What is nanotechnology? - Center For Dermal Research

Transcription

Science at the heart of medicine
The Emerging Role of Nanotechnology
in the Diagnosis, Prevention, and
Treatment of Skin Disease
Adam Friedman, MD, FAAD
Assistant Professor of Dermatology
Assistant Professor of Physiology and Biophysics
Director of Dermatologic Research
COI
• Co-inventor of technologies TBD
• Consulting/Ad board: Sanova works, Prodigy,
Oakstone institute, Liquidia, Loreal, Amgen, Onset,
Aveeno, GSK
• Textbook: Nanotechnology and Dermatology
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Agenda
• Skin - The Impenetrable Target
• Nanotechnology - A Brief Introduction
• Nanodermatology
> Research Roundup
• Nanotechnology Safety and Regulatory
Oversight
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Stratum Corneum and Topical Therapy
• Low permeability to water
soluble drugs due to lipid
enriched bilayer and
convoluted extracellular
pathway
• What lipid species provide
this?
> Ceramides
> Cholesterol
> Free fatty acids
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All skin not equal:
Different sites = Different absorption
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= .1-10% sa
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keratin
lipid
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Tricks to enhance penetration
• Solvents and surfactants
> Ethanol, acetone, detergents
> Defects in keratinocytes and rearranges bilayer
• Stripping
> Adhesive tape, cyanoacrylate glue-> increases
transepidermal water loss and reduces lipid
adhesion
• Electroporation
> Ultrashort pulses with large voltages
> Induces structural rearrangement and leads to pore
formation
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What is nanotechnology?
• Nanotechnology:
> “The understanding and control of matter at dimensions
between approximately 1 and 100 nanometers, where
unique phenomena enable novel applications.”1
1 The
National Nanotechnology Initiative, Strategic
Plan 2007
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~ 1,700,000,000 nm
Head to Head
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What’s the big (or little) deal?
• At this size, matter behaves differently
> As size , surface area relative to volume grows
exponentially
• Chemical properties are altered or even magnified:
hydrophobic, hydrophilic, or electrically charged
• The optical qualities of matter can also be manipulated
at the nano-scale.
• Physical properties change at the nano-level
Three properties of matter--chemical, optical, and physical--can be
manipulated and exploited
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Types of Nanotechnology
• Nanomaterials
> Nanostructured
fluids
> Nanocomposites
> Nanostructured
solids
• Nanocomputers
• Nanomachines
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Nanomaterials: Overview
• Plenty already out there
> Nanoparticles
> Nanoemulsions
> Nanopigments
> Nanomagnets
> Quantum dots
> Zeolites
> Nanotennis balls
> Nanofibers
> Nanoceramics
> Fullerenes
Current Nanotechnology Products
Skin care
Sunscreens, antibacterial cleansers, makeup,
toothpaste, shampoo, lipstick, face powder,
blush, anti-wrinkle cream, eye shadow,
perfume, aftershave lotion, appliances, selfcleaning surfaces
Food
Nano-nutraceuticals
Household
Antibacterial cleansers, pet litter
Clothing
Sporting goods, shoe inserts
Automotive
Tires, engines, steppers
Military
Armor, camouflague, radioprotection
Electronics
LED screens on digital cameras
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Databases
http://nano.taenk.dk/
https://www.nanomaterialregistry.org/
http://www.nanotechproject.org/cpi/
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Nanoparticles: A Generic Term
•
Small (obviously) object that
behaves as a whole unit in terms
of its transport and properties
> Can mix and match different
physical, chemical, and
optical properties at the
nanoscale
• Disperse vs aggregate
• Polymerize vs
deconstruct
• Solid vs hollow
• Increase or decrease cell
uptake
• Immediate vs controlled
release
• Targeting
> Possible to develop infinite
variety of applications
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Nanoparticles in OTC Dermatology
• Nanoparticles already have a role in cosmetics based on
current marketplace
• 54 np products 2005, 1015 in 2009, ?? 2013
> L’oreal has over 200 patents in nanotechnology!
• Facial foundations: Create illusion of smooth skin surface
• Pigmented cosmetics: Eye shadow, blush
– Pigment blending with smaller size np allow better complexion
color matching
– Can create “invisible” layer, no powder particles seen on skin
surface
• Moisturizers: Enhance skin barrier
US Patent 6335022; Simonnet; J._T., Sonneville; O., Legret; S.; L’Oreal, 1999.
www.nanoinstitute.com
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Nanoemulsions
• Classic: Oil is dispersed in water
> Lipophilic interior + Hydrophilic exterior
• Transport hydrophobic materials into the skin
– Lipids, anti-oxidants, retinoids, steroids
• As emulsified particle size , the “nano” favorable properties
emerge:
> Good sensory texture
> Invisible
> Hydrophilic exterior allows for rapid penetration into the
outer layers of the skin and hair
> Do not undergo phase separation
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A Picture is Worth….
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Nanotechnology and Anti-aging
• Example: Coenzyme Q10
> Potent antioxidant as an
electron carrier
> Susceptible to
photodegradation/
Inconsistent skin
penetration
> Nanoemulsions improved
• Incorporation into
suspension
• Biphasic release
profile
• Penetration
Biofactors. 2008;32(1):237-243.
Coenzyme Q10
Ascorbyl palmitate
Omega unsaturated
fatty acids
Retinoids
Alpha-lipoic acid
Polyphenols
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Nanotechnology and Hair Care
•
•
Hair dye: Nanostructured
liposomal emollients
> Penetrate the hair shaft
better
> Protect against degradation
> Controlled and sustained
release
Conditioners: Silicone
nanoemulsions
> Nonionic surfactant
• Promotes the delivery of
this silicone oil from the
scalp to the hair shaft
> Thermodynamic stability
> Improved silicone oil
deposition on hair surfaces.
Toll J Invest Dermatol (2004)
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Consumer Product
Cosmetics
Bionova Nano Skin Tech
Range
Serge Lutens Blusher
Manufacturer
Nanotechnology Contents
BarneyÕs New York
ÒNano complexesÓ
BarneyÕs New York
Coco Mademoiselle Fresh
Moisturizer Mist
Defy: Age Management
Exfoliator
After Glow Brush
Blush colores
Sunforgettable Corrector
Colores
Moisturizing Dermatone
Lips Ôn Face Protection
Cr me
Dr Brandt New lineless
Cream
Renutriv range
Revitalift Double Lifting
Hydra Flash Bronzer
Renergie Microlift Eye
Chanel
ÒNano dispersion
technologyÓ
Nanoemulsion
Bellapelle Skin Studio
Fullerenes
ColoreScience
ColoreScience
ColoreScience
Dermatone
Nanovitamins A and E
Nanovitamins A and E
Titanium Dioxide and Zinc
Oxide
Zinc Oxide
Dr Brandt
Fullerences
EsteÕe Lauder
LÕOreal Paris USA
Lancome
Lancome
Revlon Colorstay Stay
Natural Powder
Revlon
Novasomes
Nanosomes
Nanocapsules
Nanoparticles made of
silicon and protein
Aluminum
Who is the leader?
Raj S . J Pharm Bioall Sci 2012;4:186-93
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What’s being used?
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Simple benefits of nanomaterals
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Simple benefits of nanocosmetics
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Nano for Medical Dermatology
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Nanotechnology for the Prevention,
Diagnosis and Treatment of Skin Cancer
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Nanopigments
• Rely on the property of
particle size rather than
photochemical interaction to
scatter/absorb light
> Can be used to generate
brilliant colors
• Samsung TVs
– The Official TV of
the NFL!
> Can be used to hide
color
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Nanopigments
• Sunblocks
> SunVex Dailywear
Lotions
> D-Fense Antioxidant
Moisturizer with SPF 17
> Cotz SPF 58
> Daily Sun Defense SPF
20
> Solar Rx SPF 30+ NanoZinc Oxide Sunblock
> Sport UV Defense SPF
45
> ZinClear Nano Zinc Oxide
www.koboproducts.com
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Molecular Diagnosis of Melanoma
• Melanoma is a heterogeneous disease
> Different mechanisms with different gene mutations
> GREAT NEED to identify the molecular signatures for
each melanoma patient
• Personalized medicine
– BRAF inhibitor for for those with a BRAF mutation
> Nanotechnology?
• Microcantilever arrays using a BRAF-specific
oligonucleotide probe
– Detect mutated BRAF at the concentration of 500 pM
but normal BRAF at a 50-fold higher concentration
– No PCR needed
Nat Nanotechnol. 2013;8(2):125-129.
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Quantum Dots
•
•
•
Semiconductor nanocrystals
> Semiconductor core
encapsulated by another
shell
• 3rd silica shell for water
solubility
Unique optical and electronic
properties such as:
> Tunable fluorescence
emission from visible to
infrared wavelengths
> Range and very high levels
of brightness
Can be covalently linked to
biorecognition molecules
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QD for the Diagnosis of Melanoma
• PEG-COOH capped highly
fluorescent CdSe/ZnS
core/shell QDs conjugated
with antibody against CD146
> + cells = high brightness,
photostability, and
specificity.
• Coculture system to test QDs
conjugated with antibodies
(Ab732 or Ab733) against
melanoma.
> Distinguished between
melanoma and
melanocytes
Analyst. 2012;137(6):1440-1445
Photochem Photobiol Sci. 2011;10(5):842-851
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Vom paper
• Volatile organic compounds (VOC) distinct in cancer
• Attempts to distinguish melanoma from nevi using
chromatography/mass spectrometry and gas sensor array
• Nanotechnology-enabled e-nose system - 100s of sensors
> Functionalized DNA-coated carbon nanotube sensors
• Qualitative and quantitative differences in volatile sulfur
compounds such as dimethylsulfone, dimethyldi- and trisulfide
> Owing to altered metabolism
• Differences in VOCs from normal and melanoma cells, as well as
different types of melanoma cells by their total expressed VOCs.
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Going Mainstream?
Episode 8.3 “Loophole”
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Nanomagnets
• Nano sized magnetic
materials no longer
exhibit a net
magnetic force
> Paramagnetic
• Allows for magnetic
field directed
imaging/therapy
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Diagnosis/treatment of melanoma?
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Gold Nanoparticles
• Coupled with antibody
• Binds to cancer cells
• The gold absorbs laser
emission
> Near- infrared
• Allows for selective
photothermolysis of
tumor
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Targeted Photothermal Ablation of Murine Melanomas with
Melanocyte-Stimulating Hormone Analog–Conjugated Hollow Gold
Nanospheres
Lui W et al Clinical Cancer Research 2009: 15; 876
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Heavy chain of human ferritin-based
nanoplatform theranostic
Vannuci et al. International Journal of Nanomedicine 2012:7 1489-1509
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EGFR knockdown by spherical nucleic acid
nanoparticle conjugates correlates with biological
effects in vivo
Suppresses downstream ERK
phosphorylation, and reduces
epidermal thickness by ~40%.
Zeng, D et al. Proc Natl Acad Sci U S A. 2012 Jul 24;109(30):11975-80.
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The mechanism of RNA interference via
exogenous siRNA
siRNAs (21-23
nucleotides)
siRNAcontaining
nanoparticles
Endosomal
escape
Formation of
RISC-siRNA
complex
Formation of
RISC-mRNA
complex
Cleavage of
sense strand
Internalization
Degradation of
target mRNA
J Drugs Dermatol. 2012; 11(11): 1373-1377
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Barriers to siRNA utility
• Degradation
• Uptake
• Immunogenicity
• Nano is the solution!
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siRNA-np and wound healing
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siRNA nanoparticles targeting FL2 mediated
microtubule cleavage accelerates wound healing
Day 2
Day 3
Day 6
Day 8
Day 10
4 mm
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Histopathology (H&E)
Control
FL2 si-NP
4x
10x
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Histopathology (trichrome)
Control
FL2 si-NP
4x
40x
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Nanoparticles for the Prevention of Contact
Dermatitis
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Nanoparticles reduce nickel allergy by
capturing metal ions
• Calcium carbonate or
calcium phosphate
nanoparticles
• The nanoparticles
captured nickel ions by
cation exchange
> Remained on the
surface of the skin
> Removed by simple
washing with water.
Vemula P et al .Nat Nanotechnol. 2011;6(5):291-5.
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Nanoparticles reduce nickel allergy by
capturing metal ions
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Acne Vulgaris: An Ideal Nano Target?
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Follicular targeting
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Nanotechnology as a vehicle of improved
delivery
Clindamycin
Tea tree oil
Salicylic acid
Cyproterone acetate
Finasteride
Benzoyl peroxide
All-trans retinoic acid
Benzoyl peroxide
Cyproterone acetate
Isotretinoin
Castro GA. Expert Opin. Drug Deliv. (2008) 5(6)
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Almost there…
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What’s New: Triclosan Nanoparticles
• Potent antimicrobial
• ? Risks with hormone
disruption
> “FDA is reviewing all
of the available
evidence.”
• Improved delivery and
skin retention with nps?
European Journal of Pharmaceutics and Biopharmaceutics Volume 79, Issue 1 2011 102 - 107
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What’s New: RU-58841 and Cyproterone
acetate Nanoparticles
• Big Idea: Topical Antiandrogens
> Decrease epithelial
turnover and sebum
production
> Concentrate drugs in
pilosebaceous unit
> Avoid SE in systemic
administration
• Neither ingredients approved
in US
• Studies limited - in vitro and
ex vivo
JID 2009; 129: 1868-1877
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What’s New: Anti-androgen Nitric oxidedonating Nanoparticle Gel
• NO is a lipophilic,
diatomic, free radical
• Inhibits androgen and
PGD2 synthesis
> Tryosine nitration of
cyclooxygenase
> Inhibition of p450
enzymes
• CYP11A1 and
CYP17A1
Novan white paper
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What’s New: Anti-Acne Nanoemulsions
Disrupts outer lipid
membrane
www.nanobio.com
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What’s New: Lauric Acid Liposomes
• LA is an amphiphilic molecule
consisting of a hydrophobic
hydrocarbon chain +
hydrophilic carboxylic acid
headgroup.
• >BPO against P. acnes
• But!
> Poor water solubility
• Good candidate for bilayered
wall of liposomes
Yang D. Biomaterials 2009; 30(30): 6035-6040
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What’s New: Chitosan Nanoparticles
•
•
Natural polysaccharide biopolymer
Antimicrobial properties
> Polycationic character at
weakly acidic pH
• Favors interaction with
negatively-charged
Higher surface
to volume
microbial
cell ratio = higher surface charge density = increased
membranes/walls microbial affinity
– Decreased osmotic
stability
– Membrane disruption
» Eventual leakage of
intracellular
elements
• Enter the nuclei
– Bind to microbial DNA
> Chelator : Metals, Lipids
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P. acnes is susceptible to chitosan
Champer J et al AMB Express. 2013 6;3(1):37.
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350 nm
Friedman,
et heart
al. JofInvest
Dermatol. 2013;133(5):1231-9.
Science AJ
at the
medicine
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SEM
TEM (low power)
P. acnes
P. acnes
+ NP
P. acnes
+ BP 0.1%
P. acnes
+ [BP0.1%] NP
Friedman, AJ et al. J Invest Dermatol. 2013;133(5):1231-9.
TEM (high power)
a. Nanoparticle inhibition of P.
acnes induction of IL-6 from human
keratinocytes
Friedman, AJ et al. J Invest Dermatol. 2013;133(5):1231-9.
b. MTT assay with human keratinocytes
Can We “ESKAPE” This Crisis With Nano?
• Multidrug-resistant (MDR) pathogens are
rising at an alarming rate
• ‘ESKAPE’ pathogens
> Enterococcus faecalis, Staphylococcus
aureus, Klebsiella pneumoniae,
Acinetobacter baumannii,
Pseudomonas aeruginosa and
Enterobacter spp.
> Emphasize the fact that they ‘escape’
the effects of many antibacterial agents.
• Public health threat of epidemic
proportions!!
Boucher HW et al. Clinical Infectious Diseases. 2009;48(1):1-12.
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Nano-cillin: Approach 1
1. Drug loaded nanoparticles (Nps)
1. Physical encapsulation,
adsorption, or chemical
conjugation
> Benefits
• Improve serum
solubility
• Prolong systemic
circulation lifetime
• Sustained and
controlled release
– Tissues and cells
specific deliver
•
•
Concurrent therapy
Deliver previously
undeliverable actives
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Nano-encapsulated drugs galore…
• Enhanced antimicrobial action topically
> Tobramycin
> Silver Sulfadiazine
> Doxycycline
> Azole antifungals
> Terbinafine
> Penciclovir
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Amphotericin Nanoparticles
Content Release Profile of
Ampho-nps
Nanomedicine. Published online 6/14/13.
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Day 0
Day 3
Day 5
Infected
Control
Ampho-Sol
Ampho-np
Amphotericin-np effectively treat C. albicans infected
burn model
Nanomedicine. Published online 6/14/13.
Day 7
Day 9
Day 11
Nitric Oxide Nanoparticles: A Hybrid
Technology
• Novel composite
material
> Combines the robust,
malleable, and
porous properties of
silane-based sol-gel
matrices with the
thermal reduction
potential of sugar
glasses1,2
1Ray
et al. J Am Chem Soc 200 124: 7270-1
et al. Nitric Oxide 2008 19(1): 12-20.
2Friedman
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Topical NO Delivery
• Anti-infective
• Wound healing accelerant
• Pro-erectile agent
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Mechanisms of Direct Antimicrobial Action:
Cytostatic and Cytotoxic
Jones ML, et al. Appl Microbiol Biotechnol 2010 Aug 3. [Epub ahead of print]
Fang FC. J Clin Invest. 1997 Jun 15;99(12):2818-25
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NO-np Accelerate Wound Closure in MRSA
Infected Excisional Wound
Martinez et al. J Invest Dermatol. 2009: 129; 2463–2469
NO-np Accelerate Intramuscular Abscess
Clearance
Control
Vancomycin
NO-np TP
NO-np IL
Schairer D.Virulence 2012; 3(1):1-6.
A.
Control
Vancomycin
a.
b.
4x
10x
B.
NO-np TP
NO-np IL
NO-np Accelerate Wound Closure in A. baumanii
Infected Excisional Wound
Mihu et al, Virulence. 2010; 1(2): 1-6.
3/28/12
7/31/12
R leg
L leg
JAMA Dermatol. 2013. In Press
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NO-np Effectively Treat Candidal Burns
Front. Microbio. 2012;3:193.
Antimicrobial Nanomaterials: Approach #2
Ag-np
• Rely on innate nano-scaled
antimicrobial activity
> Minerals/metals
• Silver
• Copper
• Magnesium
• Zinc
> Carbohydrates/lipids
• Chitosan
• Soybean oil
Chitosan-np
soybean-np
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MOA of Nanosilver
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Nanotechnology for Procedural Dermatology
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Nanoneedles
120 mm
SPE™
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Nanosutures
Tsao S, et al. BJD. 2012; 166(3):555-563
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Tsao S, et al. BJD. 2012; 166(3):555-563
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Nano-BoNTA
•
•
Big idea: Needle-less Botox
At least two companies
> Transdermal Corp., Birmingham,
Michigan
• Ionic nanoparticle
technology
– Mixed micelles +
penetration enhancers
> Revance Therapeutics, Newark,
California
• Combination 150kD BoNTA
+ peptidyl macromolecule
transport system.
– Bound to BoNTA through
electrostatic interactions
•
FDA trials underway
> So far so good
Revance Therapeutics. http://www.revance.com/385-rt0010lcl?side.
Trasdermal Corp. http://www.transdermalcorp.com/
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Hyperhidrosis; Before and After ( at week 16)
Botulinum toxin type A
gel BID x 1 week;
6 units per day (42
units at the end of the
study).
www.transdermalcorp.com
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Nanoproducts in Development
• Topical g-amino butyric
acid (GABA)
• Topical hyaluronic acid
• Topical siRNA
• Topical vaccines
• Topical botulinum toxin
• Topical sirolimus
• Topical minoxidil
•
•
•
•
•
Topical anesthetics
Topical chemoagents
Topical melanin
Topical antioxidants
Topical pro-erectogenic
agents
• Topical enzyme
replacement
• Scarless sutures
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Nanotechnology Safety
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Nano-scare??
New Products Bring Side Effect:
Nanophobia
By NATASHA SINGER December 4, 2008
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Safety
• Theoretical standpoint,
nanoparticles are predicted
to be harmful.
• As size , the surface to
volume ratio exponentially 
, making nanosized
materials that are
potentially/predicted to be
toxic and highly reactive
even more dangerous.
> As size , its ability to
penetrate most if not all,
human tissues, also
exponentially 
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Attention:
Game
Changer!
ACS nano paper
• “Our findings suggest that differentiating material
hazards by size can be misleading.“
• “We find that all silver, whether nano- or macro-scale,
generates AgNPs when exposed to humid air or
water”.
• “The fact that nanoparticles are spontaneously
produced suggests that Ag and Cu NPs have been
present as incidental nanomaterials and in contact
with humans for several thousand years.”
Glover et al. ACS Nano. Online 10/11
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Sunscreen and Nanotechnology
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Care to comment Nancy?
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A look back…
4/2011
“Although more research is needed to solidify
the environmental and occupational risks, the
Nanodermatology Society believes
that nano-based sunscreens do not pose
6/2011
serious health risks to consumers”
“Zinc and titanium nanoparticles
are effective in sunscreens,
but avoid sprays and powders”
6/2011
“FDA takes first step toward
greater regulatory certainty
around nanotechnology”
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FDA Draft Guidance 4/2012
• Safety assessment of nanomaterials when used in
cosmetic products:
> The legal requirements for cosmetics manufactured
using nanomaterials
• Cosmetics not subject to premarket approval,
– Legally responsible for the safety of their products
> Modification of standard safety tests
• Companies are encouraged to consult the FDA
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The NDS Responds
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The AAD Responds
• “While widespread use of nanotechnology in medicine
is currently under evaluation, one of the main benefits
of nanoparticles in sunscreens is that the small
molecules can provide more protection and more even
coverage on the skin surface than larger particles,”
said Dr. Siegel. “Considerable research on the use of
nanoparticles on healthy, undamaged skin has shown
that the stratum corneum, the outermost layer of the
skin, is an effective barrier to preventing the entry of
nanoparticles into the deeper layers of the skin.”
• 5.16.2012
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Progress?
8.2012
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And now what?
• 5/8/2013
> Open forum - public invite
• 6/ 2013
• Cosmetic Good Manufacturing Practices
> Draft Guidance – no nano?
• 8/26/2013
> EPA has issued its final significant new use rules (SNURs) for
17 substances, mostly constituting substances at the
nanoscale.
> If intend to manufacture, or process any of these 17 chemical
substances for significant new use --> notify EPA at least 90
days before commencing that activity.
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Worldwide directions for the future
•
•
Europe
> 7/ 11/2013: European Cosmetics Regulation EC No. 1223/2009 fully
enforced across EU.
> Definition: Nanomaterial means an insoluble or biopersistent
and intentionally manufactured material with one or more
external dimensions, or an internal structure, on the scale from
1 to 100 nm.
> 3 requirements for industry
• Notification to the European Commission (EC) 6 months prior to
placing the product on the market
• Safety assessment of the cosmetic product with particular
attention to nanomaterials
• Labeling of ingredients that are nanomaterials.
Australia - Government rejected mandatory labeling of nanomaterials in
sunscreens - postponed to re-discuss in 2013
1. H.R. 5786,
2. Regulation (EC) No. 1223/2009, November 30, 2009
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The Nanodermatology Society
http://www.nanodermsociety.org/membership.php
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The Dermatology Foundation
v
has supported & advanced my career.
Thank you for your attention
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What is nanotechnology? - Center For Dermal Research

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