Department of Chemistry, University of Rome La

Steroidal Surfactants for Nanotechnological
Applications
Reference person: Luciano Galantini
Senior Scientists: Nicolae V. Pavel, Andrea D’Annibale, Mauro Giustini
PhD students: Jacopo Cautela
MSc students: Rosaceleste Zumpano, Camilla Bisceglie, Gretha Di Donato, Alessio Di Giuseppe
Supramolecular structures formed by amphiphiles act as
soft materials, which find useful applications in many fields
of nanoscience ranging from biomedical to technological.
Bile salts (BSs) are anionic natural steroidal surfactants with
appealing amphphilic features for various applications:
preparation of transferosomes, dispersion and drug
delivery, solubilization of carbon based material such as
carbon nanotubes (CNT) and graphene, template synthesis
of inorganic nanoparticles. Based on this, we design and
synthesize BS derivatives (BSDs) with improved features.
We also study their self-assembly and we test their
improved features in the above mentioned applications.
BDSs self-assembling in nanotubes (Figure ) and fibers,
sometimes stimuli responsive, have been prepared that are
currently employed as templates to align nanoparticles and
to synthesize nanowires. Other derivatives containing
aromatic groups showed improved CNT dispersant ability.
TECHNIQUES
- Small Angle X-ray Scattering
- Dynamic Light Scattering
- Circular Dichroism
a
O
O
OH
Na
HO
O
HO
O
OH
OH
O
b
O- Na+
b
HO
OH
OH
Sodio Colato (NaC)
c
O
O- Na+
O
NH2
N
H
OH
1a -L-PheC
1b -L-PheC
Figure. Sugar (a) and aminoacid (c)
substituted sodium cholates (b) form
monodisperse nanotubes
COLLABORATIONS
- Division of Physical Chemistry, Lund University, SE
- Facultad de Ciencias, Univ. de Santiago de Compostela, SP
- Universidad de Costa Rica, S. Josè, Costa Rica
- Dep. of Chem. Eng., Ben-Gurion University, Beer-Sheva, IL
PUBLICATIONS
M. Gubitosi, L. Travaglini, M. C. di Gregorio, N. V. Pavel, J. V. Tato, S. Sennato, U. Olsson, K. Schillén, L.
Galantini Angew. Chem. Int. Ed. 2015, 54, 7018 –7021
L. Travaglini, A. D’Annibale, K. Schillén, U. Olsson, S. Sennato, N. V. Pavel, L. Galantini Chem. Commun.,
2012, 48, 12011–12013
M. C. di Gregorio, M. Varenik, M. Gubitosi, L. Travaglini, N. V. Pavel, A. Jover, F. Meijide, O. Regev and L.
Galantini RSC Adv., 2015, 5, 37800
http://www.chem.uniroma1.it/en/ricerca/linee-di-ricerca/linea-7670
Synthesis, characterization and spectroscopic
properties of supramolecular assembly
Università “La Sapienza”
Dipartimento di Chimica
P.le Aldo Moro 5 - 00185 Roma
Reference person: Mauro Giustini
Group Participants: Nicolae Viorel Pavel; Luciano Galantini; Marco D’Abramo
1. Reverse micelles hosting polynucleotides as
templating media for NP synthesis.
Polynucleotides of high molecular weight can be easily
solubilized in the water core of cationic reverse
micelles. In the presence of salts, polynucleotides
undergo strong compaction in their dimensions,
leading to ultracondensed forms with peculiar
spectroscopic properties. Metal ions such as Cd2+ or
Ni2+ strongly interact with polynucleotides in reverse
micelles and this interaction could be used to
synthetize semiconductor NP (CdS, for example) with
morphological characteristics that can be influenced
by the templating polynucleotides used.
2. Anthracyclines based gels: structure and
properties
Anthracyclines are a family of antibiotics often used in
cancer chemotherapy. Doxorubicin (DX, also called
Adriamycin) and its semisynthetic derivative
Epirubicyn (EPI), despite their extremely close
chemical formula, show in solution markedly different
behaviour. While in the presence of salts DX gives rise
to the formation of gels, EPI shows only the wellknown
self-association
phenomena
already
documented in literature.
3. Physico-Chemical properties of bacterial Reaction
Centre reconstituted in different media.
Bacterial Reaction Centre (RC) is an integral
membrane protein whose photochemical properties
are deeply influenced by the medium where the
protein is reconstituted. Kinetic and spectroscopic
studies performed on RC solubilized in buffer with
different salts and/or water activity will help in
expanding our knowledge on the early events of
photosynthesis.
TECHNIQUES
Steady-state and time resolved fluorescence; laserphotolysis equipment; UV-Vis-NIR spectroscopy.
PUBLICATIONS
M. Giustini et al. Phys. Chem. Chem. Phys. 13 (2011) 12293; M. Giustini et al. Biochemistry 53
(2014) 2197; M. Giustini et al. J. Am. Chem. Soc. 130 (2008) 9353
COLLABORATIONS
Prof. Gerardo Palazzo, Dipartimento di Chimica., Università di Bari, Italy
INSTITUTION WEBSITE: http://www.chem.uniroma1.it/dipartimento/persone/mauro-giustini
UNIVERSITY OF ROME “LA SAPIENZA”, Department of
Chemistry, Biopolymers and Biomaterials Lab
INNOVATIVE PROCESSES FOR THE FABRICATION
OF SCAFFOLDS FOR TISSUE ENGINEERING
Reference person: Andrea Barbetta
Group Participants: Marco Costantini, Cristina Colosi, Mariella Dentini, Piotr Garstecki, Wojciech
Święszkowski
IMAGES
1.Research line
Development of a new bioprinting paradigm
that allows the deposition of a low viscous
bioinks consisting of hydrogels precursors and
cells. The cell suspension is instantaneously
gelled contextually to the deposition. The cell
laden constructs find application in tissues
regeneration.
2. Research line
Fabrication of injectable monodisperse porous
microparticles through a novel method based
on microfluidics. The internal porous structure
(pore and interconnect dimensions) is
completely tailorable as well as microparticles
dimensions.
Such microparticles find application as cells
carriers that can be injected through a needle to
the desired site inside the human body
necessitating regeneration.
TECHNIQUES
-bioprinting
-microfluidics
-rheology
-X-ray m-tomography
-mechanical testing
1
Top row: (d) bioprinting of endothelial (HUVEC) cells
laden scaffolds; (a) photograph of the as printed
scaffold; 3D CT reconstruction of the final bioprinted
3D structure. Bottom row: (b) bioprinted HUVECs
forming a pre-vascular network; (c) HUVEC cells
forming a tubular structure at the periphery of a single
fiber; (d) fiber junctions showing interconnected
structures among HUVECs tubules.
2
Monodisperse porous microparticles produced via
microfluidics. Top row: emulsion droplets of decreasing
dimension. Bottom row: images of single gelled
microparticles of decreasing dimension.
PUBLICATIONS
C. Colosi, S.-R. Shin, V. Manoharan, S. Massa, M. Costantini, A. Barbetta, M. R. Dokmeci, M. Dentini, A. Khademhosseini
Advanced Materials, 2016, 28, 677-684
M. Costantini, C. Colosi, J. Jaroszewicz, A. Tosato, W. Swieszkowski, M. Dentini, P. Garstecki, A. Barbetta ACS
Applied Materials & Interfaces, 2015, 7, 23660-23671
C. Colosi, M. Costantini, R. Latini, S. Ciccarelli, A. Stampella, A. Barbetta, M. Massimi, L. Conti Devirgiliis, M. Dentini
Journal of Material Chemistry B, 2014, 2, 6779-6791
COLLABORATIONS
-Harvard-MIT Division of Health Sciences and Technology Cambridge ,
MA 02139 , USA
-Institute of Physical Chemistry, Polish Academy of Sciences, 01224 Warsaw, Poland
-Tissue Engineering Lab, Università Campus Bio-Medico di Roma, 00128 Rome, Italy
-Warsaw University of Technology, Faculty of Materials Science and Engineering, 02507 Warsaw, Polland
Interaction of Carbon Nanotubes, CNTs, with Biopolymers Reference person: Camillo La Mesa Group Participant Scientists: Franco Tardani, Gianfranco Risuleo, Anita Scipioni The outstanding properties of CNTs are hindered by their poor solubility in aqueous media. For this reason methods favoring their dispersibility are needed. Among possible dispersants, proteins, DNA, and lyotropic liquid crystals are used. DNA-­‐based dispersions, mostly, ensure high solubility and the possibility of further interactions with proteins, cells, and tissues. At high content of DNA, DNA/CNT complexes form liquid crystalline phases, with two-­‐dimensional order while at low DNA content dispersions are obtained. DNA-­‐CNT media are capable of interactions with other colloids, vesicles and biological tissues. Our work aims at determining the optimal working conditions for preparing biocompatible matrices; in particular, protein and DNA coverage of CNT surface are currently investigated. TECHNIQUES -­‐
Zeta potential -­‐
Dynamic Light Scattering -­‐
Circular Dichroism -­‐
NMR -­‐
Rheology COLLABORATIONS -­‐ Department of Chemistry, Calabria University, Italy -­‐ INSTEC, LA Habana, Cuba -­‐ IBMC, CNRS, Unistra, Strasbourgh, France -­‐ Inst. Paul Pascal, CNRS, Bordeaux, France PUBLICATIONS Muzi L, Tardani F, La Mesa C, Bonincontro A, Bianco A, Risuleo G. Nanotechnology. 2016, 27,155704. Tardani F, La Mesa C. Colloids Surf B Biointerfaces, 2014,121,165-­‐70. Bomboi F, Tardani F, Gazzoli D, Bonincontro A, La Mesa C. Colloids Surf B Biointerfaces, 2013,108,16-­‐22. Tardani F, Gentile L, Ranieri GA, La Mesa C. J. Phys. Chem. C, 2013, 117, 8556–8562. Tardani F, Strobbia, P, Scipioni, A, La Mesa C. RSC Adv., 2013, 3, 25917-­‐25923. Tardani F, La Mesa C. J. Phys. Chem. C, 2011, 115, 9424–9431. Tardani F, La Mesa C, Poulin P, Maugey M. J. Phys. Chem. C, 2012, 116, 9888–9894. Cat-­‐anionic vesicles for transfection technologies Reference person: Camillo La Mesa Group Participant Scientists: Gianfranco Risuleo, Anita Scipioni Mixing cationic and anionic surfactant in non stoichiometric ratios provides size-­‐ and charge-­‐modulated vesicles. After thermal cycling, vesicles with a single bi-­‐ layer can be obtained. Proteins, RNA, or DNA can be accommodated on the vesicle outer surface by electrostatic interactions. Vesicles and corresponding association complexes with biomacromolecules are characterized by DLS, z-­‐potential, SAXS and circular dichroism spectroscopy. Size and properties of the resulting adducts are suitable for use in transfection technologies. It is known, in fact, that the experimentally determined cytotoxicity of cat-­‐anionic vesicles is moderate and always much lower than the single surfactants that form them. TECHNIQUES -­‐
Zeta potential -­‐
Dynamic Light Scattering -­‐
Circular Dichroism -­‐
Cytotoxicity screening -­‐
SAXS COLLABORATIONS -­‐ Department of Chemistry, Calabria University, Italy -­‐ Institut de Quimica Avancada de Catalunya, CSIC, Spain -­‐ INSTEC, LA Habana, Cuba PUBLICATIONS Pucci C, Pérez L, La Mesa C, Pons R. Soft Matter, 2014, 10, 9657-­‐9667. Sciscione F, Pucci C, La Mesa C, Langmuir, 2014, 30, 2810-­‐2819. Pucci C, Barbetta A, Sciscione F, Tardani F, La Mesa C, J Phys Chem B, 2014, 118, 557-­‐566. Russo L, Berardi V, Tardani F, La Mesa C, Risuleo G. Biomed Res Int. 2013, 734596. Pucci C, Scipioni, A, La Mesa C, Soft Matter, 2012, 8, 9669-­‐9675. Barbetta A, Pucci C, Tardani F, Andreozzi P, La Mesa C, J Phys Chem B, 2011, 115, 12751-­‐12758. Anion recognition through the use of
lipophilic receptor/micelle systems
Reference person: Antonella Dalla Cort
Group Participants: Luca Leoni
The use of micelles to transpose lipophilic receptors into
an aqueous environment is a valuable and versatile tool.
Receptors based on metal salophen complexes have been
developed in the years by this group, exploring different
functionalisation of the basic skeleton to make them
efficient receptors for anions and ion pairs in organic
solvents, but also in water through the use of micelles.
We have recently reported that Receptor1, which is easily
synthesized through the one-pot reaction of 1,2phenylenediamine with two moles of salicylaldehyde in
the presence of uranyl acetate, can be transposed into
water with the help of CTABr (cetyltrimethylammonium
bromide) micelles. Remarkably the supramolecular
receptor/micelle assembly exhibits an affinity for fluoride
of the order of 104 M−1 which is one of the highest values
ever reported for fluoride binding by a neutral receptor in
water and, very interestingly, higher than the one
observed with the hydro-soluble version of Receptor 1.
Thus the group works to the development of simple and
efficient supramolecular devices to bind analytes in water
using lipophilic receptors/micelle systems.
TECHNIQUES
NMR
Uv-vis spectroscopy
Organic synthesis
COLLABORATIONS
Universitè Libre de Bruxelles
Universidade de Barcelona
PUBLICATIONS
F. Keymeulen, P. De Bernardin, I. Giannicchi, L. Galantini, K. Bartik, A. Dalla Cort Org. Biomol. Chem.,
2015, 13, 2437-2443
F. Keymeulen, P. De Bernardin, A. Dalla Cort, K. Bartik J. Phys. Chem. B 2013, 117, 11654−11659.
http://www.chem.uniroma1.it/ricerca/linee-di-ricerca/linea-7667