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Weonsun SHIN

Professor
DEPT of FOOD & NUTRITION
HANYANG UNIVERSITY

NANOENCAPSULATION:
PERSPECTIVES OF FOOD
INGREDIENTS AND BIOACTIVES
 Encapsulation can be defined as a process to entrap
one substance within another substance, thereby
producing particles with diameters of a few nm to a
few mm
Key Terms:
 Substance encapsulated: core material, the
active agent, fill, internal phase, or payload
phase.
 Substance encapsulating: coating,
membrane, shell, carrier material, wall
material, external phase, or matrix
 The carrier material of encapsulates used in food
products or processes should be food grade and
able to form a barrier for the active agent and its
surroundings
Food & Functional Supplement

 Applications
 Functional foods
 Taste masking
 Color masking
 Flavor stabilization
 Oxidation stability

 Features
 Improved shelf life
 Formulation compatibility
 Liquid to solid

SwRI Business Development


The possible benefits of microencapsulated ingredients
in the food industry could be:
• To protect core compounds from the environments (heat, moisture, oxygen & light)
• To reduce the loss from vaporization
• To modulate the intact properties of the compounds(polymers) for easy control
during processing
 Superior handling of the active agent (e.g., conversion of liquid active agent into a
powder, which might be dust free, free flowing, and might have a more neutral
smell)
 Immobility of active agent in food processing systems
 Improved stability in final product and during processing (i.e., less evaporation of
volatile active agent and/or no degradation or reaction with other components in
the food product such as oxygen or water)
 Improved safety (e.g., reduced flammability of volatiles like aroma, no
concentrated volatile oil handling)
 Creation of visible and textural effects (visual cues)
 Adjustable properties of active components (particle size, structure, oil-/water-
soluble, color)
 Off-taste masking
 Controlled release (differentiation, release by the right stimulus)
Such benefits should overcome the
following possible hurdles:

 Additional costs
 Increased complexity of production process
and/or supply chain
 Undesirable consumer notice (visual or touch)
of the encapsulates in food products
 Stability challenges of encapsulates during
processing and storage of the food product
Encapsulation methodologies

 Physical processes such as spray drying-


coating, extrusion, and spray drying
 Physiochemical processes such as simple or
complex coacervation and entrapment into
liposomes
 Chemical processes : interfacial
polymerization and molecular inclusion
3 Microencapsulation
Techniques
3.1 Spray Drying
3.2 Spray Cooling and Spray Chilling
3.3 Fluidized Bed Coating
3.4 Extrusion
3.5 Centrifugal Extrusion
3.6 Lyophilization
3.7 Coacervation
3.8 Centrifugal Suspension Separation
3.9 Cocrystallization
3.10 Liposome Entrapment
3.11 Interfacial Polymerization
3.12 Inclusion Complexation : Molecular
Inclusion
3.13 Nanoparticulate Delivery Systems
Dripping method:

 consisting of extruding droplets from a nozzle


in gentle conditions. Droplets may be
solidified by cooling or by gelification.
Productivity may be increased by forming a
liquid jet and breaking it into small droplets,
multiplying nozzles or working with spinning
devices. The main advantage of this
technology is the low size dispersion of the
microcapsules. The main drawback is the
productivity.
Spraying method:
 One of the oldest approaches for producing
capsules
 The small droplets are either cooled down (hot
melt system) or dried (polymer solution).
 Largely used in food industry, producing classical
food powder (e.g. milk powder).
 High productivity, low protective effects on
active compounda
3.1 Spray Drying

 분무건조는 식품산업에서 캡슐화


하는데 많이 사용
 건조에 안정한 식품첨가물, 기능
성 소재, 그리고 향미를 캡슐화함
 분무건조는 경제적이고, 캡슐화
재료를 다양하게 사용하며, 조작
이 쉬우며, 좋은 품질의 입자를 생

 충분한 유화능력의 캡슐재료를 선
택해야 함
 분무건조 된 입자의 크기는
100um로 아주 작음
Emulsifying method:

 Dispersed emulsion droplets may be turned into


microcapsules
 First, dispersing an oil phase (containing the
active to encapsulate) in a polymer solution, and
then inducing the precipitation of the polymer(s)
at the interface of the droplets
 Productivity is very good, this method has an
important drawback: crosslinking with
glutaraldehyde, a non food grade molecule, is
necessary most of the time to obtain stable
microcapsules.
Layer-by-layer deposition adds new properties
and stability to existing shell systems.

How to measure the stability

The creaming profiles of BSA-stabilized emulsion in the absence (A) and presence (B) of
fucoidan (1.0 wt%) during 24 h. The mean value kinetics of emulsion as a function of time
(a, b) [Macromolecular Research, 2009, Kim & Shin et al.]
Particle size & AFM
35

30
B0
25

% channel
20

15

10

0
350.001 0.01 0.1 1
size (µm)

30
BF 0
25
% channel

20

15

10

0
0.001 0.01 0.1 1
35
size (µm)

30
BF 96hr
25
% channel

20

15
Kim & Shin, 2013, submitted
10

0
0.001 0.01 0.1 1
Smaller particle, Larger surface area

Particle size is one of many parameters that may be adjusted to


control release rates of encapsulated ingredients.
Spray coating method:

 Consisting of fluidizing a powder (in a fluid


bed or a pan) and spraying a coating solution
on the fluidized particles.
 The coating is solidified by drying (polymer
solution) or cooling (melt system).
 This is the most promising method in terms
of performances and flexibility, but high
processing costs.
Fluidized Bed Coating

 유동층코팅은 서스펜션 코팅이나


Wurster 가공으로 불림
 입자크기는 50~500um이 최적이
며 35~5000um까지 가능
 가격이 효과적이며, 몇몇 캡슐화
된 식품에 표준화가 되있으며. 큰
입자생산이 가능, 입자크기와 모
양이 일정
[Burgain et al., J Food Eng. 2009]
Coacervation
• Amorphouse shape, core compounds solubilized protein solution:
controlled with temperature, pH, salt concentration
• Electrostatically driven micellization is a useful way of assembling
functional nanostructures because of the ability to tune intermolecular
interactions using pH and salt.
• Using molecular design, the macroscopic phenomenon of complex
coacervation can be achieved at the nanoscale by coupling the
polyelectrolyte to a neutral yet hydrophilic block, forming micelles with a
coacervate coe and a hydrophilic corona
Encapsulation Matrix

1. Carbohydrates
 Maltodextrins and Corn Syrup Soilds
 Modified Starch
 Cyclodextrins
 Modified Cyclodextrins
 Sucrose
 Cation polysaccharide: chitosan etc
 Anion polysaccharide: gum arabic etc
 Cellulose

2. Gums
 Seaweed Extracts
 Exudate Gums

3. Lipids
 Waxes
 Acetoacylglycerols
 Lecithins
 Liposomes

4. Proteins
Coating Materials for encapsulation of food, functional food, and
Nutraceutical ingredients

Carbohydrate Starch, maltodextrins, corn syrup soilds, dextran, modified


starch, sucrose, cyclodextrins, marine
carbohydrates(anionic.cationic)
Cellulose Carboxymethylcellulose, methylcellulose, ethylcellulose,
nitrocellulose, acetylcellulose, cellulose acetate-phthalate,
cellulose acetate-butylate-phthalate

Gum gum acacia, agar, sodium alginate, carrageenan

Lipid Wax, paraffin, beeswax, tristearic acid, diacylgylcerols,


monoacylglycerols, oils, fats, hardened oils

Protein Gluten, casein, gelatin, albumin, hemoglobin, peptides


Cyclodextrins
• Produced from starch by means of enzymatic conversion.
They are used in food, pharmaceutical, drug delivery, and
chemical industries, as well as agriculture and
environmental engineering
• Many metabolically important compounds, such as lipid-
soluble vitamins and hormones, have very low solubilities
in aqueous solutions. A frequently used approach is to use
cyclodextrin as a “carrier” molecule to facilitate the
dissolution of these compounds.
Chitin, Chitosan, Cellulose

• Chitin: β-(1-4)-linked 2-acetamido-2-deoxy-D-


glucopyranosyl
• Chitosan: Commercially produced deacetylated chitin,
β-(1-4]-linked 2-deoxy-2-aminoglucopyranose, gel-
formation reacted with small moleculaes, used as
coating-material for functional food or pharmaceutical
purposes, lower cholesterol
• Cellulose: cell wall components, β-(1-4)-linked
glucopyranose, used for edible-film, capsulating material
for enzyme & cells
Gums

 Mostly, water-soluble,
 Formation of viscous colloidal solution or/and gel network
under temperature control

 Emulsion stabilizer, crystal formation protector &


encapsulating materialas

 Marine (carrageenans, alginates), seeds (locust bean, guar),


plants (acacia), microbials (xanthan, gellan) & chemically
modified polysaccharides
Seaweed gums

 Alginate: giant kelp-sourced, forming


concentrated/viscous/stable sol & gel under optimal
concentarion, forming size-controllable capsule with Ca++,
used as stabilizer, hardness & resilience controlled with
addition of glycerol

 Agar: strong gelling agent, flavoring-capturing material


(chlorella-sourced agar)

 Carrageenan: extracts from red seaweed, powerful


gelling agent, control of viscosity, emulsion stabilizer
• carrageenan, pectin coating for encapsulating the meat
stock or/and juice
Gum exudates

 Gum acacia: capsulating material fo spray-dried flavor,


high solubility, natural emulsifier, low viscosity, no effect
on capsulating at high conc.

 Gum ghatti: similar to gum acacia in viscosity & emulfying


effect, limited supply

 Gum karaya & Gum tragacanth: high solubility, high


viscosity, colloidal stabilizer for dressing, sauce & ice
cream

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