In the present work, we describe hydrogels consisting of a polyacrylamide network with
additional crosslinks made of DNA double strands grafted to the network. The DNA crosslinks are physical
and can be opened by a complementary oligonucleotide in the process of competitive displacement, leading
to swelling of the gel. The hydrogels can be mounted at the end of an optical fiber for interferometric monitoring of the swelling with a resolution of 2 nm1. In order to gain more insight into the interrelated processes,
the free and gel-bound DNA are labelled with fluorescent dyes and quenchers which allows to monitor the
migration of the target DNA and the opening of the crosslinks using a confocal laser scanning microscope.
The use of DNA as both a target and sensing molecule allows controlling and tuning the binding properties
by selecting DNA sequences with different extent of base pair complementarity, and studying their effect on
the other processes. Initial results focus on the effect of binding properties on the migration pattern of the
invading strand. For stronger and faster binding, the migration is slowed down due to increased binding and
a sharp advancing boundary is observed instead of a gradual blurring.
1.
Tierney, S.; Hjelme, D. R.; Stokke, B. T., Determination of Swelling of Responsive Gels with
Nanometer Resolution. Fiber-Optic Based Platform for Hydrogels as Signal Transducers. Analytical Chemistry 2008, 80 (13), 5086-5093.
79
O-31
Oral
Rational Design of Molecularly Stimuli-responsive Hydrogels
Using Supramolecular Crosslinks
Takashi Miyata1, 2 Akifumi Kawamura1, 2
1
Department of Chemistry and Materials Engineering and 2ORDIST, Kansai University,
3-3-35, Yamate-cho, Suita, Osaka 564-8680, Japan
Swelling ratio (m3/m3)
Stimuli-responsive hydrogels have been developed because of their many potential applications as smart
materials for diagnosis, drug delivery systems and cell cultures. However, there have been few studies on
molecularly stimuli-responsive hydrogels that undergo changes in the volume in response to a target molecule.
We proposed a new strategy for designing molecularly stimuli-responsive
hydrogels, which uses molecular complexes as dynamic crosslinks of their
networks1). For example, using glycopolymer-lectin complexes, antigenantibody bindings and DNA duplexes, we have strategically prepared a
variety of molecularly stimuli-responsive hydrogels that can swell or shrink
1.1
in response to a target biomolecule such as glucose, an antigen, a tumor
PAAm Gel
1.0
maker glycoprotein and DNA2-3). In this study, supramolecular complexes
0.9
based on cyclodextrin (CD) were utilized as dynamic crosslinks for designing
0.8
Non IMP Gel (CD=5 mol%)
molecularly stimuli-responsive hydrogels that exhibited unique shrinkage
0.7
in response to a target molecule. This paper focuses on rational design of
IMP Gel (CD=5 mol%)
0.6
supramolecularly crosslinked hydrogels with CD ligands and their responsive
0.5
behaviors.
0.4
Molecularly stimuli-responsive hydrogels that shrink in response to
bisphenol A (BPA) as a target molecule were prepared by molecular
imprinting using CDs as ligands and a minute amount of crosslinker4). BPAimprinted hydrogels showed greater shrinkage than non-imprinted hydrogels
because CD ligands arranged at suitable positions formed CD–BPA–
CD complexes that acted as crosslinks. BPA-responsive microsized
hydrogels with CDs were also prepared by photopolymerization using
a fluorescence microscope5). The microsized hydrogels showed ultraquick shrinkage in response to target BPA. Furthermore, the flow rate
of a microchannel was autonomously regulated by the BPA-responsive
shrinking of the microsized hydrogels as smart microvalves. This
paper focuses on the effect of structure on responsive behavior of
various molecule-responsive gels with CDs.
0
10
20
30
Time (hr)
40
50
Fig. 1. Swelling ratio changes of
a BPA-imprinted (○), non-imprinted (●) and PAAm (□) hydrogels in a water containing BPA.
Fig. 2. (a) Flow rate change of channel A (●)
with a BPA-imprinted gel and channel B (〇)
without gel as a function of the time when
deionized water and an aqueous BPA solution
(120 µg mL−1) were flowed through the microchannel at a rate of 0.1 mL min−1.
References
1) Miyata, T. Polym. J. 2010, 42, 277.
2) Miyata, T.; Asami, N.; Uragami, T. Nature 1999, 399, 766.
3) Miyata, T.; Jige, M.; Nakaminami, T.; Uragami, T. Proc. Natl. Acad. Sci. USA 2006, 103, 1190.
4) Kawamura, A.; Kiguchi, T.; Nishihata, T.; Uragami, T.; Miyata, T. Chem. Commun. 2014, 50, 11101.
5) Shiraki, Y.; Tsuruta, K.; Morimoto, J.; Ohba, C.; Kawamura, A.; Yoshida, R.; Kawano, R.; Uragami, T.;
Miyata, T. Macromol. Rapid Commun. 2015, 36, 515.
80
Oral
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GOLD-DECORATED POLY(N-VINYLCAPROLACTAM) GEL PARTICLES
Joonas Siirilä, Mikko Karesoja, Heikki Tenhu
University of Helsinki
[email protected]
Poly(N-vinylcaprolactam), PVCL, is a biocompatible [1] thermoresponsive polymer which has been shown to
bind charged surfactants, as well as phenols, in aqueous solutions [2,3]. Macroscopic particles of PVCL have
been produced by adding aqueous polymer solution dropwise into aqueous salicylic acid. Hydrogen bonds
stabilize the particles and these can be used as drug carriers.[4]
Controlled polymerization of N-vinylcaprolactam is not as
easy as with many other vinyl monomers. Recently, several groups have successfully polymerized NVCL, e.g., with
ATRP. Quite often the control of the molecular mass is far
from ideal, however. We have prepared diblock copolymers
of NVCL and dimethylaminoethylmethacrylate, thus obtaining double-thermosensitive polymers. Solution properties
of the polymers is affected by the tendency of caprolactam
units to complex with the amine groups. Thermal collapse of
the polymer is step-wise, and has been studied by various
techniques.[5]
Recently we synthesized PVCL gel particles (size is of the
order of 100 nm) to the surfaces of which small AuNPs (2-4
nm) were bound with a click reaction.
Cryo-TEM image of the PVCL-AuNP particles in water
The particles are thermo and light sensitive. Binding and release of various probe substances has been
studied as function of temperature. While studying the effects of uv irradiation it was observed that PVCL and
AuNPs show in some cases very different catalytic activities.[6] The use of PVCL supported gold nanoparticles as catalysts will be discussed.
References
[1]Vihola, H, Laukkanen A, Valtola L, Tenhu H, Hirvonen J. Biomaterials (2005), 26(16), 3055-64
[2] Makhaeva E E, Tenhu H, Khokhlov A R; Macromolecules (1998), 31, 6112-6118
[3] Makhaeva E E, Tenhu H, Khokhlov A R; Polymer (2000), 41, 9139-9145
[4] Vihola H, Laukkanen A, Tenhu H, Hirvonen J; J Pharm Sci (2008), 97, 4783-4793
[5] Karesoja M, Karjalainen E, Hietala S, Tenhu H; J Phys Chem B (2014), 118, 10776-10784
[6] Siirilä J, Karesoja M, Pulkkinen P, Tenhu H, to be published
81
Oral
O-33
IPN hydrogels of poly(2-hydroxyethyl methacrylate) and poly(2,3-dihydroxypropyl methacrylate) with tunable deformation responses
Zhansaya Sadakbayeva, Miroslava Dušková-Smrčková, Adriana Šturcová, Miloš Steinhart,
Karel Dušek
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague
6, Czech Republic,
[email protected]
Designing hydrogel biomaterials for application in tissue engineering and ophthalmology implies fine adjusting of mechanical properties within certain range of moduli. Interpenetrating network (IPN) technology
with two different types of monomers is one of the ways of performing materials with tunable moduli. The
formation of poly(2,3-dihydroxypropyl methacrylate), PDHPMA, network by free-radical polymerization in the
heterogeneous environment of the porous poly(2-hydroxyethyl methacrylate), PHEMA, network was studied.
The structure of the primary network was attained by polymerization-induced phase separation – leading to
particulate morphology or cryogelation – leading to oriented macropores. As a result, the final PHEMA-PDHPMA hydrogel includes areas with interpenetrating network structure and areas with single network only that
show very different mechanical and swelling behavior and even different course of crosslinking.
The presence of the first polymer network significantly influenced the kinetics of the polymerization of the second network as well as the second critical conversion. The crosslinking of PDHPMA second network within
the environment of heterogeneous macroporous first PHEMA network was much faster than in homopolymerizing PDHMPA. The final conversion of the second network was achieved using heating above the glass
transition temperature of PHEMA-PDHPMA system (that was approx. 111°C). PHEMA in IPNs exhibited surprisingly high swelling capacity when incorporated into the IPN with more hydrophilic PDHPMA. The chains
of heterogeneous spherical-morphology hydrogel were stretched upon swelling up to 95 times compared to
their dry state, while in the cryogel-based IPNs this stretching factor was of 45. This phenomenon was caused
by osmotic pressure exerted by swelling of a very hydrophilic second network that remarkably stretches the
chains of the first network. In turn, the framework of the first network prevents the second network from the
rupture at high swellings. The gels were macroscopically strong and resisted mechanical failure. Young’s
modulus of cryogel-based IPNs increased to 510 kPa while it was 85 kPa in case of single networks and this
increase was from 10 kPa to 620 kPa for IPNs based on spherical-morphology single network hydrogels.
Acknowledgement. This work was supported by the Grant Agency of the Czech Republic, project number No.
13-00939S.
82
Oral
O-34
Recent trends in telechelic amphiphilic gelators: the use of random
copolymers as building blocks for tuning the network properties
Constantinos Tsitsilianis1, Georges Gotzamanis1, M.M. Soledad Lencina,1, Margarita A. Dyakonova2,
Chia-Hsin Ko2, Christine M. Papadakis2,Maria Rikkou- Kalourkoti3 and Costas S. Patrickios3
1
Department of Chemical Engineering, University of Patras, 26504, Patras, Greece.
2
3
TU München, Physik-Department, Garching, Germany.
Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus.
[email protected]
Water-soluble associative polymers (AP) belong to a very interesting class of polymeric materials with fascinating properties due to their spontaneous self-organization in aqueous media and have attracted considerable interest in recent years due to their unique rheological properties, that make them very useful materials
as rheology modifiers in cosmetics and coatings, suspension stabilizers, drug carriers and injectable hydrogels in pharmaceutical formulations and other water-based applications.
Traditional associative polymers consist of a neutral water soluble polymer containing hydrophobic associative groups (stickers). Telechelic polymers (chains end-capped by hydrophobic groups) are often considered
as model gelators thanks to their precise macromolecular topology. In aqueous media, and above a critical
association concentration, the polymer chains self-associate forming flower-like micelles, constituted of a
hydrophobic core, surrounded by a corona of hydrophilic polymer chain loops. With increasing concentration,
loop to bridge transitions occur, leading to the interconnection of the flower-like micelles into a 3D network,
inducing a sol-gel transition manifested by a steep increase of the viscosity (thickeners).
In this presentation we address a macromolecular engineering route, toward the design of telechelic APs
bearing statistical copolymers as building blocks. This idea was dictated by the need to further tuning the
gelling properties of APs, aiming to fabricate “smart” nanostructured gelators. Two examples will be presented and discussed: 1) telechelic polyampholytes [PMMA-P(DEA-co-MAA)-PMMA], that self assemble through
hydrophobic interactions forming networks, the bridging chains of which are very sensitive to pH, in terms of
degree of ionization and charge sign and 2) telechelic polyelectrolytes [P(TEGMA-co-nBMA)-PDMA-P(TEGMA-co-nBMA)] in which the exchange dynamics of the stickers (end-blocks) can be tuned by temperature.
83
Oral
O-35
ULTRAFAST GELATION OF INJECTABLE REACTIVE MICROGELS:
THE POWER OF TAD CLICK CHEMISTRY
Rémi Absil
Université de Mons, Belgium
[email protected]
Injectable polymer networks are gaining increasing attention as scaffolds for drug release or tissue engineering owing to their ability to fill ill-defined locations upon injection. In that context, doubly crosslinked microgels (DX gels) appear as a highly interesting candidate as primarily crosslinked microbeads can be injected
with a reactive crosslinker to generate in situ macroscopic networks filling and fitting cavities at perfection to
optimize their action. Compared to other injectable networks, this new class of injectable hydrogels offers a
better tuning of hydrogel hierarchisation, swelling and mechanical properties.[1] However, these DX gels are
mainly obtained by radical coupling of vinyl functionalized particles, making this gelation mechanism inconvenient for in vivo applications.[1-4] Herein, we describe a new approach towards DX gels synthesis by using
the ultrafast triazolinedione[5] (TAD)-based click reaction to promote the formation of DX microgel networks.
Cyclopentadienyl (Cp) functional microgels were prepared by conventional water in oil radical suspension
copolymerization of poly(ethylene glycol methyl ether methacrylate) (Mn = 500 g/mol) with glycidyl methacrylate and ethylene glycol dimethacrylate as crosslinkers. Post-modification of the microgels was subsequently
achieved by reacting glycidyl functions with NaCp.[6] The effective surface modification as well as the control
of reactive Cp density were assessed by fluorescent microscopy after clicking N(1-pyrenyl) maleimide. In a
last step, the microgels were mixed with a bis-TAD functional crosslinker and self-assembled within adequate
rate to form doubly crosslinked microgel networks. Our findings demonstrate that click chemistry is a suitable
and efficient technique to synthesize doubly crosslinked microgels with a very fast gelation process, free of
any metal.
Reference:
[1] Liu, R.X., et al., Soft Matter, 2011. 7(19): p. 9297-9306.
[2] Milani, A.H., et al., Soft Matter, 2015. 11(13): p. 2586-2595.
[3] Lane, T., et al., Soft Matter, 2013. 9(33): p. 7934-7941.
[4] Farley, R., et al., Polymer Chemistry, 2015. 6(13): p. 2512-2522.
[5] De Bruycker, K et al., Chemical Reviews, 2016. 116(6) : p 3919-3974.
[6] Kaupp, M., et al., Polymer Chemistry, 2012. 3(9): p. 2605-2614.
84
Oral
O-36
ENGINEERING GLYCOSAMINOGLYCAN HYDROGELS TO CONTROL
SWELLING, MODULI AND FRACTURE PROPERTIES
Stevin H. Gehrke, Lawrence M. Chen, Bradley S. Harris, Anahita Khanlari, Colton E. Lagerman, Lauren E.
Pickens, Jack J. Rogers, Joshua D. Schroeder, Justin D. Smith-Cantrell, Tiffany C. Suekama,
Erik Van Kampen, Devany W. West
Dept. of Chemical & Petroleum Engineering, Univ. of Kansas, Lawrence, KS, 66045, USA
The mammalian extracellular matrix (ECM) fits the definition of a hydrogel in terms of water content, but
its mechanical properties are superior to synthetic hydrogels due to a complex set of interactions between
the different macromolecular components of the ECM. To develop synthetic networks with comparable
properties, combinations of physical entanglements with covalent crosslinking of two or more components
will likely be required. In this work, multicomponent hydrogels based upon the glycosaminoglycans
chondroitin sulfate (CS) and hyaluronic acid (HA), major components of the ECM, and synthetic monomers
and macromers were developed to cover a broad range of moduli and fracture properties. Several routes
were taken to achieve this: copolymerization of photopolymerizable methacrylated CS or HA macromers
(MCS, MHA) with monomers to improve crosslinking efficiency, photocrosslinking of pentanoatefunctionalized HA (PHA) by thiol-ene chemistry and the creation of CS and HA double network (DN) gels.
A key goal was to improve the crosslinking effectiveness of photopolymerized GAG hydrogels to improve
moduli and fracture properties. Considering the high persistence lengths of GAGs, it was hypothesized
that copolymerization of GAGs with small amount of oligo(ethylene glycol) diacrylates (OEGDA) would
reduce crosslinking inefficiencies resulting from the steric hindrances of the macromers in solution.
Copolymerization of MCS or MHA in water with small amounts of OEGDAs increased the shear modulus
of MCS homopolymer up to five times and lowered the swelling degree to a third of its value in water.1
The dependence of moduli and swelling on the OEGDA length and the fact that monoacrylates equally
increased moduli suggested that crosslinking occurs primarily by methacrylate kinetic chains rather than
the OEG linker. In contrast, photocrosslinking of HA using thiol-ene chemistry enabled formation of gels at
much lower macromer concentrations (down to 2 wt%), indicating a more efficient crosslinking reaction.
Additionally, the fracture strains of thiol-ene PHA gels were notably improved relative to MHA. This
suggests that thiol-ene chemistry results in more efficiently and uniformly crosslinked HA gels.
The generality of the double network combination of a brittle polyelectrolyte gel with a ductile nonionic
second network to achieve superior properties was demonstrated by synthesizing MCS and MHA-based
DN using polyacrylamide (PAAm) as the second network. The resulting DN hydrogels have properties
comparable to the well-known tough double-network gels of poly(2-acrylamido-2-methylpropane-sulfonic
acid)/PAAm developed by J.P. Gong and coworkers at Hokkaido University in Japan.2
REFERENCES
[1] Khanlari, A.; Suekama, T. C.; Detamore, M. S.; Gehrke, S. H. J. Polym. Sci. B Polym. Phys. (2015), 53,
1070.
[2] Suekama, T. C.; Hu, J; Kurokawa, T.; Gong, J. P.; Gehrke, S. H. ACS Macro Letters, (2013) 2,137.
85
Oral
O-37
Modelling Thermo-mechanical Aspects of Thermosetting Polymers and How
Monomer Composition Impacts Properties
Chris Lowe
Becker Industrial Coatings Ltd, Greate Britain
[email protected]
The most common coil coatings are based on polyester resins cross-linked with alkoxy melamines through
an acid catalysed trans-etherification reaction. The resulting thermoset coatings must be hard and formable
in order to meet the demanding conditions that they experience in service. Models of the crosslinked matrix in
which small groups of atoms are replaced by beads of particular properties using the Martini approach were
reported in the recent past. Mechanical behaviour of the matrices has also been attempted using the constitutive equations available for polymers. These two approaches will be brought together to consider how they
inform on the behaviour of polyester melamine based coatings over a range of temperatures.
86
Oral
O-38
Multilayer coil coating – placing properties
Per-Erik Sundell
SSAB EMEA, S-781 84 Borlänge, Sweden
[email protected]
Coil coating is a large-scale, continuous process where metal coils are uncoiled, cleaned, pretreated, coated
with one or two layers of paint on both sides, cured and then recoiled again. The major application is within
the exterior building industry as roofs, facades and rainwater management but other uses include automotive
and white goods indutries. Warranties up thirty years put extremely high demands on performance such as
scratch resistance and outdoor durability, i.e. color and gloss retention.
Enhanced properties of coil coated steel can be realized by the introduction of alternative curing technologies to make economical, multilayer coated products with functional nanostructured layers. Fully non-volatile
formulations, applied and cured in a few seconds allow for the enhancement of a manifold of desirable properties. Extreme hardness in combination with good flexibility, effective barriers towards aggressive environment, aesthetic appeal as well as almost any functional surface are plausible assets of future coil coatings.
Particularly, research efforts for developing exterior coatings that endures long wet times and extended periods of solar radiation as well as attractive and functional surfaces that break ways into new applications of
pre-coated steel has been and still are of high significance. All new functional surfaces and interphases as
well as processes are the result of environmental aspects being the most important driver for development.
The latest result of this development trend, are new coil coatings with improved performance that contain
considerable amounts of biorenewable material. This presentation will give some examples of enhanced that
can be achieved by placing properties in an industrial, multilayer coating process.
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O-39
Acrylate and Methacrylate Polymers and Coatings Derived from Terpenes
S.M. Howdle a, M. Fuentes Sainz a J.A. Souto a D. Regentová a D.J. Irvine b R.A. Stockman a
a
School of Chemistry and b Faculty of Engineering, Department of Chemical and Environmental
Engineering University of Nottingham, Nottingham UK NG7 2RD
[email protected]
The use of readily available and naturally occurring feedstocks to overcome our reliance upon petroleum derived materials is a growing challenge for our society. Terpenes are derived from waste (eg. d-limonene from
orange peel) and from wood waste (eg. the α- and β-pinenes) and are readily available on the multi-tonne
scale There have been significant efforts in the past to create polymers directly from terpenes but extensive
studies have to date yielded only low molecular weight, low Tg or cross-linked polymers, and very little opportunity to construct useful renewable materials.
We have developed a new route to create easily polymerisable terpene based acrylate and methacrylate
monomers applicable across a very broad range of terpenes.
Figure 1 –simple one step route to new monomers
Figure 2: new terpene polymers
O
O
HO
O
Catalysis
(1R)-(-)-β-pinene
O
HO
Catalysis
O
O
(1R)-(+)-limonene
These monomers can be polymerized by free radical and controlled/living routes to create new polymeric
materials with glass transition temperatures ranging from -18 to >140°C – giving access to a wide range of
mechanical properties[1].
We also describe the introduction of cross-linking leading to the formation of new renewable based powder
coatings.
[1]. A facile and green route to terpene derived acrylate and methacrylate monomers and simple free radical
polymerisation to yield new renewable polymers and coatings M. F. Sainz, J. A. Souto, D. Regentova, M.
K. G. Johansson, S. T. Timhagen, D. J. Irvine, P. Buijsen, C. E. Koning, R. A. Stockman and S. M. Howdle
2016,7, 2882-2887
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O-40
Magnetic Liquid Silicone Rubber
Dirk W. Schubert and Alexander Heitbrink
University Erlangen - Nürnberg, Institute of Polymer Materials
Martensstrasse 7, 91058 Erlangen, Germany
In electronics, magnetic materials play an important role in transformers, e.g. in high frequency applications
for impedance matching and balancing of antenna systems. Furthermore, this class of materials is in general
relevant for transport of energy, with respect to medical application the transcutaneous energy transport
from outside to inside the human body is a challenging task to charge pace pacers or other inside built in
supporting systems. Therefore, it is desirable to have rather flexible coil systems. Here we focus on liquid
silicone rubber (LSR) as matrix material.
To achieve a high permeability µr a high degree of filler is necessary while on the other hand a high degree
of filler would yield that the rubber turns into a solid rigid body. Also a high degree of filler would strongly
increase the viscosity of the LSR before crosslinking and thus limits the process ability.
Therefore it is the purpose of this work to reveal the viscosity and permeability of LSR filled by three different
magnetic fillers, respectively, as a function of the degree of filler in the composite. In particular, we suggest
a novel simple physical based model offering a fit function to describe the permeability as a function of the
degree of filler, having only one adjustable parameter.
Fig. : Permeability of LSR as a function of the degree of filler. Neosid F, Neosid G and Vitroperm are
different magnetic fillers.
References: Schubert, D.W.; Heitbrink A. in preparation
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O-41
Nonionic Double and Triple Network Hydrogels
Aslıhan Arğun, Oğuz Okay
Istanbul Technical University, Graduate School of Science, Engineering & Technology, Department of
Chemistry, 34469, Maslak, Istanbul, Turkey
Hydrogels are swollen polymeric networks which have the ability to absorb high amounts of water without
dissolving. Smartness, softness and high water uptake capacity endow hydrogels to be unique materials
for various areas. In spite all favorable properties, they usually exhibit brittle character which hinder their
applications under stress-bearing conditions. The poor mechanical performance of chemically cross-linked
hydrogels originates from their very low resistance to crack propagation due to the lack of an efficient energy
dissipation mechanism in the gel network. In recent years, a number of techniques for toughening of gels
have been proposed. Among others, double network (DN) hydrogels exhibit the highest and so far unsurpassed compression strength, toughness, and fracture energies [1,2]. This feature is gained to DN gels with
the help of its brittle first network (SN) component, which fractures under large strains to form clusters by
propagated macroscopic cracks inside the gel sample, while the second ductile component of network keep
clusters together [1-3]. However, in these pioneering researches, these mentioned outstanding mechanical
properties can only be obtained using a polyelectrolyte component which limits their widespread applications.
In the present study, we prepared nonionic DN and triple network (TN) hydrogels consisting of a chemically
cross-linked first network as the brittle component which maintains sacrificial bonds, and linear or/and crosslinked polymers as the second and third networks. Nonionic DN and TN hydrogels, synthesized by sequential polymerization reactions base on poly(N,N-dimethylacrylamide) (PDMA) and exhibit a high mechanical
strength. In order to increase the degree of inhomogeneity of first network, an oligomeric ethylene glycol dimethacrylate was used as a cross-linker instead of the classical cross-linker N,N′-methylenebis(acrylamide)
[3]
.
Herein, we unveil for the first time to our knowledge nonionic DN and TN hydrogels with outstanding mechanical properties. TN hydrogels containing 89−92% water sustain high compressive fracture stresses (up to 19
MPa) and exhibit a compressive modulus of up to 1.9 MPa. The concentration and the type of the first network cross-linker as well as the molar ratio of the second and third to the first network units have a significant
effect on the hydrogel properties.
References
[1] “Large Strain Hysteresis and Mullins Effect of Tough Double-Network Hydrogels” R.E. Webber, C. Creton,
Hugh R. Brown, J. P. Gong, Macromolecules, 40 (8), 2919-2927 (2007)
[2] “Super tough double network hydrogels and their application as biomaterials” Md. A. Haque, T. Kurokawa,
J. P. Gong, Polymer, 53, 1805-1822 (2012)
[3] “Non-ionic double and triple network hydrogels of high mechanical strength” A. Argun, V. Can, U. Altun, O.
Okay, Macromolecules, 47, 6430-6440 (2014)
90
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O-42
Self-assembled nanogels of chitosan
Philippova O.E. and Korchagina E.V.
Physics Department, Moscow State University, Moscow 119991, Russia
[email protected]
Nanogels formed as a result of aggregation of chitosan and hydrophobically modified (HM) chitosan macromolecules in dilute aqueous solutions were studied by light scattering and transmission electron microscopy (TEM). It was demonstrated that the size of nanogels and their aggregation numbers increase at the
introduction of hydrophobic side groups into polymer chains. The key result concerns the effect of the chain
length of individual macromolecules on the aggregation behavior. It was shown that both for unmodified and
HM chitosan the size of nanogels is independent of the length of single chains, which may result from the
electrostatic nature of the stabilization of their size. At the same time, the number of macromolecules in one
nanogel increases significantly with decreasing length of single chains in order to provide a sufficient amount
of associating groups to stabilize the nanogel. The analysis of the light scattering data together with TEM results suggests that the nanogels of chitosan and HM chitosan represent spherical particles with denser core
and looser shell covered with dangling chains.
Acknowledgment. The financial support of the Russian Foundation for Basic Research (project 14-03-00934а) is gratefully acknowledged.
91
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UCST-LCST double thermosensitive block copolymers
Sami Hietala, Lauri Mäkinen, Divya Varadharajan, Heikki Tenhu
Laboratory of Polymer Chemistry, Department of Chemistry, University of Helsinki
Thermoswitchable polymer aggregates were prepared from AB diblock and ABC triblock copolymers with different block lengths and block orders by reversible addition-fragmentation chain transfer (RAFT) polymerization.1 Polyethylene oxide macro-RAFT agent was used to polymerize either N-acryloylglycinamide (NAGA)
or N-isopropyl acrylamide (NIPAM) to diblock copolymers. These diblocks exhibited typical thermoresponsive
character of PNAGA (Upper Critical Solution Temperature, UCST, type of transition) and PNIPAM (Lower Critical Solution Temperature, LCST, type of transition) in aqueous solutions leading to formation of nanoscale
aggregates both at low and high temperature, respectively. Chain extension of these polymers lead to double
thermosensitive triblock copolymers that showed both UCST and LCST type of transition. The effect of the
length and order of the blocks (PEO-b-PNAGA-b-PNIPAM or PEO-b-PNIPAM-b-PNAGA) on the thermoresponsive properties as well as the size of the aggregates were studied.
Figure 1. Switchable aggregates of PEO-PNAGA-PNIPAM
References
1. L. Mäkinen, D. Varadharajan, H. Tenhu, S. Hietala Macromolecules, 49 (2016) 986-993.
92
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Ring shape formation of nanogel-crosslinked matrials by using
non-equilibrium process
Sada-atsu Mukai,1,2 Tatsuya Fujimoto,1 Shin-ichi Sawada,1,2 Yoshihiro Sasaki,1 and Kazunari Akiyoshi1,2
Graduate School of Engineering Kyoto University, Kyotodaigaku-katsura, Nishikyo-ku, Kyoto 615-8530, Japan: 2JST ERATO.
1
A dissipative structure formation under non-equilibrium process has been attracted attention as a method
for preparing materials with micro- or nano-scale organized structure. In this study, we focused on wellknown coffee-ring phenomena; ring-like deposit formation on drying colloid dispersions. We intended to
accumulate photo-reacting polysaccharide nanogels and to form a ring-like structure of nanogels. Nanogels
are hydrogel particles in size of nanometer scale with three-dimensional networks of cross-linked polymer
chains. They have attracted a great deal of interest over a decade due to their application potential in biomedical fields, such as drug delivery systems, and tissue engineering. Recently, we proposed a new methodology for preparation of hierarchical-structured gel materials using polymerizable nanogels as building
blocks, which we call “nanogel tectonics”.1-4 Here, we report a new type of ring-shaped nanogel-crosslinked
(NanoClik) materials composed of cholesterol-bearing pullulan (CHP) nanogels with reactive moieties by
using non-equilibrium process.
Fig.1 (a) Schematic illustration of coffee ring formation in Nanogel crosslinking system, (b) fluorescent image of the obtained ring-like NanoClik material.
Ten µl of the CHP pregel solution (20 mg/ml) with photo-initiator was dropped on the substrate. Chemical
crosslinking reaction between self-assembled nanogels was occurred under UV light radiation in parallel
with solvent evaporation. We evaluated structural characteristics of the obtained gels by fluorescent microscopy, and 3D laser scanning microscopy. The observations revealed that nanogels were mainly distributed
in circumference of a circle, and the film had center-concave surface (Fig.1).
[1] Y. Sasaki et. al., The Chem. Record, 10, 366 (2010). [2] Y. Hashimoto et. al., Biomaterials, 37, 107 (2015).
[3] Y. Tahara et. al., Adv. Mat., 27, 5080 (2015). [4] Y. Hashimoto et. al., ASC Biomaterials., in press.
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Temperature tuning of hybrid nanogels surfaces
Gaio Paradossi, Fabio Domenici, Barbara Cerroni, Letizia Oddo, Mark Tellingç, Sarah Rogersç, Anca
Mateescu, Sharad Pasale, Ahmed Bakry§
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor Vergata, Via della
Ricerca Scientifica 1, 00133 Rome, Italy.
ç
ISIS Facility, STFC, Rutherford Appleton Laboratory, Chilton, OX11 OQX, UK
§
Department of Chemistry, Faculty of Science, Helwan University, Cairo, Egypt
In the design of a thermoresponsive polymer hydrogel, the poly(N-isopropylacrylamide) (p(NiPAAm)), moiety
is often included. Its lower critical solubility temperature (LCST) displayed in water is close to the physiological
temperature and is used to obtain a “smart” structural responsivity, consisting in the hydrogel shrinking
[1]. However, in a hybrid network, the presence of other components is equally important in determining
the overall hydrogel behaviour. In this respect, hyaluronic acid (HA) has recently gained considerable
attention as co-participant with p(NiPAAm), to assemble a novel type of hybrid nanogels showing intriguing
thermoresponsive features. HA is known to be stable, biodegradable, and able to interact preferentially
with tumour cells overexpressing integrins, thus adding a huge therapeutic value to the construct. In this
framework, we recently realized nanosized, chemically cross-linked, HA-p(NiPAAm) hydrogel particles, in
which HA is derivatized with azyde-bearing side chains and “clicked” with a telechelic p(NiPAAm) synthetized
by reversible addition-fragmentation chain transfer, RAFT, and bearing terminal alkyne groups [2].
In this contribution, we highlight the peculiar temperature behaviour of the HA-p(NiPAAm) hybrid nanohydrogels in connection to their biomedical relevance. Photon correlation and z-potential spectroscopies
show that at 25°C the nanogel particles have a size of ~150 nm. Around a temperature of 33 °C, in the place
of the expected shrinking, a change of the surface properties of the hybrid HA-pNiPAAm nanogel particles
occurs. In particular, we observe a dramatic change of the zeta-potential of the water-hydrogel particles,
suggesting a prevalence of HA at the surface and a transfer of p(NiPAAm) in the core of the nanogel particles.
This process was monitored by small angle neutron scattering (SANS) and atomic force microscopy (AFM)
to corroborate such hypothesis and to give a further detailed description of the process at the nanoparticle
interface. We found that that below LCST the particles surface is biphasic and patchy (Fig. 1), probably
reflecting a limited compatibility between the two polymer components. Approaching the temperature of 33°C,
the particles form clusters, which break apart once they reach physiological temperature, where they exhibit
a smoothest surface of almost only HA. Moreover, we demonstrated that such a reorganizational process of
the nanogel surface has remarkable fallout in terms of selective targeting of anticancer drugs in tumour cells.
In particular, the delivery of doxorubicin drug via the HA/p(NiPAAm) nanogel particles reduced by 50% the
viability of HT 29 tumour cells with respect to healthy fibroblasts NIH3T3.
Fig. 1. Tapping mode AFM topography (left side) and phase images of HA-pNiPAAm nanogels laid on a flat
silicon surface in water condition.
References
[1] Hamner, K. L.; Alexander, C. M.; Coopersmith, K.; Reishofer, D.; Provenza, C.; Maye, M. M. ACS Nano
2013, 7, 7011. [2] Cerroni B.; Pasale S. K.; Mateescu A.; Domenici F.; Oddo L.; Bordi F.; Paradossi G.
Biomacromolecules 2015, 16, 1753.
94
O-46
Oral
Structure-property relations for equilibrium swelling of cationic
polyelectrolyte hydrogels
A.D. Drozdov and J. deClaville Christiansen
Department of Mechanical and Manufacturing Engineering, Aalborg University, Denmark
Governing equations are developed for equilibrium swelling of a cationic gel in aqueous solutions with various pH and molar fractions of a monovalent salt [1,2]. The novelty of the model consists in the account for
(i) self-ionization of water molecules, (ii) formation of ion pairs between fixed cations and mobile anions, and
(iii) changes in conformation of chains driven by repulsive interactions of bound charges. The model involves
six material constants with transparent physical meaning that are determined by fitting swelling diagrams on
several homo- and copolymer gels. Two types of water uptake tests are studied: when gels are swollen in
water baths with various pH, and when they are swollen in aqueous solutions of salt with pH=7 and various
molar fractions of salt θ. To confirm validity of the model, adjustable parameters are determined by matching
observations in one type of tests, and its predictions are compared with experimental data in the other type
of experiments. To develop structure-property relations, equilibrium swelling is analyzed of cationic gels with
various mass fractions of monomers in pre-gel solutions ρm, molar fractions of ionic monomers ρi, and molar
fractions of cross-linker ρc. Good agreement is demonstrated between observations and results of simulation
when only two adjustable parameters are affected by ρm and ρi and three parameters evolve with ρc. Phenomenological relations are suggested for the effect of total volume fraction of monomers in a pre-gel solution,
molar fraction of ionic monomers, and molar fraction of cross-linker on material parameters. An advantage
of these relations is that they allow equilibrium degree of swelling to be predicted for cationic gels with given
compositions.
Financial support by the Danish Innovation Fund (project 5152-00002B) is gratefully acknowledged.
References:
1. A.D. Drozdov, C.-G. Sanporean, J. deC. Christiansen, Mater. Today Comm. 6 (2016) 92-101.
2. A.D. Drozdov, J. deC. Christiansen, Eur. Polym. J. 79 (2016) 23-35.
95
Oral
O-47
Nucleophilic Polymers. Formation of hydrogels, particles and scavenging of
inflammatory mediators.
Tim Bowden,
Polymer Chemistry, Department of Chemistry Ångström Laboratory, Uppsala, Sweden.
[email protected]
An essential part of organic synthesis describes the making of chemical bonds through the reaction of nucleophiles and a complementary electrophile. When multiple nucleophilic groups are present in a polymer it
creates a reactive functional material. This reactivity can be used in different ways; the nucleophile can be reacted with low molecular electrophiles to modulate the polymer properties; or be reacted with an electrophilic
polymer to produce a network material; or used as a scavenger where unwanted electrophiles are present
e.g. in a reaction mixture, a physiological fluid or in a tissue under oxidative stress.
This paper presents synthetic strategies for the selective introduction of nucleophiles to polymers, i.e. introduction of hydrazine derivatives to polyhydroxy-polymers. Examples where nucleophilic polymers are use for
the making of hydrogels applicable in regenerative medicine or functionalised in such a way that nanoparticles are formed will be presented. Finally, it will be explained how nucleophilic polymers can attenuate inflammatory reactions though the scavenging of electrophilic reactive components present in vivo as a result
of oxidative stress.
96
O-48
Oral
Next-Generation Matrix-Free Graphene Composites with Tuneable Orientation
and Shape-Memory Effect
M. Wåhlander,1* F. Nilsson1, A. Carlmark1, Ulf W. Gedde1 S. Edmondson2, E. Malmström1
1
KTH Royal Institute of Technology, Department of Fibre and Polymer Technology, Stockholm,
Sweden; 2University of Manchester, School of Materials, Oxford Road, Manchester, UK;
The extraordinary properties of graphene have made graphene-based fillers extremely popular for composites.1 In this work, we demonstrate a novel route to synthesize next-generation graphene composites without
the need of polymeric matrices. Graphene oxide (GO) sheets were grafted by Surface-Initiated Atomic Transfer Radical Precipitation Polymerisation (SIARGET ATRPP) forming hydrophobic matrix-free composites
with GO in isotropic state. The SI-ARGET ATRPP was performed from a synthesised cationic macroinitiator
immobilized on anionic GO. Matrix-free GO-composites were melt-processed directly from the grafted GO,
which aligned during the melt-processing. After processing, birefringence was observed, attributed to nematic states. The matrix-free GO-composites demonstrated enhanced thermo-mechanical properties, promising
membrane effects and thermo-responsive shape-memory effect. Further, permeability models were developed, which predicted the isotropic or nematic states of GO from oxygen-permeability data. These GO-composites are promising candidates for a range of applications, such as selective membranes and sensors.2, 3
Figure 1: A) Illustrations of the grafts on the macroinitiator decorated GOs in organic solvents. B)
Flexible isotropic matrix-free GO-composites. C) Nematic modified GOs observed between crossed polarizers as a single giant Maltese-cross covering the entire film (3.4 cm across).
References:
1.
A. C. Ferrari, F. Bonaccorso, et al., (2015) Nanoscale, 7, 4598-4810.
2.
J. Yang, C. Liu, et al., (2015) RSC Adv., 5, 101049-101054.
3.
M. Zhang, Y. Li, et al., (2015) Polym. Chem., 6, 6107-6124.
97
Oral
O-49
Early Stage Kinetics and structure of Polyelectrolyte Complexes Studied by
Stopped-Flow and Neutron scattering
X. Liu,a M. Haddoua, J. Giermanska, C. Puccia, Ch. Schatzb, J.P Chapel a
a
b
Centre de Recherche Paul Pascal CNRS- Bordeaux University, Pessac, France
Chimie des Polymères Organiques, ENSCBP - Bordeaux University, Pessac, France
[email protected]
Polyelectrolyte complexes (PECs) are the association complexes formed between oppositely charged macromolecules. A large body of work has been devoted to the preparation, morphology characterizations and
performances of PECs. Much less attention was paid on the microscopic structures and formation kinetics of
such strongly interacting systems, which often occurs under non-equilibrium conditions due to the relatively
low mobility of macromolecular chains and the possibility of multivalent interactions. The Stopped-flow very
fast mixing technique (~ms) combined with neutron scattering was used to probe the structure and early
stage assembly kinetics in the poly(acrylic acid) (PAA) poly(diallyldimethylammonium chloride) (PDADMACk)
system. We have shown that PEs complexation is indeed a very fast process (~10 ms) through three distinct
reorganization/complexation stages under different out-of-equilibrium conditions as a function of PEs molar
charge ratio z-/+. Furthermore, an experimental phase diagrams (z, Mw, κ-1) = fct (morphology & kinetics) was
developed in line with theoretical considerations. Finally no pathway dependence was observed when PEs
are assembled under SF conditions.
In term of local structure, Small-Angle Neutron scattering experiments have shown that for low charge ratio
(z<0.8), the structure reminds of pure PDADMAC chains whereas at larger Z, polydisperse spherical particles
with sharp interface can be evidenced according to the Porod analysis (I(q)q4). Interestingly, the pure complex coacervate phase obtained at stoichiometry (Z~1) shows a mesh size ζ smaller than the PDADMAC Rg
indicating that the polymer chains are indeed overlapping (φ>φ*) with the presence of an astonishing nematic
correlation peak seen at very high q.
Light Scattering @90°
(onic strength)
PAA
PDADMAC
(charge ratio Z)
98
Posters
99
P-1
Poster
New Metal Ion Recovery Method Using Protanated Hydrogel
PNG2016
Takehiko Gotoh, Daiki Nakata, Asuka Ogawa and Takashi Iizawa
Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University
1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, Japan
1. Introduction
Many industrial wastewaters such as electroplating factory effluents contain heavy metals ions, which
are required to be removed, as they are harmful to living things. On the other hand, they sometimes contain
very useful metal ions worth recovering. The coagulation and adsorption methods have been used to remove
the heavy metals from wastewater. However, the coagulation method has some difficulties in the solidliquid separation. The adsorption method needs strong acid to desorb the metal ions from the adsorbent for
recovery. The acidic solution then becomes the secondary waste. Therefore, a simple metal ion recovery
method with low waste was required.
The hydrogel with tertiary amino group is protonated in water and release hydroxyl ion that is retained in
the gel by ion interactions. When the gel is immersed in aqueous solution of metal ion, the metal ions diffuse
into the hydrogel then react with the hydroxyl ions in the gel to make metal hydroxides. The hydrogel within
metal hydroxides is separated and recovered from the solution easily.　In this study, a simple metal ion recovery method using a hydrogel with tertiary amino group was proposed
and the recovery characteristics of the hydrogel were investigated.
2. Materials and methods
The hydrogel was prepared from N-[3-(dimethylamino)propyl]acrylamide (DMAPAA) with N,N’methylenebis(acrylamide) as a cross-linker. The monomer and the cross-linker aqueous solution was mixed
with an initiator aqueous solution, and then poured into Teflon tubes of 6 mm inner diameter. The radical
polymerization was performed at 10°C under nitrogen atmosphere. After the polymerization, the gels were
cut into pieces with the length of 6 mm then washed with methanol and dried at 50°C. The dried gels were
mixed with an aqueous solution of nickel nitrate. The solutions were shaken with the gel in a water bath at
25°C for 24 hours. Then, the concentration of nickel ion was measured. Recovery ratio was calculated from
the difference in the concentrations before and after the recovery.
3. Results and discussion
Fig. 1 shows the effect of the gel dosage on recovery ratio of nickel ions 24 hours after the gel was added
to the Ni(NO3)2 solution. The recovery ratio increased with an increase of the gel dosage when the initial
concentration of the nickel ion was 100 ppm. However, the recovery ratio did not increase well when the initial
concentration was 10 ppm. It is suggested that low initial concentration resulted in the decrease of transport
rate of the nickel ions into the gel. Fig. 2 shows the change in recovery ratio of nickel ions with time when the
initial concentration was 10 ppm. It is found that the hydrogel successfully recovered 85 % of the nickel ions
after 72 hours. The recovery ratio of the nickel ion can be improved by the longer immersion time.
4. Conclusion
New metal ion recovery method using hydrogel was proposed. The gel could recover the metal ions in a
wide concentration range. The recovery ratio depends on the metal ion concentration and could be improved
by the gel dosage and immersion time.
100
Poster
P-2
An improved one-particle microrheometer by a combination of magnetic
tweezers and total internal reflection microscope in living cells
LIU, Wei
225B, Science Center, North Block, The Chinese University of Hong Kong,
Shatin, New Territories, Hong Kong, China
Rheology properties play important roles through the whole life of a cell. In our previous design of a magnetic tweezer (MT) based microrheometer, a maximum force with several pN limits the achievable modulus in the range of 1-100 Pa, much smaller than the modulus of common biological systems such as cells
(100~10,000 Pa). Therefore, we propose here several improvements on the performance of such an active
microrheometer which incorporating a MT to Total Internal Reflection Microscope (TIRM), aiming at precise
rheological measurements of living cells. Firstly, to generate a stronger force for cell microrheology, we
design a new setup of magnetic poles with a much closer distance between poles and samples. In this new
setup, probe particles under the evanescent wave illumination were activated by a well-modulated sinusoidal magnetic force and oscillated in a small amplitude vertically to a solid/liquid interface. Furthermore,
employing a lock-in amplifier and a logarithmic operation circuit, an additional phase delay induced by the
electromagnetic solenoids was confirmed and removed. Thus the frequency-dependent delay time between
the displacement of the probe particle and the force can be resolved, and leads to precise measurements
of the local viscous and elastic modulus.
1. X. J. Gong, L. Hua, C. Wu and T. Ngai, Rev. Sci. Instrum. 84, 033702 (2013);
2. Y. Wang and G. Zocchi, Phys. Rev. Lett. 105, 238104 (2010).
101
Poster
P-3
Design of Drug-Loaded Polypeptide Hydrogels via Molecular Imprinting and
Their Controlled Release by Helix-Coil Transition
K. Matsumoto1, Y. Ito1, A. Kawamura1, 2, T. Miyata1, 2
1
Stimuli-responsive hydrogels have recently received much attention as smart biomaterials for diagnosis, drug
delivery systems and cell cultures because they exhibit reversible swelling/shrinking properties in response
to external stimuli such as pH and temperature. We proposed a novel strategy for preparing biologically stimuli-responsive hydrogels that undergo changes in the volume in response to a target biomolecule, which uses
biomolecular complexes as dynamic crosslinks in hydrogel networks1-3). Resveratrol (RSV) that is successful
agents currently in use for the chemotherapy of cancer forms a complex with two molecules of cyclodextrin
(CD). For constructing self-regulated RSV release systems, CDs as ligands for RSV were introduced into
poly(L-lysine) (PLL) that undergoes a structural change in response to a pH change. By chemical crosslinking
of the resulting CD-modified PLL (CD-PLL) after its complex formation
pH 7
pH 12
with bisphenol A (BPA) that forms a complex with two CDs similarly to
RSV, BPA as a model drug of RSV was loaded within CD-PLL hydrogel networks. Release of BPA from the hydrogels was investigated by
conformational change of PLL chains in response to a change in pH.
CH3
HO
C
OH
CH3
H
HO
O
H3
C
C
C
H3
CH3
C
CH3
O
H
OH
CH3
HO
OH
C
CH3
BPA-loaded
CD-PLL gel
Drug release
by structural change
α-Helix
100
80
30
60
40
20
20
10
6
7
8
9
10
pH
11
12
0
13
Fig. 1. . Effect of pH on the amount of BPA
released from BPA-loaded CD-PLL hydrogel (●)
and α-helix content of BPA-imprinted CD-PLL
hydrogel (○).
References
1) Miyata, T. Polym. J. 2010, 42, 277.
2) Miyata, T.; Jige, M.; Nakaminami, T.; Uragami, T. Proc. Natl. Acad. Sci. USA 2006, 103, 1190.
102
Relative α-helix content [%]
Random coil
40
Released BPA [%]
CD-PLL was synthesized by reaction of PLL with carboxy group-introduced CD as a ligand for BPA. BPA-loaded CD-PLL hydrogels
were prepared by crosslinking of the resultant CD-PLL with poly(ethylene glycol) diglycidyl ether in the presence of template BPA at pH
7, at which PLL forms a random coil structure. After the swelling of
BPA-loaded CD-PLL hydrogel attained equilibrium in a buffer solution at pH 7, the BPA release behavior was investigated in a buffer
solution with various pH (Fig. 1). In a buffer solution at neutral pH,
the release of BPA from the BPA-loaded CD-PLL hydrogel was suppressed due to the formation of stable CD-BPA-CD complexes. At
basic conditions above pH 11, however, BPA was effectively released
from the BPA-loaded CD-PLL hydrogel. The BPA release above pH
11 was attributed to lowering stability of CD-BPA-CD complexes by
structural transition of PLL chains. In conclusion, the release of BPA
from BPA-loaded CD-PLL hydrogel can be regulated by pH because
a pH change induced structural change of its network with recognition
sites.
P-4
Poster
Carbon composites based on liquid crystalline epoxy resin
Beata Mossety-Leszczak1, Henryk Galina1, Natalia Puczkowska1, Piotr Szałański1, Urszula Szeluga2,
Magdalena Włodarska3
1
2
3
Faculty of Chemistry, Rzeszów University of Technology, Al. Powstańców W-wy 6, 35-959 Rzeszów,
Poland, e-mail: [email protected]
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, Sowińskiego 5, 44-121 Gliwice,
Poland
Faculty of Technical Physics, Information Technology and Applied Mathematics, Institute of Physics, Łódź
University of Technology, Wólczańska 219, 90-924 Łódź, Poland
The need for new materials with specific properties affects the research and development of new composites. Liquid crystalline epoxy thermosets (LCE) have many desirable characteristics, including good dielectric
and mechanical properties in the direction of mesogen orientation, low coefficient of thermal expansion and
good dimensional stability, increased fracture toughness and very good barrier properties. Therefore, LCE
are suitable for being used as matrices of advanced composites and can be applied into high performance
devices [1,2].
The attractive properties of liquid crystalline thermosets are provided when the mesomorphic phase structure
can be retained as well as its orientation throughout the cure process. The LCE’s morphology and degree of
order are strictly related to curing conditions. Depending on the cure temperature liquid crystalline precursors
can form an isotropic or liquid crystalline phase structure, monodomain or polydomain morphology. LCE’s
cured in the absence a force field typically display polydomain liquid crystalline properties. Thermosets with
oriented monodomain structure are of great interest due to their high anisotropic mechanical and optical
properties. A magnetic or electric field, or even glass test cell containing a substrate with a special surface
pattern can be employed to induce the macroscopic alignment of mesogenic molecules of liquid-crystalline
precursors. The macroscopic orientation of liquid crystalline epoxies was also reported as being spontaneously induced by cure on a carbon fiber surface [3,4] and multi-walled carbon nanotubes [5].
In our work, we synthesized composites in which the matrix was the liquid crystalline epoxy resin containing a
triaromatic mesogenic group. It was cured by 4,4’-diaminodiphenylmethane. The anthracite thermally treated
at 2000°C to a graphite-like structure was used as a filler. The samples were oriented by applying an external
magnetic field during their cure. The result on morphology and thermomechanical properties of the resulting
samples was analyzed by the DSC, DMA, X-ray analysis: WAXS and SAXS.
References:
[1] Carfagan C., Amendola E., Giamberini M., Prog. Polym. Sci., 1997, 22, 1607.
[2] Douglas E.P., J. Macromol. Sci. Part C: Polym. Rev., 2006, 46, 127.
[3] Lee J.Y., Jang J., Polym. Bull., 2007, 59, 261.
[4] Guo H., Lu M., Liang L., Zheng J., Zhang Y., Li Y., Li Z., Yang Ch., J. Appl. Polym. Sci., 2014, 131(online
article 40363:1-9).
[5] Hsu S.-H., Wu M.-C., Chen S., Chuang C.-M., Lin S.-H., Su W.-F., Carbon, 2012, 50, 896.
103
Poster
P-5
Formation of the hydrophobic thermosetting polyurethane powder
clear coatings
Beata Mossety-Leszczak, Barbara Pilch-Pitera, Łukasz Byczyński
Faculty of Chemistry, Rzeszów University of Technology, Al. Powstańców W-wy 6, 35-959 Rzeszów,
Poland,
In recent years significant progress has been achieved in the technologies of thermosetting powder coatings production and application. This is a result of the excellent chemical and mechanical properties of powdercoatings and the long-term protection provided by them in comparison to the analogous thermoplastic
powder systems [1]. During the curing process, the thermosetting systems melt and the resin reacts with a
cross-linker forming a polymer network. Because the curing reaction is irreversible, the obtained product is
no melting and insoluble. Thermoplastic products melt and flow at a higher temperature, yet it has the same
chemical composition and structure when it solidifies after being cooled down. No chemical reactions occur
in thermoplastic products, and for this reason they have a poor solvent resistance.
In this work we would like to report a convenient way of preparing hydrophobic thermosetting polyurethane
powder clear coating systems. This way cover the synthesis of polysiloxane modified blocked polyisocyanate, which was used as a crosslinking agent for preparing of powder clear coating systems. The linear
organopolysiloxanes having at both ends hydroxyalkyl and hydroxyalkoxy groups or terminated at one end
with two hydroxyl groups we used to modify of polyisocyanates. The hydroxyl groups of the modifier were
reacted with the isocyanate groups of the polyisocyanate and were incorporated into its structure. FT-IR and
NMR spectra as well as GPC analysis allowed for confirming the expected structure of such polyisocyanates
and made it possible to rule out the presence of by-products: uretdione and isocyanurate. Polyurethane
powder compositions contained polyisocyanate modified by means of polysiloxane characterized with lower
viscosity at 120°C, which facilitated extrusion process. The better levelling of modified powder composition
was the cause of the reducing the orange peel on the coating. Polyurethane powder coatings cross-linked
using polyisocyanates with built-in polysiloxane, resulted in improved surface properties: lower surface free
energy values and higher contact angles as well as higher scratch, abrasion and organic solvents resistance.
With increase in the polysiloxane content in the coating adhesion to steel and gloss decreased. The coating
containing 1-3wt.% of polysiloxane showed improvement in all measured parameters. This phenomenon can
be explained by migration of polysiloxane to the coating surface [2]. Increase of polysiloxane content in the
coating, due to lower compatibility with polyurethane matrix, adversely impacts the properties of coating.
This work was supported by the Polish National Science Centre (NSC) under grant no. N N507 503338 and
by the Polish National Centre for Research and Development (NCRD) under grant no. TANGO1/268877/
NCBR/2015.
References:
[1] Spyrou E., Powder coatings chemistry and technology, Vincentz Network Gmbh., Hannover, 2012.
[2] Pilch-Pitera B., Prog. Org. Coat., 2014, 77, 1653.
104
Poster
P-6
Nanohybrid Injectable Gels Composed of Polymer Micelles, Clay Nanodisk, and
Doxorubicin for Efficient Focal Tumor Treatment
Koji Nagahama, Daichi Kawano and Naho Oyama
Department of Nanobiochemistry, Frontiers of Innovative Research in Science and Technology (FIRST),
Konan University, 7-1-20 Minatojima-minamimachi, Chuo-ku, Kobe 650-0047, Japan.
Among the various antitumor drugs used clinically, doxorubicin (DOX) is one of the most common chemotherapy drugs in the treatment of a wide range of cancers. We recently developed a nanocomposite injectable gel
made through hierarchical self-assembly of biodegradable poly(DL-lactide-co-glycolide)-b-poly(ethylene glycol)-b-poly(DL-lactide-co-glycolide) (PLGA-PEG-PLGA, Figure 1a) copolymer micelles and clay nanodisks
(CNDs).1 The nanocomposite injectable gel exhibits unique molecular adsorption property which is originated from the ability of CNDs to adsorb various kinds of molecules including DOX, amoxicillin, proteins, and
DNA. Based on this, we hypothesized that the composite gels have a potential as focal DOX delivery carriers
enabling DOX slow release due to the stable interactions of DOX and the CNDs. The purpose of this
study is to develop a safe and effective DOX-delivery
system using the nanocomposite injectable gels.
Herein, we prepared a biodegradable nanohybrid
injectable gels consisting of PLGA-PEG-PLGA copolymer micelles, CNDs, and DOX through self-assembly of these components.2 It was found that the
DOX molecules loaded in the hybrid gels was incorporated into the gel networks as cross-linking points
Figure 1. a) Structures of PLGA-PEG-PLGA. b) Schematto facilitate the formation of gel networks (Figure 1b).
ic illustration of hydrogel networks of PLGA-PEG-PLGA
Note that, long-term sustained release of DOX from copolymer gel, PLGA-PEG-PLGA/CND gel, and PLhybrid injectable gels without initial burst release was GA-PEG-PLGA/CND/DOX hybrid gel.
achieved. Interestingly, the release rate of DOX was
decreased with increasing of DOX content, i.e., the DOX incorporated into gel networks controlled its own
release rate by varying the cross-linking density. Thus, the hybrid injectable gel is a self-controlled DOX release system. A single injection of PLGA-PEG-PLGA/CND/DOX hybrid gel to tumor-bearing mice provides
long-term sustained antitumor activity, suggesting the potential utility as local DOX-delivery platform for cancer focal therapy.
REFERENCES
[1] Oyama, N.; Minami, H.; Kawano, D.; Miyazaki, M.; Maeda, T.; Toma, K.; Hotta, A.; Nagahama,
K. Biomater. Sci. (2014) 2, 1057.
[2] Nagahama, K.; Kawano, D.; Oyama, N.; Takemoto, A.; Kumano, T.; Kawakami J. Biomacromolecules (2015) 16, 880.
105
Poster
P-7
Adsorption and desorption properties of acrylate-acrylic acid gel
for VOC observed by QCM-A
Yoshimi Seida and Takahiro Suzuki
Toyo Univ., Nat. Sci. Lab. 5-28-20 Hakusan, Bunkyo-ku, Tokyo 112-8606 Japan
[email protected]
Reduction of VOC emission is important to reduce air pollution and global warming in the world. Activated
carbon, zeolite and hydrophobic polymer are the major adsorbents used in the practical separation and
recovery of VOC. High temperature heat treatment, high vacuum treatment and solvent leaching are used
in desorption and recovery of VOC from the adsorbents in conventional methods. The desorption process
is energy consuming heating process so that development of cost effective and simple recovery method of
VOC is one of the attractive and important engineering subjects. Temperature responsive adsorbent with
adsorption-desorption function of organic substances has been developed in the case of hydrogels through
molecular design using amphiphilic main-monomer and co-monomers with various hydrophobicity that is different from the main monomer [1]. The design concept of hydrogel adsorbent with desorption function in its
physical property was applied to the development of organogel adsorbent for VOC. Organogels are known to
absorb various organic solvents depending on their chemical structure. Stearyl acrylate (SA) based copolymer ogranogels were synthesized in various solvents system in this study. The adsorption–desorption properties for VOC gas was investigated as a function of the monomer composition, solvent in their preparation
stage and environmental temperature using quartz crystal microbalance (QCM). Characteristic absorption
behaviors of the gels for various VOC were observed depending
on the monomer composition of the gels. The SA gels prepared in
this study absorbed 14 times large volume of toluene and 8 times
larger volume of hexane but did not absorb water and ethanol.
Decrease of absorption amount of toluene and hexane with the
increase of hydrophilic monomer (acrylic acid; AA) was observed.
Fig.1 indicates the response of the QCM coated with the SA/AA
gel in contact with toluene gas (10000ppm). The bare QCM did
not show obvious response of the resonance frequency fs (mass
effect index) and the resonance resistance R (viscosity index).
On the contrary, the QCM coated with the SA/AA gel revealed
the drastic large decrease of the fs and the large increase of R
in the toluene atmosphere. The fs and the R attained stable values respectively due to relaxation of the gel [2]. The temperature Fig. 1 Time courses of the fs and the R in the QCM
coated with the organogel in contact with toluene
dependence of the QCM response was studied to evaluate the gas
potential of the organogel for the recovery of VOC.
References:
[1] Seida, Y., in “Science and Technology Handbook of Gels”, NTS Inc., Tokyo, 292(2014)
[2] Seida, Y. Proc. 25th MRSJ Annual Meeting, 2015,CD-ROM(2015)
106
Poster
P-8
Synthesis of grafted pH and thermo responsive hydrogels via ring opening
polymerization of polyethyleneoxide bis(glycidyl ether) with
monoamino/diamino Jeffamine
Ahmet ERDEM, Fahanwi Asabuwa Ngwabebhoh, Ufuk YILDIZ
Department of Chemistry, Faculty of Science, Kocaeli University, Umuttepe Yerleşkesi 41380-Kocaeli.
Turkey
e-mail, [email protected]
Recent interest in stimuli-sensitive hydrogels has promoted numerous efforts in designing and developing
intelligent hydrogels which have various potential applications in biomedical field and controlled drug delivery system. Temperature and pH stimulus are the most common physical and chemical parameters used in
biotechnological and biomedical applications, respectively. One of the very important factors of this class of
hydrogels is their response rate to applied stimuli. Thus different methods have been developed and evaluated to increase the response rate. Grafting technique has been determined as the alternative simplest method
to increase the response rate of hydrogels to stimuli[1].
Dual thermo and pH responsive comb type grafted hydrogels which were comprised of mono amino terminated polyoxypropylene (Jeffamine M2005) in grafted chain, polyoxyethylene bis(glycidyl ether) (Mn:500 g/mol)
in backbone were succesfully synthesized through ring opening polymerization reactions in the presence
of diamino terminated polyoxypropylene-b-polyoxyethlene-b-polyoxyethlene triblock copolymer (Jeffamine ED 600) as a crosslinker [2]. Grafted hydrogels show faster response change due to rapid hydrophobic
aggregation of free mobile polyoxypropylene unit. In this study, hydrogels of varying grafting composition
were synthesized based on amino/epoxy ratio and modified crosslinker ratios in the range of 40-60 %. The
obtained synthesized hydrogels were then characterized by DSC, TGA and FTIR. The swelling properties of
the hydrogels were investigated for varying pH and temperature.
References:
[1]
Y. Kaneko, S. Nakamura, K. Sakai, A. Kikuchi, T. Aoyagi, Y. Sakurai, T. Okano, Polymer Gels and
Networks 6 (1998) 333.
[2]
I. Krakovský, J.C. Cayuela, R.S. i Serra, M. Salmerón-Sánchez, J.M. Dodda, European Polymer
Journal 55 (2014) 144.
107
Poster
P-9
3D hydrogel scaffold combined with piezoelectric nanorods grown on
fabric fibers
Ki-Hwan Hwang1, Daseul Jang2, Yongmin Lee1, Eunjung Choi1, Kwangwook Hong3, Jae Eun Heo2,
Bongseup Shim2, Changsik Song1, Sang H. Yun4,*
1
Department of Chemistry, Sungkyunkwan University, 16419 Suwon
Republic of Korea
2
Department of Chemical Engineering, Inha University, 22212 Incheon
Republic of Korea
3
Department of Mechanical Engineering, Inha University, 22212 Incheon
Republic of Korea
4
PACE Center, Inha University, 22212 Incheon
Republic of Korea
Abstract
One of the key aspects in tissue engineering is the scaffold. It provides a structurally relevant 3D environment that defines the shape of tissue and allows cells to adhere. Cells can behave differently in 2D and 3D
systems. As such, there has been increasing agreement that 3D matrices provide better model systems for
physiologic situations such as enhanced cell-cell contact or communications. Thus, the design and fabrication of well-defined 3D scaffold should be developed for studying the effects of 3D culture on cell behavior.
The number of parameters for controlling adhesion, growth and differentiation of cells is important in guiding
cell behavior, including geometry, size, lateral spacing and surface chemistry. In particular, it has been reported that the cell behaviors can be tuned by applying mechanical force or electrical stimuli.
To control cell behaviors we used piezoelectric ZnO nanorod array as a source of self-powered mechanical
and electrical energy. The nanorod arrays grown on fabric fibers were imbedded into 3D polyvinyl acetate–
graphene oxide (PVA-GO) hydrogel.
108
Poster
P-10
Ice adhesion affected by counterion exchange on core/shell microgels
Ki-Hwan Hwang1, Imre Varge2, Per M. Claesson3, Sang H. Yun4,*
1
Department of Chemistry, Sungkyunkwan University, 16419 Suwon, Republic of Korea
2
3
Institute of Chemistry, ELTE, Budapest, Hunngary
Surface and Corrosion Chemistry, KTH, 10044 Stockholm, Sweden
4
PACE Center, Inha University, 22212 Incheon, Republic of Korea
Abstract
Icing on various structures is a serious and significant problem posing safety issues and system operation
problems. An ideal solution would be to prevent ice from accumulating and to reduce ice adhesion. We proposed that ice adhesion can be controlled by counterion exchange on polyelectrolyte polymers. For the purpose we prepared core/shell microgels as follows: The surface of the silicon wafers were modified using the
layer-by-layer technique. First a thin layer of polyethylene imine (PEI) was adsorbed on the surface then core/
shell microgel particles were deposited as the top layer. The core/shell microgels had a crosslinked pNIPAm
core and a 100% poly(sodium acrylate) shell. As a final step the sodium counterions of the polyacrylate shells
were exchanged for lithium, potassium, rubidium and cesium by immersing the microgel covered surfaces
into a dilute alkali metal chloride solutions. Then, the correlation of ice adhesion and the synthesized microgels with counterion exchange was investigated by a home-built adhesion testing apparatus.
109
Poster
P-11
Alginate-based electroconductive hydrogels via UV-mediated thiol-ene
reaction
Eun Jung Choi, Ki-Hwan Hwang, Changsik Song*
Department of Chemistry, Sungkyunkwan University, Suwon, 440-746
Republic of Korea
Abstract
Alginates, easily found in the cell walls of brown algae, are carboxylic acid-contained polysaccharides
and widely used in biomedical engineering due to their favorable properties, including biocompatibility, low
toxicity, relatively low cost, and easy gelation.
Alginate hydrogels have been particularly attractive in wound healing, drug delivery, and tissue engineering
applications owing to their structural similarity to the extracellular matrices in living tissues. However, upon
sonication the hydrogels physically synthesized by adding divalent cations such as Ca 2+ are readily broken
their structures through releasing the added ions.
Furthermore, the hydrogel reveals poor electric conductivity, which limits biomedical applications. In this
study, alkene-functionalized alginate hydrogels were synthesized with a dithiol crosslinker under UV irradiation via thiol-ene reaction. To enhance electric conductivity carbon nanotubes were imbedded in the synthesized hydrogels.
The electrical and mechanical properties of the hydrogels were characterized as a function of the imbedded
carbon nanotubes by electrochemical impedance spectroscopy and rheology. In addition, we investigate the
conductivity of thiol-ene hydrogel affected by adding various metal ions because the carboxylate in alginate
can be trapped the ions.
110
Poster
P-12
Supramolecular polyampholyte hydrogels formed via hydrophobic and ionic
interactions
Esra SU1, Oguz Okay1
1
Istanbul Technical University, Faculty of Art and Sciences, Department of Chemistry, Istanbul, Turkey.
[email protected]
Hydrogels are one of the most studied systems for biomedical applications such as controlled release systems. Because the conventional hydrogels are soft and brittle materials, there has been significant progress
in recent years to increase their mechanical strength and to generate self-healing and shape memory effects[1, 2]. Here, we introduce a simple non-covalent approach and bulk photopolymerization method to create
high-strength stimuli-responsive self-healing hydrogels. We use hydrophobic and ionic interactions to generate a 3D network of hydrophilic polymer chains. Supramolecular polyampholyte hydrogels were synthesized
by photopolymerization of the monomers N,N-dimethylacrylamide (DMA), 4-vinylpyridine (VP), acrylic acid
(AAc), and stearyl methacrylate (C18M) . The cationic and anionic monomers, VP and AAc, respectively,
were used in equimolar ratios between 10 and 20 mol% (with respect to the monomers) while the hydrophobic monomer C18M content in the feed was fixed at 2 mol%. As compared to chemically cross-linked
polyampholyte hydrogels,[3] present hydrogels exhibit extraordinary mechanical properties and self-healing
ability. The supramolecular hydrogels are stable in water and show a significant variation in their volume in
response to changes in pH between 2 and 10, as well as to the salt concentration. It was also found that the
hydrogels are in a collapsed state not only at the pH of the isoelectric point (IEP) but also over a wide range
of pH including pKa (4.25) , pKb (8.77) and pHIEP (4.74). Comparison of the experimental swelling data with the
predictions of the Flory-Rehner theory of swelling equilibrium including the ideal Donnan equilibria suggests
that the pH inside the gel is different from pH of the outer solution.
Keywords: Hydrogels, polyampholytes, mechanical properties, swelling behavior.
[1] Gulyuz, U., Okay, O. Self-healing poly(acrylic acid) hydrogels with shape memory behavior of high mechanical strength Macromolecules 47 (2014) 6889-6899
[2] Okay, O. Self-healing hydrogels formed via hydrophobic interactions. Adv. Polym. Sci. 268 (2015) 101142
[3] Dogu S., Kilic M., Okay O. Collapse of acrylamide-based polyampholyte hydrogels in water. J. Appl.
Polym. Sci. 113 (2009) 1375-1382.
111
Poster
P-13
Preparation of pH/Redox-responsive Gel Particles as Smart Carriers
for Intracellular Delivery
A. Kawamura1, 2, A. Harada1, S. Ueno1, T. Miyata1, 2
1
Stimuli-responsive gel particles that undergo changes in size in response to environmental stimuli such as
pH and temperature have attracted considerable attention as smart biomaterials because of their potential
applications for drug and gene delivery. We have prepared molecule-responsive hydrogels using molecular
complexes as dynamic crosslinks1, 2). Furthermore, submicron-sized glucose-responsive gel particles having
saccharide-lectin complexes as dynamic crosslinks were successfully prepared by surfactant-free emulsion
polymerization3). In this study, dual stimuli-responsive gel particles that have both N, N-diethylaminoethyl
methacrylate (DEAEMA) as a pH-responsive moiety and a disulfide bond as a redox-responsive dynamic
crosslink were prepared by surfactant-free emulsion polymerization.
100
Dox release (%)
80
The dual stimuli-responsive gel particles were prepared by surpH 5.0, DTT (+)
factant-free emulsion copolymerization of DEAEMA, poly(ethylene glycol) dimethacrylate, and cystamine bisacrylamide
60
pH 5.0, DTT (-)
(CBA). The resulting CBA-DEAEMA gel particles were colloidally stable under physiological conditions had a diameter of
40
pH 7.4, DTT (+)
approximately 170 nm. Under acidic conditions, the swelling
ratio of the CBA-DEAEMA gel particles increased drastically in
20
pH 7.4, DTT (-)
response to dithiothreitol (DTT) as a reducing agent. The drastic
swelling of the CBA-DEAEMA gel particles under acidic con0
0
10
20
30
40
50
ditions with DTT was attributed to both protonation of tertiary
Time (h)
amino groups in DEAEMA and cleavage of disulfide bonds in
CBA that acted as dynamic crosslinks. The in vitro cytotoxicity
of the CBA-DEAEMA gel particles against mouse fibroblast cell
Fig. 1. Dox release profiles of Dox-loaded
line (L929 cells) was evaluated by the WST-8 assay. The WST- CBA-DEAEMA gel particles at 37 ºC. Symbolism:
8 assay revealed that the CBA-DEAEMA gel particles had low pH 7.4 without DTT (○); pH 7.4 with DTT (□); pH
cytotoxicity. Doxorubicin (Dox), one of the hydrophobic antican- 5.0 without DTT (●), pH 5.0 with DTT (■).
cer drugs, was successfully loaded into the CBA-DEAEMA gel
particles. The Dox release from Dox-loaded CBA-DEAEMA gel
particles was inhibited at pH 7.4 without DTT (Fig. 1). On the other hand, the Dox release was significantly
enhanced by the decrease in pH and the addition of DTT. The enhanced release of Dox was attributed to the
swelling of CBA-DEAEMA gel particles under acidic and reducing conditions. These results indicate that the
CBA-DEAEMA gel particles are promising as carriers for intracellular delivery.
References
1) Miyata, T. Polym. J. 2010, 42, 277.
3) Kawamura, A.; Hata, Y.; Miyata, T.; Uragami, T. Colloid Surf. B: Biointerfaces 2012, 99, 74.
112
P-14
Poster
Effect of fluctuations on tracer diffusion in networks and liquids
Won Kyu Kim1 and Joachim Dzubiella1,2
1
Institute for Soft Matter and Functional Materials, Helmholtz-Zentrum Berlin, Hahn-Meitner-Platz 1, Berlin,
Germany
2
Institute for Physics, Humboldt-Universität zu Berlin, Newtonstr. 15, Berlin, Germany
[email protected]
We study the tracer diffusion in simple Lennard-Jones fluids and semi-flexible chain networks, using coarsegrained molecular dynamics computer simulations. For the fluid system, we find that various dynamic regimes
are nontrivially dependent on inter-(tracer-fluid) and intra-(fluid-fluid) interactions, where fluctuations arising
in the system largely affect the tracer diffusion. We compute the tracer diffusivities spanning a wide range of
the interaction strengths, and reveal that an abrupt diffusivity shift signifies the gas-liquid phase transition. For
the network system, we further extend the model towards tracer-hydrogel diffusion by imposing connectivity
and semi-flexibility between the fluid particles that constitute the hydrogel network. Depending on the network–network and the tracer–network couplings, the network structure reveals a non-monotonic behaviour,
and we discuss how the tracers diffusion and transport show a variety of dynamic regimes in conjunction with
the network rigidity and fluctuations.
113
P-15
Poster
PREPARATION OF SUPRAMOLECULAR POLYMERIC MATERIALS USING
HOSTGUEST INTERACTION BETWEEN CYCLODEXTRIN AND ALKYL CHAIN
MODIFIED WITH VIOLOGEN
Kohei Otani, Masaki Nakahata, Yoshinori Takashima, Hiroyasu Yamaguchi, and Akira Harada
Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka,
560-0043, Japan, [email protected]
We previously developed functional polymeric materials based on host-guest interactions. The guest-host
complex acts as the reversible non-covalent crosslinking point in the materials. To control the physical property of the materials through the complex formation on the polymer side chain, here we prepare redox-responsive gels (CD-MVC11 gel) cross-linked by host-guest interactions between undecane modified with viologen (MVC11) and cyclodextrin (CD) based on polyacryl amide back bone (Figure 1a). CD shows high affinity
for the alkyl chain, but does not include the dicationic viologen (MV2+) unit, meaning that MV+ functions an
electric charge stopper for CD. We prepared CD-MVC11 gel and a reference gel with βCD and dodecyl(C12)
units (βCD-C12 gel) without MV moiety. Physical properties of the gels were characterized by stress−strain
measurements.
The physical property of the βCD-MVC11 gel showed higher rupture stress and lower rupture strain than
those of the βCD-C12 gel. This result indicates that MV2+ moiety serves as an energetic barrier preventing the
complex of βCD and C11 units from dissociation. An αCD-MVC11 gel (a gel with αCD having narrower cavity)
showed higher rupture stress and lower rupture strain than those of the βCD-MVC11 gel, because αCD is
more affected by the energetic barrier because of its cavity size (Figure 1b).
The αCD-MVC11 gel and the βCD-MVC11 gel exhibited different mechanical properties in a reduced state and
an oxidized state. βCD-MVC11 gel in its reduced state showed higher rupture stress and lower rupture strain
than those of the gel in its oxidized state. MV derivatives in the reduced state form dimer. This dimer serves
as a new cross-link in the polymer. We confirmed existence of it by the absorption spectrum having a maximum near 560 nm.
In summary, we successfully prepared gels based on host-guest interaction between CD and alkyl chain
modified with viologen. The gels changed their mechanical properties depending on MV moiety, cavity size
of CD, and redox state.
Figure 1 a) Chemical structure of βCD-C11MV gel . b) The energetic barrier for CD by stress.
114
Poster
P-16
Development of polyethylene glycol-graphene oxide hydrogel composite and
its application in electrophoresis of double stranded DNA
Kateryna Khairulina, Ung-il Chung, Takamasa Sakai
Department of Bioengineering, School of Engineering, University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo
Hydrogels, which are highly swollen polymer networks, have become an integral part of many tissue
engineering and drug delivery applications. Accordingly, a need has arisen to develop hydrogel composites with multimodal functionalities. With the development of better and more affordable ways to fabricate
graphene oxide (GO) high-aspect ratio sheets, a new type of composite materials has gaining momentum
are GO-hydrogel composites.1,2
2
Electrophoretic mobilty [cm / V sec]
One of the most important applications of hydrogels is size-based separation of uniformly charged solutes
(e.g. DNA, RNA, proteins). Understanding the molecular mechanisms of separations in the complex matrices
is of fundamental interest. Although numerous studies have been done and a number of models have been
proposed, not a single model can explain full extent of the experimental data.3 To the best of our knowledge,
the effect of incorporation of 2D planar non-organic sheets on migration mechanism of DNA has never been
investigated.
10
-4
9
8
7
6
Fig.1 DNA length dependency of electrophoretic
mobility in GO doped Tetra-PEG gels
5
4
3
2
10
-5
9
8
0 g/L control
-4
5*10 g/L
-3
5*10 g/L
-2
5*10 g/L
-1
5*10 g/L
1 g/L
100
2
3
4
5
6
7
8
9
1000
DNA length [bp]
In this study, we employed tetra-armed PEG-based hydrogels doped with GO in various concentrations and
investigated migration velocity of double stranded DNA (dsDNA) fragments. Graphene oxide has layered
structure and contains hydroxyl, epoxide and carboxyl groups on its surface, and can be incorporated into the
polymer network by side-reactions with amine terminal groups of one of the PEG pre-polymers. We observed
increase in elastic modulus with a small amount of GO, confirming the incorporation of GO into the network.
The threshold overlapping concentration (c*) of GO sheets was estimated on 0.1 gL-1 using viscosity measurements and we used capillary electrophoresis to separate double stranded DNA in hydrogels containing
minute amounts of GO. We observed decrease in electrophoretic mobility of dsDNA in intermediate size
range (200-1000 bp), while for rod-like dsDNA the effect of GO addition was negligible (Fig.1). Moreover,
DNA size-dependency was enhanced in hydrogels with GO content as low as 5*10-4 g/L, indicating that presence of 2D GO sheets in hydrogels may impose entropic barriers during migration of dsDNA.
References
[1] Cirillo G., et al, Bio Med Res. Int., 2014, 825017.
[2] Hopley E.L., et al, Biotechnol. Adv., 2014, 32, 1000–1014.
[3] Viovy, J.-L., Rev Mod Phys., 2000, 72, 813-872.
115
Poster
P-17
Conductivity of Melt-Spun PMMA Composites with Aligned Carbon Fibers
Muchao Qu, Dirk W. Schubert
Institute of Polymer Materials, Friedrich-Alexander-University Erlangen-Nuremberg, Martensstr. 7, 91058,
Erlangen, Germany
Chopped carbon fibers (CF) is one of the most widely used conductive fillers. Most of Literatures have discussed the concentration of CF with maximum value of 10 vol. %. Because this is already above the percolation threshold and after which there is no significant change in the electrical properties of the composites.
Unlike carbon black (dot-like, 0-dimensinal particle), the CFs are with significant aspect ratio (AR) and should
be considered as 1-dimensinal particle. It has been found that, the orientation of CF inside also influences
the percolation threshold of the composite. With higher orientation of CF, the percolation threshold should be
shifted towards higher concentration of fillers.
Conductive properties of 1-Dimension melt-spun PMMA/carbon fibers (fibers in fibers), and a simple and
convenient method for fibers composites are reported for the first time in this work. With two steps of melt
mixing, aspect ratios of CFs are 6.2, 9.2 and 11.9, respectively. Composites with highly oriented CFs with
high concentration of fillers (up to 60 vol. %) were melt spun, the surface as well as the section of composites
are observed and discussed. The conductivity of composites under room temperature will be compared with
theory from McLachlan [1-2], simulation from E. Hyytiä [3] and model from I. Balberg [4], respectively. Due to the
special nature of the 1-D composites with well aligned carbon fibers, deviations are found from each theory.
However, the percolation threshold as well as the relationship between percolation and aspect ratio will be
discovered. Furthermore, the special nature of these 1-D composites will be concluded, the angles between
CFs are estimated from 10˚ to 30˚. At the end, some predicted applications of these particular 1-D composites
with aligned carbon fibers are given.
FIGURE 1. (a) Surface of the melt-spun composite fiber; (b) Section of the melt-spun composite fiber.
1.
2.
3.
4.
D. S. McLachlan and G. Sauti, Journal of Nanomaterials ID–30389 (2007).
D. S. McLachlan, J. Phys. C: Solid State Phys. 19, 1339–1354 (1986).
E. Hyytiä et cl., Communications Letters, IEEE, 16(7), 1064–1067 (2012).
I. Balberg et cl., Physical Review (B) 30, 3933–3943 (1984).
116
P-18
Poster
Photo crosslinked defined tetra-PEG networks
M. Rohn, J. Novak, B. Ferse, B. Voit
Professur Physikalische Chemie der Polymere, Department of Chemistry, TU Dresden, Bergstr. 66, 01069
Dresden, Germany
[email protected]
Tetra-PEG hydrogels, based on poly(ethylene glycol)-macromolecules with 4 arms of near the same length,
were synthesized by photo-crosslinking reactions through UV-irridation. The Tetra-PEG’s are terminated with
maleimide anhydride groups. Light irridation induce a [2+2] cycloaddition through the maleimide doublebonds. [1]
O
O
O
HO
O
O
O
n
O
O
O
nOH
O
N
O
X
O
hv
360nm
O
O
N
O
O
O
O
n
O
OH
n
O
O
O
O
OH
n
O
O
N
HO
X
n
O
X
n
O
O
X:
O
N
O
O
O
O
nX
O
N
O
O
O
O
N
O
O
O
O
O
In dependence of the molecular weight and concentration of the Tetra-PEG macromers investigations for
conversion and swelling behavior were carried out. Dynamic light scattering was performed to get information about the gelation mechanism of the polymer networks. [2] Rheology measurements were done to get
information about the mechanical properties of the gels. From the storage modulus G’, the concentration of
effective cains vc was calculated and compared with the values determined from the conversion. This was
done considering the affine and free fluctuating (phantom) network model. [3]
0,8
g(2)(t)-1
0,6
0,4
0,2
tetra-PEG 20k
0 sec
30 sec
60 sec
90 sec
120 sec
300 sec
600 sec
0,0
1E-4 1E-3 0,01 0,1 1 10 100 1000
decay time [ms]
tetra-PEG 20k
vc (aff)
vc - µ (ph)
1,5x10-2
vc (rheology)
2,0x10-2
vc [mol/L]
1,0
1,0x10-2
5,0x10-3
0,0
0
4
8
12
16
c(tPEG) [wt%]
20
Acknowledgement: financial support by DFG-GRK 1865.
[1] S. Seiffert, W. Oppermann, K. Saalwächter, Polymer 2007, 48, 5599.
[2] T. Sakai, T. Matsunaga, Y. Yamamoto, C. Ito, R. Yoshia, S. Suzuki, N. Sasaki, M. Shibayama, U. Chung,
Macromolecules 2008, 41, 5379.
[3] Y. Akagi, T. Matsunaga, M. Shibayama, U. Chung, T. Sakai, Macromolecules 2010, 43, 488.
117
Poster
P-19
TOUGHNESS AND SELF-HEALING MATERIALS CROSS-LINKED BY
CYCLODEXTRIN-GUEST COMPLEXES
Yuki Sawa, Kazuhisa Iwaso, Masaki Nakahata, Yoshinori Takashima, Hiroyasu Yamaguchi,
and Akira Harada
Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka,
560-0043, Japan
[email protected]
Polymeric materials functionalized by non-covalent bond have much attention due to improvement of toughness and creation of innovative functions. We choose host-guest
interactions as non-covalent bond. As host and guest molecules, we
selected α- and β-cyclodextrin (CD) and corresponding guest molecules. CDs form inclusion complexes with suitable guest molecules.
Previously, we prepared supramolecular hydrogel with βCD and adamantyl groups. The hydrogel shows highly tough and self-healing
property1-4. Here we investigate the relation between physical property, the structure of guest groups, and association constants of CD
with guest groups. (Fig. 1).
We chose octyl acrylate (Oct), isobornyl acrylate (Ibr), and hydroxyadamantyl acrylate (HAdA) as guest monomers. The structure and
association constants with guest groups affect breaking strain and
rupture stress of supramolecular hydrogels. (Fig. 2) When attaching
cut surfaces, the hydrogel showed self-healing property (Fig. 3). In
summary, we successfully obtained tough and self-healing supramolecular hydrogels.
Figure 1. Chemical structures of supramolecular hydrogels and chemical
cross-linking hydrogel (PAAm gel) as
a control gel.
References
1. Harada, A.; Takashima, Y.; Nakahata, M. Acc. Chem. Res. 2014,
47, 2128-2140.
2. Nakahata, M.; Takashima, Y.; Yamaguchi H.; Harada, A. Nat.
Figure 2. Stress-strain curves of suCommun. 2011, 2, 511.
pramolecular hydrogels and chemical
cross-linking hydrogel.
3. Kakuta, T.; Takashima, Y.; Nakahata, M.; Otsubo, M.; Yamaguchi, H.; Harada, A. Adv. Mat., 2013, 25, 2849.
4. Nakahata, M.; Takashima, Y.; Harada, A. Macromol. Rapid Commun. 2016, 37, 86-92.
a
b
Self-healing
Figure 3. Self-healing property of
αCDAAmMe-Oct hydrogel.
118
Poster
P-20
Polymer Chain Mobility-Dependent Property of Cross-Linked Polymer
Synthesized with Rotaxane Cross-Linker
Jun Sawada, Daisuke Aoki, and Toshikazu Takata
Department of Organic and polymeric materials, Tokyo Institute of Technology
Ookayama 2-12-1-H126, Meguro, Tokyo 152-8552, Japan
Rotaxane cross-linked polymers (RCPs) having rotaxane structures at the cross-link points have been
attracting considerable attention due to the unique properties, such as high swellability, extensibility and
well stress relaxing ability, caused by the movable cross-link points. However, the reason and mechanism
for generation of such excellent property and function of RCP has not been clarified yet, because of the
structural complexity of RCP. In our previous report1), RCPs were synthesized by using structure well-defined
macromolecular [2]rotaxane cross-linkers (RCs). The RCPs showed higher swellability and toughness than
the corresponding covalently cross-linked polymers (CCPs). It should be noted that RC with a longer axle
chain gave much stronger RCP than RC with a shorter axle chain, demonstrating the effect of the mobile
length of the movable cross-link point.
In this work, to reveal how the mobility of the components at cross-link points affects on the properties of
RCP, RCs with the mobility-different components were synthesized by the combination of crown ether wheel
and bulkiness-controlled polycarbonate axle. The radical polymerization of n-butylacrylate in the presence
of RC afforded RCPs. CCPs were also prepared for comparison by using CCs having same polycarbonate
chains as those of RCs.
The properties of RCPs and CCPs were evaluated mainly by the tensile test which showed that the mechanical
properties of RCPs were much stronger than those of CCPs. Although there was no difference among the
mechanical properties of CCPs, clear axle bulkiness-dependent mechnical property of RCPs was observed,
supporting the importance of the component mobility of RCs.
1)
J. Sawada et al. ACS macro lett., 2015, 4, 598–601.
119
Poster
P-21
“Living” Smart Gels Made by Bioorthogonal Cross-Linking Reactions of
Azide-Modified Cells with Alkyne-Modified Biocompatible Polymers
Ayaka Takemoto and Koji Nagahama
Department of Nanobiochemistry, Frontiers of Innovative Research in Science and Technology (FIRST),
Konan University, 7-1-20 Minatojima-minamimachi, Chuo-ku, Kobe 650-0047, Japan
The Cell itself and cellular functions have been one of the most attractive research targets for scientist. In this
study, we demonstrated a new concept to utilize the cell itself and cellular functions for the design of functional hydrogels.1 Specifically, we developed “living” cell-based smart hydrogels which cells (human leukemia cell
line, HL-60 cell) were covalently cross-linked by biocompatible polymers (Figure 1).
For the purpose, we used metabolic glycoengineering technique to incorporate reactive azide groups
on the cell surface.2 Using this technique, monosaccharide precursor modified with azide group, which
entered into cells and metabolized, is covalently
incorporated into cell-surface glycans through the
biosynthetic machinery. We synthesized tetraacetylated N-azidoacetylmannosamine (Ac4ManNAz) as
precursor for azide-modified glycans on the cell
surface. It was found that the azide-modified HL-60 Figure 1. Schematic illustration of construction
cells prepared by treatment of Ac4ManNAz (20 mM) method of cell cross-linked hydrogels.
have maximum amount of azide groups on the cell
surface without cytotoxic effects. Next, we synthesized dibenzocyclooctyne-modified poly-γ-glutamic acid
(γ-PGA-DBCO) with the ability to perform bioorthogonal click cross-linking reaction with cell-surface azide
groups. In case of the bioortogonal reactions with cell number at above 0.5 x 106 cells, assembled cell constructs were formed. These cell constructs were mechanically stable and kept the assembled structures even
after vortex shaking, indicating that these cells were connected through the covalent bonds. Accordingly, it
was found that the cell constructs were hydrogels which HL-60 cells were cross-linked with γ-PGA molecules
through specific click reaction on the cell surfaces. In the hydrogel system, the HL-60 cells could act as active
cross-linking points capable of generating a wide variety of cellular functions. Interestingly, the hydrogels
exhibited unique functionality which is originated from the functions of the HL-60 cell incorporated as living
cross-linking points. The findings of this study could provide a promising new route to generate the next-generation smart hydrogels.
REFERENCES
[1] Nagahama, K.; Takemoto, A., under the revision.
[2] Jewett, J.C.; Bertozzi, C.R. Chem. Soc. Rev. (2010) 39, 1272.
120
Poster
P-22
Influence of crosslinking and penetrant size on the diffusion properties of
cyclic siloxanes through silicone elastomers
Jonas Daenicke1, Dirk W. Schubert1, Ulf W. Gedde2, Mikael Hedenqvist2, Erik Linde2, Thomas Sigl1 and
Raymund E. Horch3
1
Institute of Polymer Materials, Friedrich-Alexander-University Erlangen-Nürnberg (FAU), Martensstraße 7,
91058 Erlangen, Germany
2
3
Departement of Fibre and Polymer Technology, Royal Institute of Technology Stockholm (KTH),
Teknikringen 56, 100 44 Stockholm, Sweden
Plastisch- und Handchirurgische Klinik, Friedrich-Alexander-University Erlangen-Nürnberg (FAU),
Krankenhausstraße 12, 91054 Erlangen, Germany
Due to the ongoing discussion on safety and quality of silicone breast implants, they have been in focus of
research and public media in the recent years [1]. Silicone breast implants attract interest of this study with
respect to the increased amount of potentially toxic low molar mass components in the PIP silicone breast
implants [2, 3].
Driven by the investigation of the diffusion coefficient of low molar mass siloxanes through silicone breast
implant shells, the influence of crosslinking and penetrant size on the diffusion properties arose interest. The
study was focused on the diffusion of cyclic siloxanes, Octamethylcyclotetrasiloxane (D4), Decamethylcyclopentasiloxane (D5) and Dodecamethyl-cyclohexasiloxane (D6).
Tailor-made silicone elastomer samples varying in a deliberate adjusted degree of crosslinking were utilized
for the analysis of the diffusion behavior. Therefore, sorption experiments according to past studies of Gedde
and his team were carried out. The subsequent analysis of the sorption data yields to the corresponding diffusion properties [4]. On the basis of the diffusion coefficient related to the crosslinking a model was developed
to describe the material behavior.
References
1.
D. W. Schubert et al., Polym. Int. 63, 172–178 (2014).
2.
Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR), “Preliminary
Opinion on the safety of Poly Implant Prothèse (PIP) Silicone Breast Implants,” (European Commission,
2013 update).
3.
K. Mojsiewicz-Pieńkowska, “Chapter 16: Safety and Toxicity Aspects of Polysiloxanes (Silicones)
Application,” in Concise Encyclopedia of High Performance Silicones, edited by A. Tiwari and M. D. Soucek
(Scrivener Publishing LLC, Beverly, 2014), pp. 243–251.
4.
U. W. Gedde et al., Polym. Eng. Sci. 36 (16), 2077–2082 (1996).
121
Poster
P-23
Quasi-2D polymer networks as shells of acoustic responsive microvesicles
and microbubbles
Gaio Paradossi, Barbara Cerroni, Fabio Domenici, Letizia Oddo,
Angelico Bedini&, Sabrina Capece
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma Tor Vergata, Via della
Ricerca Scientifica 1, 00133, Rome, Italy
&
Dipartimento Innovazioni Tecnologiche, INAIL, Via Fontana Candida,1 Monteporzio Catone, 00040 Italy
e-mail:[email protected]
Lipid shelled microvesicles and microbubbles have received much attention over the years as drug carriers
and ultrasound (US) contrast agents, respectively. However, in the last decade microvesicles and microbubbles with crosslinked polymer shells have appealed researchers for their distinguished properties. A quasi-2D
polymer network of about 200 nm thickness wraps around liquid- or gas-filled microvesicles or microbubbles
of a few microns changing dramatically their properties as compared to those of lipid shelled microparticles.
Microbubbles: we first illustrate the increased stability and the chemical versatility of the polymer network shells in microbubbles with an average diameter of 3 microns. We report on the crosslinked poly (vinyl alcohol), PVA, shelled microbubbles, on their ultrasound acoustic properties and
the targeting toward inflammation (see Figure 1) and cancer tissues for molecular imaging purpose.1
Microvesicles: the perfluorocarbon core of lipid shelled microvesicles can be subjected to a liquid ↔ gas
phase transition upon US irradiation. What happens when the lipid monolayer is replaced with a quasi-2D
biodegradable dextran polymer network shell (see Figure 2)? We have characterized the interface properties
of the crosslinked polymer shell, included the dynamics of reconversion of the gas core to liquid, once the US
field was switched off. From this study it is possible to extract microrheological parameters of the shell, such
as bulk elastic modulus and shear viscosity of the crosslinked polymer shell.2 The control and reversibility of
the core phase transition from microvesicles (liquid core) into microbubbles (gas core) open to the theranostic
use of such phase-changing systems, i.e. as selective drug delivery carriers as well as efficient US imaging
We acknowledge financial support by FP7 EU project “TheraGlio” n. 602923.
Figure1. Targeting inflammation through antibody-PVA MBs. Merged transmission and confocal micrographs
of (A) non inflamed and (B) inflamed endothelial cells incubated with fluorescein labeled antibody MBs. (C)
Cytofluorimetry analysis of inflamed cells treated with no MBs (black lines), isotype MBs (green line) and
antibody MBs (pink lines).
Figure 2. Schematic description cycle undergoing a microvesicle
upon ultrasound irradiation.
References
[1]Barbara Cerroni, Ester Chiessi, Silvia Margheritelli, Letizia Oddo, and Gaio Paradossi; Biomacromolecules, 2011, 12,
593-601
[2] Sabrina Capece, Fabio Domenici, Francesco Brasili,
Letizia Oddo, Barbara Cerroni, Angelico Bedini, Federico
Bordi and Gaio Paradossi; Phys. Chem. Chem. Phys., 2016,
18, 8378 – 8388
122
Poster
P-24
One-Component Thiol-Alkene Functional Oligoester Resins Utilizing Lipase
Catalysis
Maja Finnvedena, Samer Nameerb, Mats KG Johanssonb and Mats Martinellea
KTH Royal Institute of Technology, Division of Industrial Biotechnology, AlbaNova University Centre,
106 91 Stockholm, Sweden
b
KTH Royal Institute of Technology, Department of Fibre and Polymer Technology, Teknikringen 56-58,
a
Lipases are powerful catalysts for producing polymers that could be difficult to obtain with conventional
synthesis [1]. The reaction conditions used in the industry may: limit the chemical and structural characteristics
of the polymer, destroy reactive functional groups by heat and induce extensive cis/trans isomerization of
unsaturated monomers which can lead to poor crystallinity of the product [2].
In the present study, a chemo-enzymatic route to synthesize polymer-networks with intact alkenes, that
facilitate post-modification, has been developed. Bio-based monomers are utilized as building blocks for
one-component thiol-alkene functional resins that form networks by thiol-alkene addition. The thiol addition
to alkenes is a fast free-radical process, which in some cases is spontaneous. Since the spontaneous
process increases with temperature, the incorporation of thiols and alkenes in the same thermoset resin is a
challenging task using traditional synthesis routes at high temperatures [3].
MeOH
O
O
O
O
HO
OH HS
4
HS
OH
Novozyme 435
(CALB)
4
O
O
O
O
O
O
DP
O
O
4
SH
Figure 1 Enzymatic route to thiol-alkene functional oligoesters.
Using immobilized Candida antarctica lipase B (CALB) as a catalyst we have synthesized thiol-alkene
functional resins with different degrees of polymerization (DP), see Figure 1. The synthesis is possible due
to the chemoselectivity of CALB towards the hydroxyl group rather than the thiol [4]. The one-component
oligoesters enabled cross-linking via thiol-alkene chemistry. By increasing the DP of the oligoesters the
alkene-to-thiol ratio increased which resulted in more alkenes within the final network.
____
[1] Yu Y., Wu D., Liu C., Zhao Z., Yang Y., Li Q., Process Biochem., 2012
[2] Binns F., Roberts S., Taylor A., Williams, C., J. Chem. Soc. Perkin Trans, 1993
[3] Cramer, N.B. and C.N. Bowman, Journal of Polymer Science Part A: Polymer Chemistry, 2001
[4] Cecilia Hedfors, Karl Hult, Mats Martinelle, Journal of Molecular Catalysis B: Enzymatic, 2010.
123
P-25
Poster
Network-like structure formed by inorganic polyphosphate
through p-stacked cationic porphyrins
Olga Ryazanova1, Victor Zozulya1, Igor Voloshin1,
Mykola Ilchenko2, Igor Dubey2, Victor Karachevtsev1
B. Verkin Institute for Low Temperature Physics and Engineering of NAS of Ukraine,
47 Lenin ave., 61103, Kharkov, Ukraine
E[mail: [email protected]
2
Institute of Molecular Biology and Genetics of NAS of Ukraine, 150 Zabolotnogo str., 03143, Kyiv, Ukraine
1
The polymers with alternating phosphate groups in the chain are widespread in the living organisms and
in the all biological systems. Inorganic polyphospate (PPS) represents a linear chain of orthophosphate
residues each carrying a monovalent negative charge, therefore it can serve as polyanionic scaffold to
assemble cationic macromolecules [1]. The rotational flexibility of the P-O-P bonds allows the conformational
adjustment of PPS chains to the π-π stacks of cationic organic dyes.
Cationic meso-porphyrins are well-known macrocyclic compounds possessing by unique photophysical
properties and high photosensitizing ability, which can form ordered aggregates on polyanionic scaffolds that
makes them promising agents for applications in nanomedicine and nanotechnology including design of new
photonic materials and devices etc.
Comprehensive study of PPS binding to tetra- and tricationic meso-porphyrins, TMPyP4 [2] and TMPyP3+
[3], was performed in aqueous solutions in a wide range of molar phosphate-to-dye ratios using different
spectroscopic techniques and DFT calculation method.
It was established that stoichiometric mixture of inorganic polyphosphate with tri- ad tetracationic mesoporphyrins results in transformation of absorption and fluorescence spectra, quenching of porphyrin emission,
substantial increase in the sample viscosity and appearance of strong light scattering. After analyzing of data
obtained we assume that formation of network-like structure is occurred where multiple polymer strands are
interconnected by π-stacked porphyrin molecules.
So, Coulomb interaction of oppositely charged methylpyridyl groups of porphyrins and phosphate residues
leads to charge neutralization and formation of the stable p-p stacking porphyrin aggregates onto PPS chains:
H-type in the case of TMPyP4, and mixture of J- and H-types in the case of TMPyP3+. Molecular modeling
shows that the flexibility of PPS strand allows a realization of spiral or “face-to-face” one-dimensional
structures formed by porphyrin molecules. It enables formation of two porphyrin stacks on opposite sides of
polymer strands and their integration in higher order aggregates. Their size estimated from light scattering
data reaches several hundred nanometers. At that PPS strands form network-like partially ordered structure.
[1] Brown M.R.W., Kornberg A. (2004) Proc. Natl. Acad. Sci. USA, v. 101, 16085-16087.
[2] Zozulya V., Ryazanova O., Voloshin I., Glamazda A., Karachevtsev V. (2010) Journal of Fluorescence,
v. 20, 695-702.
[3] Zozulya V., Ryazanova O., Voloshin I., Ilchenko M., Dubey I., Glamazda A., Karachevtsev V. (2014)
Biophysical Chemistry, v. 185, 39-46.
124
Poster
.
P-26
Adsorption of reactants on a PNIPAM polymer
Matej Kanduč1, 2 and Joachim Dzubiella1, 2
1Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, D-14109 Berlin, Germany
2Institute for Physics, Humboldt-Universität zu Berlin, Newtonstr. 15, Berlin, Germany
Thermoresponsive hydrogels, such as Poly(N-isopropylacrylamide) (PNIPAM), are recently becoming very
popular as ‘smart’ carriers in modern nanoscience. By changing the temperature, the PNIPAM hydrogel
structure can undergo a sharp transition from a swollen into a collapsed state, which alters the selectivity for
the solute particles that diffuse through the hydrogel. Catalytic model reactions of the reduction of p-nitrophenol and nitrobenzene nicely demonstrate such a selectivity [1], where the reaction rates of both reactants
dramatically change after the transition. In order to gain insights into the nanoscale structure, binding kinetics,
and diffusion in such systems, we employ Molecular Dynamics simulations of PNIPAM polymer in explicit
water. We model an extended PNIPAM polymer chain in the presence of various solutes dissolved in water,
which mimics the hydrogel in the swollen state. We put particular attention on benzene and its derivatives and
explore the influence of temperature, polymer stretch, and polymer tacticity on the solute binding affinities.
[1] Shuang Wu, Joachim Dzubiella, Julian Kaiser, Markus Drechsler, Xuhong Guo, Matthias Ballauff, and
Yan Lu, Angew. Chem. Int. Ed. 51, 2229 (2012).
125
Poster
P-27
Self-catalyzed thermal crosslinking of fully bio-based epoxy resins
Samer Nameer1, Mats Johansson1
1
KTH Royal Institute of Technology, Department of Fibre and Polymer Technology, Division of Coating
Technology, SE-10044 Stockholm, Sweden;
During the last decades the need to move away from fossil-based raw materials has increased due to
environmental reasons. One way to address this is to utilize renewable monomers found abundant in nature
as an alternative raw material. Today bark is considered as a low value waste and is mainly utilized for energy
recovery. Appreciable amounts of renewable monomers such as hydroxy, epoxy, and dicarboxylic acids can
be found in outer birch bark (Betula pendula) [1-3]. One such renewable monomer found in outer birch bark
is cis-9, 10-epoxy-18-hydroxyoctadecanoic acid (EFA), Figure 1, which contain an acid, an alcohol and an
epoxy group in the same molecule.
Epoxy resins are commercially used in various applications such as coatings and in structural components
[4]. The epoxy resins have gained interest due to the broad variety of chemical reactions that can be used
to obtain different final materials properties. They are also known for their good mechanical and adhesion
properties when cured. Furthermore, in contrast to vinyl polymerizations, epoxy resins demonstrate less
shrinkage when cured [5].
In the present study a thermal curable coating is prepared from a renewable monomer by a self catalyzed
step. One advantage of using a self catalyzed system is that no external catalyst is used and that no remaining
catalyst will be present in the final product. To fully understand the curing mechanism model reactions
were prepared to follow the different reactions that can occur from EFA. The curing rates of the resin were
reasonable and occured by two parallel reactions. The curing performance of EFA was studied by RTIR and
NMR analysis. Details on the results will be presented at the conference.
Figure 1 cis-9,10-epoxy-18-hydroxyoctadecanoic acid from birch bark.
References
1.
Torron, S., et al., Polymer Thermosets from Multifunctional Polyester Resins Based on Renewable
Monomers. Macromolecular Chemistry and Physics, 2014. 215(22): p. 2198-2206.
2.
Ekman, R., The Suberin Monomers and Triterpenoids from the Outer Bark of Betula verrucosa Ehrh.
Holzforschung-International Journal of the Biology, Chemistry, Physics and Technology of Wood, 1983.
37(4): p. 205-211.
3.
Kolattukudy, P., Polyesters in Higher Plants, in Biopolyesters, W. Babel and A. Steinbüchel, Editors.
2001, Springer Berlin Heidelberg. p. 1-49.
4.
Chattopadhyay, D.K., S.S. Panda, and K.V.S.N. Raju, Thermal and mechanical properties of epoxy
acrylate/methacrylates UV cured coatings. Progress in Organic Coatings, 2005. 54(1): p. 10-19.
5.
May, C., Epoxy resins: chemistry and technology. 1987: CRC press.
126
Poster
P-28
Double Networks Bearing the Mechano-Responsive Moiety of Spiropyran
Costas S. Patrickios and Elina N. Kitiri
Department of Chemistry, University of Cyprus, P. O. Box 20537, 1678 Nicosia, Cyprus
[email protected]
In recent years, stimuli-responsive materials have received increasing attention. While common stimuli include temperature and light, a less common, but equally important, stimulus is mechanical force. This work
reports the preparation and characterization of mechanically robust double polymer networks, capable of
sensing their own damage through the mechanochromic response of the spiropyran moieties they possess.
The syntheses of the mechano-responsive first networks, which were amphiphilic, were performed by the
sequential controlled radical polymerization of a hydrophilic and a hydrophobic monomer as well as a crosslinker, using a bifunctional initiator. The spiropyran moiety was located either in the initiator or in the crosslinker. The second network, comprising acrylamide and N,N΄-methylenebisacrylamide, was prepared via
conventional photopolymerization within the first network, using 2-oxoglutaric acid as the photoinitiator. All
networks prepared were characterized in terms of their degrees of swelling in different solvents, and also in
terms of their mechanical properties in compression and tension.
127
Poster
P-29
Amphiphilic Polymer Conetworks: Prediction of Their Ability for
Oil Solubilization
Costas S. Patrickios and Constantina Varnava
[email protected]
In this work, we develop a molecular thermodynamic theory predicting the ability of amphiphilic polymer conetworks (APCN) to selectively solubilize organic solvents. The present APCNs were assumed to have an
ideal structure, comprising amphiphilic ABA triblock copolymers of well-defined size and composition, endlinked at cores of exact functionality. The formulated theory calculates and minimizes the Gibbs free energies
of the various possible morphologies of the conetworks, spherical, cylindrical and lamellar, as well as disordered, and it, therefore, provides the prevailing morphology. All necessary components of the Gibbs free energies were taken into account, including the elastic, mixing, electrostatic and interfacial. Unlike our previous
model on APCN aqueous swelling, the present model requires two independent variables for minimization;
these were chosen to be the polymer volume fractions in the aqueous and oil nanophases. The effects
various parameters were investigated, including the size and composition of the polymer chains, the core
functionality, and the Flory-Huggins interaction parameters among the four components in the system, i.e.,
the hydrophilic and the hydrophobic polymer segments, and the two solvents (the oil and water). Outputs of
the model include a phase diagram and the equilibrium degrees of swelling of the two polymeric nanophases.
128
Poster
P-30
Amphiphilic Dynamic Covalent Hydrogels: Synthesis and Characterization
Costas S. Patrickiosa, Demetris E. Apostolidesa, Miriam Simonb and Michael Gradzielskib
a
b
Department of Chemistry, University of Cyprus, Nicosia, Cyprus
Institute for Chemistry, Technical University of Berlin, Berlin, Germany
[email protected]
In the last decade self-healable polymeric materials have attracted the interest of the research community
due to their ability to expand their lifetime via self-repairing mechanisms. These materials have the potential
to self-heal any cracks, preventing, on the one hand, the total collapse, and, on the other hand, maintaining
their integrity and mechanical properties. A simple strategy to achieve that is by introducing reversible crosslinks between the polymeric chains, such as dynamic covalent bonds, supramolecular bonds or physical
interactions.
We present the synthesis of a novel amphiphilic hydrogel cross-linked via dynamic covalent acylhydrazone
(reversible) bonds, simply by mixing two identical amphiphilic star block copolymers, bearing acylhydrazide
and benzaldehyde terminal groups. The gelation rate and degree of swelling can be tuned by varying the
synthesis pH and temperature, respectively. Furthermore, the conformation of the amphiphilic star block
copolymer in the dynamic hydrogel was examined using atomic force microscopy and small-angle neutron
scattering. The dynamic features of the amphiphilic hydrogels were proved by performing sol-to-gel and gelto-sol transitions and self-healing experiments. Finally, the mechanical properties of the amphiphilic dynamic
hydrogels were evaluated in compression and tension.
129
Poster
P-31
Synthesis and Characterization of End-linked Amphiphilic Polymer
Conetworks Based on ABA Triblock Copolymers of N,N-Dimethylacrylamide
and N-Laurylacrylamide
Costas S. Patrickios and Panayiota A. Panteli
[email protected]
Polymer networks are important materials with remarkable properties which lead to a multitude of applications. Although these materials are usually prepared via conventional free radical polymerization, in this
presentation network synthesis was accomplished through a controlled radical polymerization method, and,
in particular, reversible addition-fragmentation chain-transfer (RAFT) polymerization. The materials prepared
were amphiphilic polymer conetworks based on end-linked ABA triblock copolymers of the hydrophilic N,N-dimethylacrylamide and the hydrophobic N-laurylacrylamide, covering a range of molecular weights and compositions. The linear precursors to the conetworks were characterized in terms of their molecular weights and
compositions using gel permeation chromatography and 1H NMR spectroscopy, respectively. Furthermore,
the self-assembly of these precursors in ethanol was explored using dynamic light scattering, atomic force
microscopy, and 1H NMR spectroscopy. Finally, the prepared networks were characterized in terms of their
degrees of swelling in water and ethanol, and their mechanical properties in compression and tension.
130
Poster
P-32
Strong and Tunable Wet Adhesion with Rationally Designed Layer-by-Layer
Assembled Triblock Copolymer Films
Andrea Träger, Samuel A. Pendergraph, Torbjörn Pettersson, Anna Carlmark, Lars Wågberg
KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Fibre and
Polymer Technology, Teknikringen 56, SE-100 44 Stockholm, Sweden
[email protected]
The wet-adhesion of Layer-by-Layer (LbL) assembled films of triblock copolymer micelles has been evaluated with colloidal probe AFM, opening up yet another application area for block copolymers – as nanometer
thin adhesive films with tailored thickness and properties. A network of energy dissipating polymer chains
with electrostatic linkages can be built through the LbL assembly of triblock copolymer micelles with long, hydrophobic, low Tg middle blocks and short, charged outer blocks. Four triblock copolymers were synthesized
through Atom Transfer Radical Polymerization, one pair having poly(ethyl hexyl methacrylate) (PEHMA) and
the other poly( n-butyl methacryate) as middle block. One triblock copolymer with cationic and one with anionic outer blocks was made from each middle block. It has been found earlier that the wet adhesion of an LbL
system with poly(allylamine hydrochloride) (PAH) and hyaluronic acid (HA) was 20 times higher than that of
bone and collagen. The pull-of force for the PEHMA system studied here was in turn more than 400% higher
than that of PAH/HA. This study has shown that the devised concept can yield films with high wet adhesion
which could find numerous uses where a nanometer-thin adhesive joint is desired.
131
P-33
Poster
Renewable UV-curable Polyesters Based on Itaconic Acid: Synthesis and
characterization
Sara Brännström1, Mats Johansson1, Eva Malmström1
1
KTH Royal Institute of Technology, Department of Fibre and Polymer Technology, Teknikringen 56-58,
[email protected]
Increased environmental awareness has led to a high interest in replacing non-renewable petroleum-based
polymeric materials with renewable ones [1]. Itaconic acid is a fully bio-based and relatively inexpensive
monomer that can be obtained from fermentation of carbohydrates by the fungi Aspergillus terrus [2]. There
have been several recent studies on polymerizing itaconic acid with different diols to make unsaturated polyesters for various applications [3-5].
UV curing has the capability of effectively curing high performance coatings. At the same time it has low energy consumption and low VOC emissions.
The combination of using bio-based materials with UV curing to make coatings therefore provides a good
method for making renewable green thermosets. Materials developed in previous studies within this area
have shown great potential [6, 7]. However, despite the many studies on polyesterification of itaconic acid
and the use of these unsaturated polyesters as coatings the curing reaction and the effect of the molecular
weight have not been investigated thoroughly.
The aim of this study is to make bio-based unsaturated polyesters with hydroxyl-ends based on monomers
that can be made completely renewable, including itaconic acid, with different molecular weights and different
crosslinking density. The photo initiated radical crosslinking has been studied with real time FTIR and the
properties of the crosslinked materials was evaluated.
[1]
T. Robert and S. Friebel, “Itaconic acid - a versatile building block for renewable polyesters with enhanced functionality,”
Green Chemistry, 2016.
[2]
S. Choi, C. W. Song, J. H. Shin, and S. Y. Lee, “Biorefineries for the production of top building block chemicals and their
derivatives,” Metabolic Engineering, vol. 28, pp. 223-239, 3// 2015.
[3]
A. C. Fonseca, I. M. Lopes, J. F. J. Coelho, and A. C. Serra, “Synthesis of unsaturated polyesters based on renewable
monomers: Structure/properties relationship and crosslinking with 2-hydroxyethyl methacrylate,” Reactive and Functional
Polymers, vol. 97, pp. 1-11, 12// 2015.
[4]
O. Goerz and H. Ritter, “Polymers with shape memory effect from renewable resources: crosslinking of polyesters based
on isosorbide, itaconic acid and succinic acid,” Polymer International, vol. 62, pp. 709-712, 2013.
[5]
T. J. Farmer, R. L. Castle, J. H. Clark, and D. J. Macquarrie, “Synthesis of Unsaturated Polyester Resins from Various
Bio-Derived Platform Molecules,” International journal of molecular sciences, vol. 16, pp. 14912-14932, 2015.
[6]
J. Dai, S. Ma, X. Liu, L. Han, Y. Wu, X. Dai, et al., “Synthesis of bio-based unsaturated polyester resins and their application in waterborne UV-curable coatings,” Progress in Organic Coatings, vol. 78, pp. 49-54, 1// 2015.
[7]
J. Dai, S. Ma, Y. Wu, L. Han, L. Zhang, J. Zhu, et al., “Polyesters derived from itaconic acid for the properties and biobased content enhancement of soybean oil-based thermosets,” Green Chemistry, vol. 17, pp. 2383-2392, 2015.
132
Upcoming conferences
Save the Date
82nd Prague Meeting on Macromolecules
Polymer Networks Group Meeting 2018
Prague, 17-21 June, 2018
organized by Institute of Macromolecular Chemistry,
Academy of Sciences of the Czech Republic
imc.cas.cz
Advanced Polymers via
Macromolecular Engineering
Ghent, Belgium | May 21-25, 2017
Coatings Science International 2017
June 26-30, Noordwijk, The Netherlands
Confirmed plenary speakers :
Conference topics
Prof. Craig HAWKER (University of California, United States)
Prof. Ludwik LEIBLER (ESPCI, France)
Prof. Mitsuo SAWAMOTO (Kyoto University, Japan)
Prof. Martina STENZEL (UNSW, Australia)
▶ Recent Advances in Macromolecular Synthesis
▶ Complex Macromolecular Structures
▶ Dynamic and Supramolecular Polymers
▶ Stimuli-responsive and Functional Polymer
Architectures
▶ Self-healing and Reprocessable Polymer Systems
▶ Polymers at Surfaces and Interfaces
▶ New Industrial Developments for Polymeric Materials
▶ Polymers meet Biology/Biochemistry
▶ Polymers from Renewable Resources
▶ Polymers for Energy Applications
Organisers
Chairman
Prof. F. DU PREZ (Ghent University, Belgium)
Co-Chairs
Prof. R. HOOGENBOOM (Ghent University, Belgium)
Prof. M. MISHRA (Altria Research Center, United States)
Prof. Y. YAGCI (Istanbul Technical University, Turkey)
Honorary Chairmen
Prof. T. ENDO (Kinki University, Japan)
Prof. E. GOETHALS (Ghent University, Belgium)
http://www.coatings-science.com
APME 2017 Symposium Secretariat
LD Organisation sprl
Scientific Conference Producers
T +32 10 45 47 77
[email protected]
Find out more about the 40 keynote speakers and 30 invited lectures for the 12th APME-meeting on : www.apme2017.org
133
List of participants
A
Rémi
Absil
[email protected]
Université de Mons
BELGIUM
Kazunari
Akiyoshi
[email protected]
Kyoto University
JAPAN
Ann-Christine
Albertsson
[email protected]
KTH Royal Institute of Technology
SWEDEN
Selda
Aminzadeh
[email protected]
SWEDEN
Per
Antoni
[email protected]
Carmeda AB
SWEDEN
Daisuke
Aoki
[email protected]
Tokyo Institute of Technology
JAPAN
Aslihan
Argun
[email protected]
Istanbul Technical University
TURKEY
Juan
Baselga
[email protected]
Universidad Carlos III de Madrid
SPAIN
Jonas
Bengtsson
[email protected]
GE Healthcare
SWEDEN
Patrice
Bourson
[email protected]
lmops
FRANCE
Tim
Bowden
[email protected]
Uppsala University
SWEDEN
Sara
Brännström
[email protected]
SWEDEN
Jean-Paul
Chapel
[email protected]
CNRS - Bordeaux University
FRANCE
Orsolya
Czakkel
[email protected]
Institut Laue-Langevin
FRANCE
Marc
von Czapiewski
[email protected]
SWEDEN
Jonas
Daenicke
[email protected]
Friedrich-Alexander-University
Erlangen-Nuremberg
GERMANY
Anders E.
Daugaard
[email protected]
Technical University of Denmark
DENMARK
David
Diaz Diaz
[email protected]
Universität Regensburg
GERMANY
Aleksey
Drozdov
[email protected]
Aalborg University
DENMARK
Filip
Du Prez
[email protected]
Ghent University
BELGIUM
Jan-Erik
Edetoft
[email protected]
PerkinElmer
SWEDEN
Joakim
Engström
[email protected]
SWEDEN
Ahmet
Erdem
[email protected]
Kocaeli University
TURKEY
Maja
Finnveden
[email protected]
SWEDEN
Linda
Fogelström
[email protected]
SWEDEN
Forcada
[email protected]
University of the Basque Country UPV/
EHU
SPAIN
Aaron
Gehrke
[email protected]
University of Kansas
UNITED
STATES
Stevin
Gehrke
[email protected]
University of Kansas
UNITED
STATES
Takehiko
Gotoh
[email protected]
Hiroshima University
JAPAN
Viktor
Granskog
[email protected]
SWEDEN
Jürgen
Groll
[email protected].
de
University of Würzburg
GERMANY
Daniel
Gylestam
[email protected]
PerkinElmer
SWEDEN
Hedenqvist
[email protected]
SWEDEN
FINLAND
SWEDEN
B
C
D
E
F
Jacqueline
G
H
Mikael
Sami
Hietala
[email protected]
Laboratory of Polymer Chemistry,
Alexandra
Holmgren
[email protected]
134
Jonna
Holmqvist
[email protected]
SWEDEN
Dominique
Hourdet
[email protected]
École Supérieure de Physique et de
Chimie Industrielles de la Ville de Paris
FRANCE
Steve
Howdle
[email protected]
University of Nottingham
UNITED
KINGDOM
Geng
Hua
[email protected]
SWEDEN
Anders
Hult
[email protected]
SWEDEN
Ki-Hwan
Hwang
[email protected]
Sungkyunkwan University
REPUBLIC
OF KOREA
Søren
Hvilsted
[email protected]
DTU Technical University of Denmark
DENMARK
Niklas
Ihrner
[email protected]
SWEDEN
Olli
Ikkala
[email protected]
Aalto University School of Science
FINLAND
Tobias
Ingverud
[email protected]
SWEDEN
Béla
Iván
[email protected]
Hungarian Academy of Sciences
HUNGARY
David
Jansson
[email protected]
GE Healthcare
SWEDEN
Morten
Jarlstad Olesen
[email protected]
Aarhus University
DENMARK
Marcus
Jawerth
[email protected]
SWEDEN
Li
Jia
[email protected]
The University of Akron
UNITED
STATES
Apichaya
Jianprasert
[email protected]
King Mongkut’s Institute of Technology
Ladkrabang
THAILAND
Mats
Johansson
[email protected]
SWEDEN
Tahani
Kaldéus
[email protected]
SWEDEN
Matej
Kanduc
[email protected]
Helmholtz Zentrum Berlin
GERMANY
Akifumi
Kawamura
[email protected]
Kansai University
JAPAN
Kateryna
Khairulina
[email protected]
University of Tokyo
JAPAN
Won Kyu
Kim
[email protected]
Institute for Soft Matter and Functional
Materials, Helmholtz-Zentrum Berlin
GERMANY
James P.
Lewicki
[email protected]
Lawrence Livermore National Laboratory
UNITED
STATES
Xiang
Li
[email protected]
University of Tokyo
JAPAN
Susanna
Lindberg
[email protected]
GE Healthcare
SWEDEN
Pär
Lindén
[email protected]
SWEDEN
I
J
K
L
Wei
Liu
[email protected]
The Chinese University of Hong Kong
CHINA
(HONG
KONG
S.A.R.)
Chris
Lowe
[email protected]
Becker Industrial Coatings Ltd
GREAT
BRITAIN
Michael
Malkoch
[email protected]
SWEDEN
Eva
Malmström
[email protected]
SWEDEN
Kazuya
Matsumoto
[email protected]
Kansai University
JAPAN
Anna
Melker
[email protected]
SWEDEN
Pierre
Millereau
[email protected]
SIMM ESPCI
FRANCE
Takashi
Miyata
[email protected]
Kansai University
JAPAN
M
135
Beata
Mossety-Leszczak
[email protected]
Rzeszow University of Technology
POLAND
Sada-Atsu
Mukai
[email protected]
Kyoto University
JAPAN
Koji
Nagahama
[email protected]
Konan University
JAPAN
Masaki
Nakahata
[email protected]
Osaka University
JAPAN
Samer
Nameer
[email protected]
SWEDEN
Daniel
Nyström
[email protected]
Carmeda AB
SWEDEN
Karin
Odelius
[email protected]
SWEDEN
Bradley
Olsen
[email protected]
MIT
UNITED
STATES
Kohei
Otani
[email protected]
Osaka University
JAPAN
Gaio
Paradossi
[email protected]
University of Rome Tor Vergata
ITALY
Eleonora
Parelius Jonasova
[email protected]
NTNU, Norwegian University of Science
and Technology
NORWAY
Bourson
Patrice
[email protected]
University of Lorraine
FRANCE
Costas
Patrickios
[email protected]
University of Cyprus
CYPRUS
Olga
Philippova
[email protected]
Moscow State University
RUSSIA
Christian
Porsch
[email protected]
Carmeda AB
SWEDEN
Qu
[email protected]
Friedrich-Alexander University
GERMANY
Mathias
Rohn
[email protected]
Technical University Dresden
GERMANY
Olga
Ryazanova
[email protected]
National Academy of Sciences of Ukraine
UKRAINE
Zhansaya
Sadakbayeva
[email protected]
Institute of Macromolecular Chemistry
AS, CR
CZECH
REPUBLIC
Marco
Sangermano
[email protected]
Politecnco di Torino
ITALY
Yuki
Sawa
[email protected]
Osaka University
JAPAN
Jun
Sawada
[email protected]
Tokyo Institute of Technology
JAPAN
Felix
Schacher
[email protected]
Friedrich-Schiller-Universität Jena
GERMANY
Dirk W.
Schubert
[email protected]
University Erlangen - Nürnberg
GERMANY
Yoshimi
Seida
[email protected]
Toyo University
JAPAN
Sebastian
Seiffert
[email protected]
Johannes-Gutenberg-Universität Mainz
GERMANY
Stefan
Semlitsch
[email protected]
SWEDEN
Mistuhiro
Shibayama
[email protected]
University of Tokyo
JAPAN
Joonas
Siirilä
[email protected]
FINLAND
Anne L.
Skov
[email protected]
Technical University of Denmark
DENMARK
Patrik
Stenström
[email protected]
SWEDEN
Molly M.
Stevens
[email protected]
Imperial College London
UNITED
KINGDOM
Bjørn T.
Stokke
[email protected]
and Technology
NORWAY
Berit L.
Strand
[email protected]
and Technology
NORWAY
Emma
Strömberg
[email protected]
SWEDEN
Esra
Su
[email protected]
Istanbul Technical University
TURKEY
N
O
P
Q
Muchao
R
S
136
Zhigang
Suo
[email protected]
Harvard University
UNITED
STATES
Per-Erik
Sundell
[email protected]
SSAB
SWEDEN
Nobuyuki
Takahashi
[email protected]
Hokkaido University of Education,
Hakodate
JAPAN
Yoshinori
Takashima
[email protected]
Osaka University
JAPAN
Ayaka
Takemoto
[email protected]
Konan university
JAPAN
Heikki
Tenhu
[email protected]
FINLAND
Pitchaya
Treenate
[email protected]
King Mongkut’s Institute of Technology
Ladkrabang
THAILAND
Andrea
Träger
[email protected]
SWEDEN
Constantinos
Tsitsilianis
[email protected]
University of Patras
GREECE
Urayama
[email protected]
Kyoto Institute of Technology
JAPAN
Robert
Westlund
[email protected]
Swedish Defence Materiel Administration
SWEDEN
Cecilia
Winander
[email protected]
JOTUN AS
NORWAY
Françoise M.
Winnik
[email protected]
University of Montreal
CANADA
T
U
Kenji
V/W
Chi
Wu
[email protected]
The Chinese University of Hong Kong
CHINA
(HONG
KONG
S.A.R.)
Martin
Wåhlander
[email protected]
SWEDEN
Xu
[email protected]
Northumbria University
UNITED
KINGDOM
Yuguchi
[email protected]
Osaka Electro-Communication University
JAPAN
Alexander N.
Zelikin
[email protected]
Aarhus University
DENMARK
Yuning
Zhang
[email protected]
SWEDEN
X
Ben
Y
Yoshiaki
Z
137
138
139
140

Programme and Book of Abstracts

Transcription

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