Technology for Long Last Senses
Assoc. Prof. Ubonthip Nimmannit, Ph.D.
April 2nd, 2010
National Nanotechnology Center
NSTDA Pathumthani, Thailand
Fragrances
• Topnote
• Middle note
• Lasting note (Base note)
Topnote
• First impression
• High volatility, coefficients ranging 1-14
• No residual scent after 2 h
– Citrus, fruity, green note
– Ginger, galanga, cardamom
Middle note
• Establishing the whole fragrance
• Medium volatility, coefficients ranging
15-60
• Last for 2-6 h
– Jasmine, rose, aldehyde, spicy note
– Tuberose, coriander
Lasting note (Basic note or Fixer)
• Low volatile fixatives, coefficients
ranging 61-100
• Last for more than 6 h
– Oakmoss, woody note, animal note, civet
absolute, myrrh, velvety balsamic scent
Basic note/ Fixation
– Musk ambrette
– Ambergris extract
– Ethyl vanillin/ vanillin
– Methyl nonyl acetaldehyde
– Fixateur 404
Persistence of Perfumes
• Coefficient: ↑ nature of evaporation
↓ value of the threshold concentration
Volatility
• Odor intensity
• Threshold value
• Odor tonality
Stability of Fragrance
• Change of odor
• Change of color
Stability factors
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Oxygen
Light
Temperature
Humidity
pH of product
Microcapsules
• Small particles (1-100 μm)
• Active agent surrounded by polymeric
membrane
• Protect from oxidation (by heat, light,
humidity, exposure to other substances)
• Prevent evaporation
• Control release rate
Microcapsules
• Released by
– Mechanical
– Temperature
– Diffusion
– pH
– Biodegradation
– Dissolution
Techniques of encapsulation
(Micro/ Nano)
• Phase separation techniques
• Interfacial polymerization techniques
• Mechanical techniques
Phase separation techniques
• Aqueous phase separation
– Simple coacervation
– Complex coacervation
• Nonaqueous phase separation
– Non solvent addition
– Temperature reduction
Complex coacervation
Positive charge polymer-negative charge polymer
Phase separation
Colloidal rich phase + equilibrium liquid
stirred
Microcapsules
Nanocapsules
dry
Interfacial Polymerization Technique
Monomer A
+
Monomer B
(Hydrophobic liquid)
(Hydrophilic liquid)
Emulsifying
Polymer AB
Stirring
Microcapsules +
by product
Mechanical Techniques
• Spray dry
• Atomization
• etc.
Selection of the technique and shell material
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Application of products
Physical and chemical stability
Concentration
Desire particle size
Release mechanism
Manufacturing cost
Oil phase (HMDI)
+
Aqueous phase 1 (PVA)
Formation of oil/water emulsion
Aqueous phase 2 (PEG 400, DBTDL)
Urethane formation
Aqueous phase 3 (EDA)
Polymerization and shell formation
Urea formation
Aqueous phase 4 (HYD)
Urea formation
Separation/Washing
Microencapsulation process of limonene by interfacial polymerization.
Rodrigues, et al., Ind. Eng. Chem. Res. 2008, 47, 4142–4147
Optical microscopy of microcapsules solution. Magnification: (a) 20x (b) 100x.
Textile Impregnated with Microcapsules Characterization. SEM Analysis
Rodrigues, et al., Ind. Eng. Chem. Res. 2008, 47, 4142–4147
Macrocapsules
• Diameter over 1000 mm
Polysulfone capsules containing different vanillin concentrations.
show a different porosity distribution,
T. Gumํ et al. / Desalination 245 (2009) 769–775
Polymeric microspheres
• Fragrance incorporated in the polymer
– Controlled by
• Initial loading of fragrance
• Ability of fragrance to diffuse through polymeric
barrier
– Driving force
• Interaction between fragrance molecule and
polymer matrix
• Vapor pressure of fragrance
SEMandTEMimages of spheres obtained with the starting polymer
concentrations of (a) 2000–16,000 ppm, (b) 18,000ppmand (c) 24,000–
28,000 ppm.
(a) SEM, (b) TEM and (c) AFM images of menthol-encapsulated polymeric
nanoparticle suspension (polymer blend : EC, HPMC, PV(OH)
A. Sansukcharearnpon et al. / Int J Pharm xxx (2010) xxx–xxx
Multiarm star-block copolymer
• Multiarm star-block copolymer compared to
dendrimer
– Less complex synthesis
– Less time consuming
– Lower cost
Limitation
– Lower loading capacity than dendrimer
Multiarm star-block copolymer
Hydrophobic arms
Hydrophilic arms
Hyperbranched core structure
Amphiphilic multiarm star-block copolymers with a hydrophilic inner and hydrophobic outer
shell (top) and with a hydrophobic inner and hydrophilic outer shell (bottom).
Ternat et al., Macromolecules, Vol. 41, No. 19, 2008
Multiarm star-block copolymer
Average structures of the Boltorn H40 core and
amphiphilic multiarm star-block copolymers
H40-(PnBuMA)p-b-(PPEGMA)q and H40-(PCL)pb-(PAA)q.
Ternat et al., Macromolecules, Vol. 41, No. 19, 2008
Multiarm star-block copolymer
Benzyl acetate/ H40-(PCL)24-b-(PAA)82
Benzyl acetate
Comparison of the evaporation rates of benzyl acetate from an aqueous
solution (containing 5% of ethanol) in the presence and absence of amphiphilic
multiarm star-block copolymer H40-(PCL)24-b-(PAA)82.
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Alginate complex capsules containing
eucalyptus oil
Interfacial insolubilization reaction
Release by crashing the capsule between
fingers
Closed capsule wall
Optimum condition
– Concentration of alginate
– Concentration of calcium salt
– Cross-linking time
The capsules were prepared at
concentrations of 1.5% sodium
alginate and 1.0% calcium chloride,
and the cross-linking time of 20 min.
Microphotographs of alginate complex capsules before (a) and after (b) the
hardening process (/80).
C.P. Chang, T. Dobashi / Colloids and Surfaces B: Biointerfaces 32 (2003) 257/262
Time courses of oil release from capsules at incubation process for the samples
prepared at various conditions: At different concentrations of sodium alginate at
constant calcium chloride concentration of 1 w/v% at cross-linking time of 20
min.
The symbols (circle), (triangle), (square) and (diamond) denote concentrations of
sodium alginate of 0.25, 0.50, 1.0 and 2.0%, respectively.
Light induced controlled release of fragrances
Alkyl phenyl ketones serve as delivery systems for fragrance molecules
upon exposure to natural sunlight
Preparation of alginate nanocapsules
containing turmeric oil
Sodium alginate crosslink with calcium chloride
alginate nanocapsule
Lertsutthiwong P., Noomun K., Jongaroonngamsang N., Rojsitthisak P., Nimmannit U. 2008.
Preparation of alginate nanocapsules containing turmeric oil. Carbohydrate Polymers. 74. 209–214.
Morphology and size of turmeric oil-loaded alginate nanocapsules
TEM characterization of nanocapsules, indicating an average size of about 95 nm.
Thank you