1

Nanoencapsulation
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Encapsulation

Microencapsulation Molecular encapsulation

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Encapsulation
Application
Cosmetotextile is a textile article containing a substance or a
preparation that is released over time on different
superficial parts of the human body, notably on skin, and
claiming special properties such as cleaning, perfuming,
changing appearance, protecting, keeping in good condition
or correcting of body odors.
 Nanoencapsulation 4

 Nanoencapsulation is the coating of various substances

within another material at sizes on the nano scale.
This technique is already commonplace within a
range of industries but it is accepted that only around
10% of potential applications are being exploited.
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Microencapsulation

Microencapsulation is described
as a process of enclosing micron-
size particles of solids or droplets
of liquids or gasses in an inert
shell, which in turns isolates and
protects then from the external
environment.
 6

The properties of microcapsules had to be adapted to the

requirements of textile processing methods and uses of
final products:
– sizes,
– shapes,
– wall materials (urea-formaldehyde or
melamine- aldehyde resins,
cellulose derivatives),
– way of application (coating, covalent bonding),
– active substance release mechanisms.
 7

Mechanisms by which the core

material is released:
Rupture of the capsule wall,
– Mechanical rupture of the wall
– Dissolution of the wall
– Melting of the wall (thermal or
UV/Vis radiation)
– Biodegradation
– Enzymatic degradation
Diffusion through the wall
– Slow release
– Controlled release
 8

Grafting of Ethylcellulose
Microcapsules onto Cotton Fibres [1,2]

Rosemary oil was encapsulated in ethylcellulose

(EC) microcapsules using phase separation method
[3]. Prepared capsules were analysed by SEM and
Confocal Laser Fluorescence Microscopy.

1 Babtsov V, Shapiro Y., Kvitnitsky E., US Patent 6,932,984, 2005

2 Voncina B, et al, Carbohydrate Polymers, in press
 9

• Regular spherical shape

• The yield of the process was about
75%.
•Microcapsules in the 10-90 μm size
range were obtained (depends on
stirring speed)

Oil Stirrer speed, Yield, Diameter ± SDa,

rpm % μm
Limonene 350 57 75±12
Rosemary oil 350 68 72±8
500 58 43±13
750 67 42±5.6
1000 50 20±5.1
Without 350 75 78±15

[3] Badulescu R, et al, MEDTEX07, Bolton, UK

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 The oil content of the dried microcapsules was 20-30%.
 The average “empty space” in capsule is 40%

Confocal laser
fluorescence
microscope
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During the thermofixation at 120°C, simultaneously three
reactions of esterification can occur: anchoring or binding
ethylcellulose to hydroxyl groups of cellulose, crosslinking of
cellulose and crosslinking of ethyl cellulose.
O COOH O
Cel O C CH2 CH CH CH2 C O
H2C COOH l EC COOH
Cell, EC
HC O COOH
COOH HC Cel O O
Catalyst, H
HCOOH l O C CH2 CH CH CH2 C Cell
2C COOH
O COOH O
COOH
EC O C CH2 CH CH CH2 C O EC
COOH
 12

Molecular encapsulation

Involves all intermolecular interactions where covalent bonds are not established
between the interacting species - SUPRAMOLECULAR CHEMISTRY [7]

The majority of these interactions are of the

host-guest type.

Among all potential hosts, the

cyclodextrins (CD) are to be the
most important ones

[4] Szejtli J., Chem Rev 1998, 98, 1743-1753

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Structure and dimensions of cyclodextrins

- -cyclodextrin -cyclodextrin
cyclodextri
0.65 0.85
n 0.5 nm
nm nm
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Complexation of odour molecules β-CD.

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Modification of PET with -

cyclodextrin
• Gain on mass
14
SHPI
12

10
Gain of mass [%]

Treated samples
8
1x washed

6 5x washed
10x washed
4

0
100/10 110/10 115/10A 115/10B 120/10 125/10 160/10
Treatement conditions: T [°C] / t [min]
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Measurement of fabrics handle

Sample KOSHI* *SHARI FUKURAMI* HARI* T.H.V.**
Untreated 8.08 8.98 3.43 12.23 2.72
115C/10min 5.42 6.86 6.07 8.11 2.79
b-CD/BTCA/CA, 110C/10min 6.93 8.80 4.39 10.93 2.91!
b-CD/BTCA/CA, 115C/10min 7.00 8.94 4.47 10.90 2.89!
b-CD/BTCA/CA, 125C/10min 9.09 7.13 5.81 11.19 1.65
b-CD/BTCA/SHPI, 160C/10min 10.40 7.92 4.32 12.90 1.62

* 10 strong, 1 week
** 5 excellent, 1 poor

Adsorption of textile using ammonia gas (JIS K0804)

treated untreated
Initial conc. (ammonia) 125ppm 125ppm

One hour conc. (ammonia) 0ppm 77ppm

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Odor intensity measurements

Odour intensity of fabrics sprayed with

parfume
4
3,5
3
Smell intensity

2,5
CD,spray
2
BLIND, spray
1,5
1
0,5
0
1 2 3 4 5 7 8 9
6 10
Weeks
 18

Nano-assembly of -CD crosslinked with BTCA

COOH O
O
HO O C O O
O
O CO O H
O CO O H
O O
O
O
CO O H HO O C
O
CO O H
O
O
O O
HO O C COOH O
CO O H
O O O
O O O
O
HO O C O
O CO O H O
O O
HO O C
HO OC O
O HO O C
O COOH
CO OH
CO O H O O
CO O H
O O O
HO O C
O
O O
O HO O C O

CO O H
COOH O
COOH O
O O O O
CO O H O O
O
O O CO O H
O
O CO O H
HO O C
O
 19

Synthesis of Nano Particles and

Encapsulation

 Synthsis of Tiatnium and silica nanoparticles

 Sol-Gel Encapsulation
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Preventing UV-light damage of light sensitive materials

using a highly protective UV-absorbing Hybrid (Class
1D) coating

Absorption spectrum of the UV protecting film (1 µm) with and without the
UV-absorber molecule (34 wt%).

Chem. Soc. Rev., 2007, 36, 1270-1281

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Dyes are protected against photodegradation

by Class 1D matrix

Visible absorption spectra of Photosystem I entrapped in sol–gel at intervals

during the aging process compared with the solution spectrum of the native
preparation. The spectrum of a control gel without PSI that was aged for 29
days is also shown
H. O'Neill and E. Greenbaum, Chem. Mater., 2005,
17, 2654
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Organic dyes in a silica matrix

fluorescence - laser - NLO - photochromism

J. Livage
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Encapsulation in drug delivery

 In recent decades, significant advances in drug-delivery systems have enabled
more effective drug administration. To deliver drugs to specific organs, a
range of organic systems (e.g., micelles, liposomes, and polymeric
nanoparticles) have been designed. They suffer from limitations, including
poor thermal and chemical stability, and rapid elimination by the immune
system. In contrast, silica particles offer a biocompatible, stable, and
“stealthy” alternative. Bioactive molecules can be easily encapsulated within
silica particles by combining sol–gel polymerization with either spray-drying
or emulsion chemistry. Spray-drying faces challenges, including low yield,
surface segregation, and size limitations. In contrast, sol–gel emulsions enable
the production of nanoparticles with homogeneous drug distribution, and
permit ambient temperature processing, necessary for handling biologicals.
Independent control of the size and release rate can be readily achieved.
Preliminary in-vivo experiments reveal enhanced blood stability of the
nanoparticles, which, coupled with sustained release of anti-tumor agents,
show good potential for cancer treatment.
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Sol-gel encapsulation of drugs in silica
particles using microemulsions

Water in oil emulsions

Langmuir, 1997, 13 (24), pp 6400–6406
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Bio encapsulation: Photosynthesis system

Chem. Mater., 2005, 17 (10), pp 2654–2661

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P.Ravindran, Nanomaterials and Nanotechnology, Spring 2016: Nanoencapsulation

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Encapsulated Dendrimer


The following figure shows mono dispersed Starburst
PAMAM polyamidoamine dendrimers encapsulated in a sol-
gel matrix of silica at 25 wt. %. Surface area analysis shows
the material surface area was 617 m2/g. The dark spheres in
Figure 1 dispersed throughout the silica show
diameters similar to their hydrodynamic
matrix values
dendrimer in solution. for this
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PAMMA Dendrimer
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Sol-Gel Encapsulated Dendrimer

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Enclapsulation of liposomes in silica gel

Langmuir, 1997, 13 (19), pp 5049–5053

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Encapsulating living cells in silica

Bacteria encapsulated within a silica matrix aged for (a) 1 month

without glycerol and (b) 1 day with a layer of glycerol.
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NanoJackets
Calcium Phosphate NanoParticles (CPNPs)
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Nanojackets are Molecular Smart Bombs;

Encapsulated components are released as a function of pH

NanoJackets

34
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TEM of Indocyanine Green (ICG) -Doped

CPNPs of 16nm mean diameter
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 Limitations of free ICG

– Fluorescence instability in physiological environments
 Dimerization leads to fluorescent quenching
 Protein binding causes absorption shifts
– Rapid elimination from the body
 Plasma t1/2 = 3-4 minutes
 Taken up exclusively by hepatic parenchymal cells
 Subsequently secreted entirely into the bile

 Benefits of NanoJacket Encapsulation

– Monomer caging prevents aggregate formation
– Solvent protection improves photostability
– Surface passivation affords long-term in vivo circulation
– Tumor localization via the EPR-Effect
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Colloidal Stability of
CPNPs in PBS
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Absorption and Fluorescence

Spectra of Free ICG and ICG-Doped
CPNPs in Aqueous Solution
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Fluorescence Lifetime of Free

ICG and ICG-CPNPs
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Comparative Spectral Effects of Various Solvents

on the Emission Response of Free ICG and ICG-
CPNPs
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EPR effect

41
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In Vivo Administration of PEGylated

ICG-CPNPs

 Accumulation within tumors via enhanced permeation retention effect

 Internalization into tumor cells via endosome pathway
 Application of encapsulated NPs in 43

food sector
 Nutrient Delivery Systems by encapsulation of vitamins,
antimicrobials, antioxidants

 Improvement of taste, texture, and consistency based using nano-structured

food ingredients

 Contaminant and Pathogen (Salmonella, E. coli) detection by nano-biosensors

 Novel antimicrobial solutions, e.g. nanosilver in food contact materials.

 Enhancement of the functional properties of packaging materials => ↑ shelf-

life, food spoilage warning

 Nanotube-reinforced composites (e.g. hydrophobic surfaces) to coat

food- processing equipment
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Potential applications of encapsulated NPs

• Use of nanosurfaces in active packaging

• Potential organoleptic & health benefits

• Anti-sticking products using super-hydrophobic nanoparticles

• Better understanding of products , (ink formulae)

•Use for colour and flavour delivery

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Risk Assessment-Health Effects of

encapsulated NPs
 No information on oral toxicity after long-term exposure

 Is toxicity related to size, mass, number of particles….?

 Behaviour, interaction and fate of NPs in the GI tract is unknown

 Long-term exposure by other routes may trigger effects on immune,

inflammatory, and cardiovascular systems

 No sufficient data on genotoxicity, teratogenicity and

carcinogenicity

 Nanotechnologies must be assessed on a case by case basis.

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ZEOLATE CAPPED SEMICONDUCTOR CLUSTERS

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ZEOLAT
E
LIGAND

Crown ether - zeolate ligand analogy - metal coordination chemistry of zeolites

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TOPOTACTIC MOCVD
Intrazeolite reaction of acid zeolite Y
(HY) with known amounts of Me2Cd
or Me4Sn vapors

Gives anchored MeCdY and Me3SnY,

which react with H2S or H2Se to
create encapsulated and zeolate
capped nanoclusters Cd4S4Y and
Sn4S6Y

Defined by Reitveld PXRD structure

refinement
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MOCVD TOPOTAXY OF INTRAZEOLITE TIN SULFIDE, CADMIUM

SELENIDE AND SILICON AND GERMANIUM NANOCLUSTERS
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INTRAZEOLITE
CVD OF SILICON

NANOCLUSTERS
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QUANTUM CONFINED SILICON - < 5 nm -MAKING

SILICON GLOW THROUGH NANOCHEMISTRY

• Si2H6 + H56Y  (Si2H5)8-Y

• (Si2H5)8-Y  (Si8)8-Y
• Superlattice of Si8 clusters in ZY
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INTRAZEOLITE
TUNGTEN OXIDE
NANOCLUSTERS
 53

Nanoparticulate Formulations
Dissolution and Release in Water

Powder particles dissolve in water and release nanoparticles.

0.3 Millimeter*
(300,000 Nanometer)

3
0
0

N
a
n
o
m
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Nanoparticles: Vitamins and Carotenoids

Principles
 Free nanoparticles of these compounds cannot exist
in air. Instantaneous oxidation occurs and
spontaneous ignition is possible.
 Nanoparticles are always embedded in a matrix and
incorporated into macroscopic powder particles.

Powder Particle, 0.3 mm

Thought experiment:
Extracting nanoparticles into air
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Fine Chemicals Division

Bioavailability
Principles: Resorption of Lipids

Digestion Liver
Intestinal
Wall

Micelles from bile acid

transport fats and Lipoproteins
carotenoids as individual Chylomicrons
(LDL, VLDL)
molecules

Other Tissues

Size ratio nanoparticle to micelle only indicatory. [after Chow et al. 2004]
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How do nano-nutrients work?

Fat-soluble nutrients like Nano-encapsulated nutrients do not
carotenoids and coenzyme Q10 cling together, thus increasing their
tend to cling together in the contact with the absorptive-cells of
digestive tract, making them the digestive lining, hence increasing
difficult to absorb. absorption.
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What Does “Nano” mean?

Difficult to absorb nutrient Nano-capsule Nano-nutrient
(example: CoQ10)

The application of nanotechnology employed by Pharmanex is a mono-molecular

encapsulation where single molecules of important nutrients are embedded into
single nano-capsule molecules. Since every single molecule of each nanoized-
nutrient is wrapped in its own individual nano-capsule there is complete molecular
dispersion of these
fat-soluble nutrients in the water soluble environment of the digestive
system.
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1. Unlike traditional fat soluble

nutrients, nano-
encapsulation allows
complete dispersion of Cell of intestinal wall
nanoized nutrients
2. The nano-capsule delivers
and releases the nanoized
nutrient to the site of
absorption.
Digestive System

4. The nano-capsule 3. The nutrient is

is digested by absorbed into the
intestinal intestinal wall where it
microflora enters the blood
stream for delivery to
body tissues.
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The Nanotechnology Difference

5-fold increase in absorption!

pmol/mg protein

γ-cyclodextrin complex

Adapted from Craft et al, FASEB Journal. 2005; 19(4):

Abstract #281.6, A449.
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Nanoparticulate Formulation: Lycopene

Confirmation of bioavailability in humans

Observation:
Continuous intake, 15mg/day over 28 days
1.0
Bioavailability of synthetic
product is similar to that
0.8 found for formulated
Serum Lycopene [µmol/l]

tomato extract (extracted

0.6 lycopene).
*P < 0.001
0.4 Bioavailability of lycopene
from fresh, non-processed
0.2 tomatoes is poor.
*
0
LycoVit® Tomat Placebo
10% o
based

Average change from initial value (n=12)

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Size Comparison Nanoformulations

Solubilizates vs. Nanoparticles

Solubilizate micelles, the

smallest nanoparticles.

20 nm 300 nm
Micelle loaded with Typical Nanoparticle
Health Ingredient