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Seminar - I

Course Teacher
Dr. Udaykumar Nidoni

Presented by,
Patil Rutuja Sanjay

Seminar Contents

• Introduction
• History of Controlled Release System
• Mechanisms of controlled Release
• Antimicrobial Packaging
• Antioxidative Packaging
• Flavour Release Packaging
• Case studies
• Conclusions
• References
 Controlled Release is defined as a process by which one or more active
ingredients are made available at a desired site and time at a specific rate.

 Controlled Release Packaging (CRP) : Innovative technology

 Active compounds : antioxidants and antimicrobials.

 Slows down the reaction kinetics of food deterioration.

 Enhances the quality and safety of foods during extended storage.

barrier film

Active Food

CRP film

Fig. CRP System

(Koontz L., 2006)
History of Controlled Release System

1952 Introduction of the first controlled release formulation by

Smith Kline & French for 12-hour delivery of Dexedrine.
1950-1980 Development of oral and transdermal sustained release
systems and establishing controlled drug release mechanisms.
1998 Han and Floros are one of the first researchers who used the
concept of controlled release in food packaging applications.
2004 Encapsulation and controlled release of active compound from
polymer matrix by Buonocore, Sinigaglia and Corbo.
2005 Development of multilayer film with controlled release of
active compound by Buonocore, Conte and Corbo.
2005 Smart blending technique for development of controlled
release packaging materials by Lacoste, Schaich and Yam.
Advantages of CRP over traditional method for prevention of food
spoilage :

 Traditional method :
 Direct addition of antimicrobials or Dipping of food material
 Ceases protection effect once the active compounds are consumed in
complex reactions of food system.
 Lack of selectivity to target the food surface.
 Excessive use of active compound.

o Controlled Release Packaging

 Active ingredients are released at controlled rates over prolonged periods

of time.
 Maintains critical concentration over the surface of food.
 Active ingredient loss during processing and cooking can be avoided
 Very less use of active compound.
 Prevent sensorial or toxicological problems

(Gemili et al., 2010) 5

Types of Controlled Release Profile
Zero-order release

First-order release

Fig. Release patterns from packaging containing the

same initial concentration of active ingredient.
(Gemili et al., 2010)
Mechanisms of Controlled Release

Mechanism of
Controlled Release

Diffusion Swelling Biodegradation
controlled induced induced
release release release

Reservoir Matrix
System System

(Mastromatteo et al., 2010) 7

1. Diffusion Controlled System

Active molecules diffuse from a region of higher concentration to

lower concentration until equilibrium is attained.

Directly proportional to the concentration gradient across the


No energy required.

Types :- ♣ Reservoir system

♣ Matrix system

(Mastromatteo et al., 2010)

Reservoir system

 Active agent contained within a rate-controlling barrier.

 Barriers may be micro porous, macro porous or nonporous.
 Release rate depends on the thickness, the area and the permeability of the
 Rate-limiting step is diffusion through the polymer.

(Mastromatteo et al., 2010)
Matrix System

 Active agent is homogeneously dissolved or dispersed throughout the

polymer mass.

 The release pattern depends on the geometry of the system, the type of
carrier material and the loading of the active agent.


(Mastromatteo et al., 2010)

Swelling-controlled Systems

 In thermodynamically compatible medium, the polymer matrix swells

owing to absorption of fluid from the medium.

 The active agent in the swollen part of the matrix then diffuses outs.

 Membrane undergoes a transition from a glassy to a gel state upon

interaction with the penetrant.

(Mastromatteo et al., 2010)
Biodegradation induced release
o In biodegradation induced matrix-type delivery system, the active agent
is dispersed within the polymer and is released when the polymer
degrades or erodes.

o The release can be controlled by diffusion, erosion or a combination of


o Two types : Heterogeneous erosion and Homogeneous erosion

(Mastromatteo et al., 2010)
Encapsulation and Controlled Release

 Microencapsulation is defined as the technology of packaging solid, liquid, or

gaseous materials in minute sealed capsules that release their contents at
controlled rates.
 Stabilization against light, heat and oxidation.
 Mechanisms of release
 Barrier controlled release  Osmotically controlled release
 Pressure activated release  pH controlled release
 Solvent activated release  Temperature sensitive release

(Mastromatteo et al., 2010)
Conceptual Framework for CRP Development

Process Variables

1. Active Compounds

 Antimicrobials, antioxidants, enzymes, flavors and nutraceuticals

 Volatile and nonvolatile active compound
 Direct and indirect contact with food
 Release kinetics of compound

2. Polymer Composition

 Film composition and its structure

 Packaging material may be single layer or multilayer
 Release rate depend upon type of polymer and its ratio

3. Processing Methods

 Properties of packaging material are depend upon process conditions

 When two or more polymers are used to form a polymer, smart blending
technology is used.

(Yam and Zhu, 2014)
Structure Variables

1. Polymer Blend Morphology

 Polymer film structures at microscopic level

2. Package Structure

 Package structures are related to package design.

 Packaging material may be single or multilayer.
 Manipulation of factors such as loading of active compounds and thickness
of layer, gives different release rates.

3. Localization of Active Compounds

 Distribution of active compound in immiscible phases in a polymer blend

 In most cases, diffusion is the rate controlling step due to the high
diffusion resistance in the polymer matrix.

(Yam and Zhu, 2014)
Property Variables

1. Release and other Properties

 The release rate should properly match the microbial or oxidation kinetics
of the food and the shelf life requirement.

 The active compounds may act as plasticizers that decrease mechanical

properties and gas permeability.

Food Variables

 Food variables include food composition, food-package contact area,

storage condition, shelf life requirement and other factors.

(Yam and Zhu, 2014) 17


Application of
mechanism in
food packaging
and Flavor Antioxidant
release Packaging

Antimicrobial Packaging

 Antimicrobial packaging is a system that can kill or inhibit the growth of

microorganisms and thus extend the shelf life of perishable products and
enhance the safety of packaged products.

 It allows a controlled release of antimicrobial agents into the food surface

during storage and distribution.

(Han H., 2013)
Methods of Antimicrobial Packaging

Addition of sachets/pads Use of antimicrobial packaging


Antimicrobial coating on
conventional Antimicrobial edible coating on 20
packaging materials foods
Controlled Release Technology in Antimicrobial Packaging System

Slow dissolution of
Unconstrained free Slow diffusion of very gaseous
diffusion low agents released from
from packaging solubility agents from
antimicrobial sachets with
material containing monolithic constant
antimicrobial packaging materials volatility

(Han H., 2013)

Chemical Natural
Agents Agents

 Organic acids  Herbs and  Lactic acid

 Fungicides Spices extract bacteria
 Metal compounds  Essential oils
 Gases  Enzymes
 Polysaccharide  Bacteriocins
 Food Sanitizers

(Han H., 2013)
1. Chemical Agents:
Organic acids  Acetic acid, benzoic acid, lactic acid, citric acid, malic acid,
propionic acid, sorbic acid, succinic acid, tartaric acid,
mixture of organic acids
 Characteristic sensitivities to micro- organisms
Fungicides  Benomyl, Imazalil, sulfur dioxide
 Non food grade antimicrobial agents.
Nanoparticles  Silver, Silver zeolite, Titanium dioxide, Zinc oxide
 Nanoparticle shows strong antimicrobial activity against
bacteria, molds, and yeasts.
Gases  Ozone, chlorine dioxide, carbon monoxide, carbon dioxide
 Gases act as effective antimicrobial agents when vaporized
in the package headspace and dissolution onto the food
Polysaccharide  Chitosan, a deacetylated chitin, possesses antimicrobial and
film-forming ability.
Food Sanitizers  Cetyl pyridinium chloride, acidified NaCl, triclosan
 Food cleansing agents, food- contact substances, or food-
contact surface sanitizers.

(Han H., 2013)
2. Natural Agents:
Herbs and Spices  Grape seed extract, grapefruit seed extract, hop beta acid,
extract and
Essential oils Brassica erucic acid oil, rosemary oil, oregano oil, basil oil,
other herb/spice extracts, and their oils
 Major components are phenolics, terpenes, and aliphatic
 Minor components are ketones and aldehydes
Enzymes  Lysozyme, glucose oxidase, lactoperoxidase
 Antimicrobial activity is very sensitive to environment and
Bacteriocins  Nisin, pediocin, subtilin, lacticin
 Bacteriocins are peptidic toxins produced by bacteria to
inhibit the growth of similar bacterial strains.
 Resistance to thermal treatment and pH.

(Han H., 2013)
3. Probiotics:
Probiotics  Lactic acid bacteria, produce
bacteriocins and nonpeptide
growth-inhibiting chemicals such
as reuterin.

 These antimicrobials can inhibit

the growth of other bacteria.

 Probiotics effectively control the

competitive undesirable

(Han H., 2013)
Commercial Antimicrobial Packaging
Products and Manufactures

Trade name Active compounds Manufacturer

Microban Triclosan Microban Products

Micro garde Clove and others Rhone- poulenc (USA)
Take guard Bamboo extract Takex. Co. (Japan)
Microfree Ag, copper oxide, zinc DuPont (USA)
Ultra-Fresh Triclosan Thomson Research
Associates (Canada)
Novaron Ag-zirconium phosphate Milliken Co. (USA)
Piatech Ag oxide Daikoku Kasei Co. (Japan)

Recent Advancement in Antimicrobial Packaging Films


 Oplon (Israel) along with Reynold group commercialized the antimicrobial

 No need for preservatives.
 Reduce the cost of refrigeration and chilling.
 Protects against antibiotic resistant and heat resistance pathogens.
 Non-toxic, environmental friendly, and do not leach or release chemicals.


 Prevention of germ-growth

 Inhibition of mold (Candida albicans)

 Hygiene-maintenance and significant bacteria reduction (E. Coli, S.


 Food Products : Baby food, Cheese, Mayyonaise

 Health care and pharmaceutical packaging 28
Antioxidative Packaging

 Incorporation of antioxidant in packaging material and its release to

the contained food in a controlled manner.

 Need of antioxidative packaging

 Reduction in shelf-life due to changes in taste and odour.

 Deterioration of the texture and functionality of muscle foods
 Reduction in nutritional quality.

 Antioxidants can be used for oil, nuts, butter, fresh meat, meat
derivatives, bakery products, fruits and vegetables.

(Dong S. L., 2014) 29

o Antioxidant helps to protect the polymer and stabilize it throughout its
o It reduces oxygen passage through polymer layer which suppress
oxidative degradation of food.

1. Synthetic antioxidants : butylated hydroxyanisole (BHA)

butylated hydroxytoluene (BHT)

2. Natural antioxidants : tocopherol, ascorbic acid, curcumin, tyrosine,

essential oils and plant extracts of barley husks,
borage, cinnamon, citronella, clove, ginger,
green tea, marigold, rosemary, oregano, and

o Non volatile and less volatile antioxidants :Liquid and semisolid food

o Volatile antioxidants : Solid foods

(Dong S. L., 2014)
Release Mechanism of Antioxidant from Packaging Material to
Antioxidative Food Packaging System

(Dong S. L., 2014) 31

Flavor Release Packaging

 Flavor-release packaging is a packaging system which incorporates and

delivers extraneous flavor to food products to enhance their flavor profiles
and improve consumer acceptability.

 In order to improve food aroma to attract consumers when the package is


 To balance any detrimental effects of aroma loss.

 To mask undesirable plastic odours.

(Arabi et al., 2012) 32

Mechanism of Aroma Release in Packaging

A. Indirect Contact System B. Direct Contact System

(Arabi et al., 2012)
Mechanism of Aroma Release in Packaging

 The diffusivity of a flavor compound is dependent on the polymer matrix,

temperature, humidity, etc.

 For volatile aromatic compounds, encapsulation is necessary.

 For controlled release of aromatic compound two steps are involved :

Triggering and Diffusion

 Types of triggering of aromatic compound: 1. Heat trigger

2. Force trigger

(Arabi et al., 2012)

A. Heat Trigger 34
B. Force Trigger

(Arabi et al., 2012)
Commercially available flavor-release packaging system

Developer Packaging system Target product

AddMaster Chocolate-flavored Chocolate-flavored

masterbatch for milk-based drink
ScentSational Encapsulated aroma release Not specified
(Compel AromaTM)
Ball Packaging Widget technology: Milk, yoghurt, milk based
Europe packaging drinks with and
system that generates without alcohol, coffee
nitrogen to form foam head based drinks
UnistrawTM Flavor coated straw Milk products
milk flavoring straws)
Süd-Chemie Canisters that incorporate Nutritional and
lemon, orange, vanilla, mint pharmaceutical
or chocolate (Aroma-Can®) products
International Aroma blended masterbatch Not specified
Flavors (PolyIFF®)
& Fragrances Inc. 36
Scented Canisters

 Manufactured by Süd-Chemie’s industry

 Encapsulated Aroma Release technology™
 Aroma compound – Lemon and Orange
 To enhance the desirability of nutritional and pharmaceutical products by
adding a pleasant scent to product packaging
 Applications: Nutraceutical, Pharmaceutical, Food, Candies and Chemicals

Case Study - I

Title : Development of activate-at-home-type edible antimicrobial

films: An example pH-triggering mechanism formed for
smoked salmon slices using lysozyme in whey protein films

Authors : Derya Boyacı, Figen Korel, Ahmet Yemenicio glu

Year : 2016

Journal : Food Hydrocolloids

Objective : To develop novel natural antimicrobial packaging system

which could be activated by consumers at home by pH-
triggering mechanism.

Material and Concentrations :

Whey protein film (WPI)

Antimicrobial Agent : Lysozome
WPI – Oleic acid blend film ( 9% oleic acid)
WPI – Beeswax composite film (30% beeswax)

Principle :

Neutral pH


Below pI
(pH 5.4)

Parameters : 1. Released LYS activity into buffer

2. Released LYS activity on smoked salmon
3. In-vitro antimicrobial activity of films
4. Antimicrobial activity of the films coated on smoked salmon
Result and Discussion :

Fig. 1. pH controlled LYS release profiles of different films in buffer


pH 4.5

pH 4.0

pH 5.0
pH 5.5

Fig. 2. Release profiles of LYS from WP, WP-OLE and WP-BW films
incubated at 4 ̊C in buffers with different pH values.
Fig. 3. Increased in LYS release from WP, WP-OLE and WP-BW
films on surfaces of coated smoked salmon discs
Table 1. Antimicrobial activity of WP, WP-OLE and WP-BW films on L.
innocua in laboratory media

Film composition Average zone area (mm2) at 4ºC

LYZ OLE BW 24 h 48 h
(5% citric acid)
(mg/cm2) (%)a (%)a

- - - - Partial zones Partial zones

- - - + Partial zones Partial zones

0.7 - - - 51.7 ± 8.5d 63.5 ±13.9c

0.7 - - + 101.1 ± 15.3c 84.6 ± 22.5b

0.7 9 - - 121.5 ± 14.9b 93.9 ± 17.4b

0.7 9 - + 141.6 ± 26.6a 124.3 ± 32.7a

0.7 - 30 - 54.5 ± 7.4d 55.6 ± 11.04c

0.7 - 30 + 58.5 ± 21.2d 88.11 ± 55.6c 43

Table 2. Antimicrobial activity of WP and WP-OLE films on L. innocua
inoculated smoked salmon slices cold stored at 4 ◦C.

L. innocua counts during storage at 4°C (log CFU/g)a

Day 0 Day 1 Day 3 Day 5 Day 7
4.98 ± 0.08a,A 4.82 ± 0.10ab,B 4.82 ± 0.10a,B 4.80 ± 0.11a,B 4.83 ± 0.13a,B

WPI/OLE (control)b
4.92 ± 0.10a,A 4.72 ± 0.10bc,C 4.73 ± 0.08b,C 4.78 ± 0.09a,BC 4.84 ± 0.11a,B

4.92 ± 0.08a,A 4.68 ± 0.07c,B 4.69 ± 0.15b,B 4.74 ± 0.12a,B 4.49 ± 0.12b,C

WPI/OLE (acidified)
4.97 ± 0.04a,A 4.84 ± 0.11a,B 4.77 ± 0.13ab,B 4.80 ± 0.12a,B 4.57 ± 0.09b,C

WPI/OLE+LYS (acidified)
4.97 ± 0.07a,A 4.49 ± 0.13d,B 4.45 ± 0.13c,BC 4.27 ± 0.19b,BC 4.24 ± 0.15c,C

Conclusion :

• LYS release mechanism based on acidification of the film was


• The films were successfully applied on smoked salmon slices

• Activation of edible films by consumer before consumption or

after for the remaining part of the food is possible

• To optimize the concentration of LYS and increase the efficieny

of film activity, further food applications are needed.

Case Study - II

Title : Development of antioxidant food packaging materials with

controlled release properties

Authors : Seyhun Gemili, Ahmet Yemeniciog lu and Sacide Alsoy


Year : 2010

Journal : Journal of Food Engineering

Objective : To show the potential of asymmetric cellulose acetate

films for controlled release of different antioxidant


Material : Cellulose acetate(CA), acetone,

antioxidant agent :-
L-ascorbic acid and L-tyrosin

Concentrations : CA/acetone/water/antioxidant agent : 1) 5/80/13.5/1.5

2) 10/80/8.5/1.5
3) 15/80/3.5/1.5
Method of film formation : Casting

Parameters : 1.

Result and Discussion :

Table 1 : Morphological characteristics of antioxidant containing cellulose

acetate films

Composition Total thickness Dense layer Pore size Porosity (%)

(w%) (μm) thickness
L-ascorbic acid containing films
5/80/13.5/1.5 11.26 ± 0.8 0 1.28 ± 0.09 47.19 ± 0.23
10/80/8.5/1.5 12.54 ± 0.58 0.82 ± 0.06 0.53 ± 0.03 35.28 ± 2.5
15/80/3.5/1.5 9.74 ± 0.69 1.73 ± 0.12 0.40 ± 0.03 8.48 ± 0.6
L-tyrosin containing films
5/80/13.5/1.5 13.94 ± 0.93 0 1.15 ± 0.17 54.43 ± 1.68
10/80/8.5/1.5 10.87 ± 3.47 0.83 ± 0.23 0.80 ± 0.05 25.83 ± 0.49
15/80/3.5/1.5 10.20 ± 0.65 3.52 ± 0.52 0.50 ± 0.04 16.28 ± 5.94

Table 2 : Antioxidant activities obtained form different CA films during release
Composition (w %) Film Surface(μm) Maximum released antioxidant activity- Recovery
reaction period 6 min (μmole trolox/cm2) (%)

L-ascorbic acid containing films

5/80/13.5/1.5 Porous 1.18 ± 0.03 90

Dense 1.19 ± 0.01 85

10/80/8.5/1.5 Porous 1.43 ± 0.03 95

Dense 1.42 ± 0.04 87

15/80/3.5/1.5 Porous 1.33 ± 0.09 82

Dense 1.01 ± 0.03 63

L-tyrosin containing films

5/80/13.5/1.5 Porous 3.05 ± 0.04 89

Dense 3.04 ± 0.03 68

10/80/8.5/1.5 Porous 1.16 ± 0.01 26

Dense 0.34 ± 0.01 8.5

15/80/3.5/1.5 Porous 1.02 ± 0.04 24

Dense 0.33 ± 0.00 15 49

Fig. 2
Fig. 1

Fig. 1 & 2. Initial change of antioxidant activity in distilled water during release of L-
ascorbic acid from different cellulose acetate films incubated at 4 ̊C

Fig. 3. Antioxidant activities of L-ascorbic acid and L-tyrosine
compared to standard antioxidant trolox.

Table 3. Immobilized antioxidant activities of films after release tests.

Composition Film surface Immobilized antioxidant activity-reaction period 60

(w %) used in release min (μmole trolox/cm2)
L-ascorbic acid containing L-tyrosine containing film
L-ascorbic acid containing films
5/80/13.5/1.5 Porous 1.10 ± 0.04 2.04 ± 0.04
Dense 0.75 ± 0.00 2.09 ± 0.02
10/80/8.5/1.5 Porous 1.18 ± 0.36 1.82 ± 0.02
Dense 0.45 ± 0.13 2.14 ± 0.07
15/80/3.5/1.5 Porous 1.91 ± 0.09 1.83 ± 0.02
Dense 1.06 ± 0.15 2.11 ± 0.02

Table 4. Effective diffusion and partition coefficient of antioxidant agents
in different cellulose acetate films.
Composition (w %) Film Surface(μm) Partition Coefficient Diffusion Coefficient

L-ascorbic acid containing films

5/80/13.5/1.5 Porous 378 15.0 x 10-10

Dense 611 15.0

10/80/8.5/1.5 Porous 169 15.0

Dense 483 8.33

15/80/3.5/1.5 Porous 893 3.33

Dense 2439

L-tyrosin containing films

5/80/13.5/1.5 Porous 343 2.50

Dense 1,371 2.00

10/80/8.5/1.5 Porous 10,464 1.00

Dense 39,327 0.17

15/80/3.5/1.5 Porous 12,553 0.83

Dense 22,344 0.83
Fig. 4. Experimental and theoretical fractional mass release of L-tyrosine and L-
Ascorbic acid from CA films (CA/acetone/water/AA) : (A) 5/80/13.5/1.5-porous surface
(B) 5/80/13.5/1.5-dense surface
Conclusion :

 Good potential of using asymmetric cellulose acetate films for

controlled release of L-ascorbic acid and L-tyrosine.

 Changing the composition of the casting solution to controls the

degree of asymmetry and pore size of the films.

 Application of either dense or porous sides of the films on food

surfaces are key points to obtain desired release rates for the
antioxidants, hence, to increase the quality and shelf life of the

 Further studies are needed to develop novel food packaging

applications by testing the effectiveness of the developed films on
selected food surfaces.

Seminar Conclusion

 The technology of controlled release, with its initial roots in drug

industry, has spread to other area such as agrochemicals,
fertilizers, veterinary drugs and food industry.

 Controlled Release technology in packaging helps in effective

utilization and targeted delivery of active components to the food.

 Manipulation of process and structural variables of packaging

material gives the packaging material with different release rate.

 Mechanism of controlled release is very much effective in

antimicrobial, antioxidant and flavour release packaging.

Future Outline

 The potential is infinite, still in developmental stage.

 Studies on release rate of active agents from CRP material in

actual food environment is necessary.

 Studies on use of smart blending technology in manufacturing

of CRP films to alter the release rate is necessary.


Arabi S. A., Chen X. and Shen L., 2012, Flavor-release food and beverage packaging:
Emerging Food Packaging and Technologies. Ed. Yam K. L. and Lee D. S.,
Woodhead Publishing Ltd., pp. 96-107.

Boyacı D., Korel F. and Yemenicioglu A., 2016, Development of activate-at-home-

type edible antimicrobial films: An example pH-triggering mechanism
formed for smoked salmon slices using lysozyme in whey protein films.
Food Hydrocolloids, 60: 170-178.

Dong S. L., 2014, Antioxidative packaging system, Innovations in Food Packaging.

Ed. Han H. J., Elsevier Ltd., pp. 111-126.

Gemili S., Ahmet Y. and Sacide A. A., 2010, Development of antioxidant food
packaging materials with controlled release properties. Journal of Food
Engineering, 96: 325–332.

Han H. J., 2013, Antimicrobial packaging system, Plastic Films in Food Packaging.
Ed. Sina E., Plastic Design Library Series, pp. 151-174. 58
Koontz J. L., 2006, Controlled release of active ingredients from food and beverage
packaging. Paper presented In: Italian Packaging Technology Award (IPTA)
Paper Competition, Department of Food Science and Technology,
Blacksburg, February 15, 2006.

Lacoste A., Schaich K. M., Zumbrunnen D. and Yam K. L., 2005, Advancing
controlled release packaging through smart blending. Packaging
Technology and Science, 18:77-87.

Mastromatteo M., Contea A. and Nobile A. D., 2010, Advances in controlled release
devices for food packaging applications. Trends in Food Science &
Technology, 21: 591-598.

Yam, K.L. and Zhu X., 2012, Controlled release food and beverage packaging:
Emerging Food Packaging and Technologies. Ed. Yam K. L. and Lee D. S.,
Woodhead Publishing Ltd., pp. 13-26.
Protein damage Cell membrane Oxidative damage DNA
Proteins are damage Antimicrobial can interference
essential for the By disrupting the causes increase in Genetic
biological system microbe membrane, levels of reactive material of
of life. the structural integrity oxygen species, bacteria is
Its damage causes of microbe is which causes disrupted,
failure of compromised, which damage to internal which stops
essential function causes essential system of the ability of
of energy nutrients to leak out microbes. bacteria to
production. and catastropic replicate.
structural failure.