11 nanoencapsulatio khare ift11

Nanoencapsulation Nanoencapsulation in Foodin Food

Atul Khare, Ph.D., M.B.A.

1111

Director, Customer Innovation and Technology Strategy

FONA International Inc.,

1900 Averill Road, Geneva, IL 60134, USA

[email protected], (630) 578-8684

Presentation at the IFT Pre-Annual Meeting Short Course on “Microencapsulation in Food Applications”.

New Orleans, LA

June 10-11, 2011© 2011 Institute of Food Technologists

Outline

� Introduction

� Examples of Nanoencapsulated systems

�Liquid-Liquid System

�Solid System�Solid System

� Emerging Nanoencapsulation forms

� Regulatory Update

� Summary

2 © 2011 Institute of Food Technologists

Why Nanoencapsulate?

� Why Nanotechnology?• Increase in surface area, may lead to improvement in

bioavailability of flavors and food ingredients• Improvement in solubility of poorly water soluble

ingredients• Optically transparent (Important in Beverage Application)

Higher ingredient retention during processing (Volatile • Higher ingredient retention during processing (Volatile Organic Carbon (VOC) Reduction)

• Closer to true molecular solution (Homogeneity in system properties such as density)

• Higher activity levels of encapsulated ingredient, e.g., antimicrobials

3

Journal of Food Science 71 (2006) R107-R116; Trends in Food Science & Technology 15 (2004) 330-347; International Journal of Food Science and Technology 41 (2006) 1-21

© 2011 Institute of Food Technologists

Nano for food encapsulates

� Size range from 10 nm to 1000 nm (1 micron)

� Examples of nanoparticles and encapsulates occurring naturally:

• Casein micelles in milk (<100 nm)

• Mitochondria (500 nm-10 microns)• Mitochondria (500 nm-10 microns)

• Viruses (10-300 nm)

� Formation of nanoparticles

• Size Reduction (Communition), Top down approach

• Particle formation (Precipitation), Bottoms up approach


Nano-materials + Tools

Nano-devices

Nano-systems

Tech

nical difficu

lty, today

Nanotechnology Nanotechnology RoadmapRoadmap

2000 2005 2010 2015 2020 Time, yrs

Nanoparticles

-Metal, metal oxides -Ceramic powders -Carbon tubes and

spheres

-Quatum dots -Dendrimers

-Porous supports -Capsules, fibers

Nanodispersions

-Films/Coatings/ Nanolaminates-Microemulsions-Micellar solutions

-Ferrofluids-Liquid crystals –Liposomes

Nanocomposites

-Fabrics -Optical components -Orthopedic material

-Polymers


Proteins

Polysaccharides 1. Control physical stability

(lower energy state)

2. Low energy processing (controlled self-

Multidisciplinary Approach is RequiredMultidisciplinary Approach is Required

LipidsWater

Air

(controlled self-assembly)Effectiveness of ingredient delivery (controlled release)

3. Improved control of food properties (e.g. flavor perception, texture)


Many potential applications for food, but overall tech is at very early stageMany potential applications for food, but overall tech is at very early stage

Food Processing Food Engineering Food Packaging

Driver

“fast-good-low cost-safe”

food processing at nanoscale

“pleasant-nutritive-high quality”

organoleptic properties, and functional food

“Cost, sustainability,

convenience, safety and quality”

value added packaging

Nanomaterials

2000-

•Molecular filters

•Nanofiltration

•Ingredient encapsulation

•Leverage intrinsic nanostructure of food stuff

•Functionality: barrier, thermal, mechanical, biodegradable

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2000-

(FACTS)

•Nanofiltration nanostructure of food stuff and food additives

biodegradable

Nanodevices

2010-

(NEAR REALITY)

•Microreactors

•Portable sensors

•Target delivery and control release

•Novel food matrixes

•Sensors for diagnostic

•RFID

•Active packaging

Nanosystems

2018-

(FICTION ?)

•Molecular Manufacturing

•Bio-mimetic materials•Intelligent/Active Packaging


Steps involved in Flavor and Food Ingredient Encapsulation

� Mixing step to obtain as homogenous mixture as possible• Particle Size

• Particle Size Distribution

• Concentration Gradients

� For Dry Powder Form: Removal of water by drying step

Mixing of Components (Liquid-Liquid), (Solid-

Removal of water to form a dry encapsulated

If dry form required

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(Liquid-Liquid), (Solid-Liquid), (Solid-Solid)

Generally Water is the main component

a dry encapsulated powder form. Drying can be done by spray drying,

freeze drying or other unit operations

required

Filtration and/or pasteurization step or other sterilization step

If liquid form required


� Micro/mini-emulsions (droplet size < 1µm)� Surfactant micelles- Reverse micelles� Emulsion bilayers – multilamellar, multivesicular, unilamellar

� Colloidosomes� Association colloids

““Structured Food Systems, and Advance Delivery Structured Food Systems, and Advance Delivery

Technologies*Technologies*” = ” = Edible Edible NanoNano sized delivery systemssized delivery systems

� Association colloids� Nanotubes� Nanocochelates� Solid Lipid Nanoparticles� Biopolymer Nanoparticles - (e.g. porous starch granules, casein micelles)

� Functional Interfacial Nanolayers – biopolymers, surfactants, lipids

© 2010 Institute of Food Technologists9

Goal: Maximize protection, trigger and control the release pattern of

encapsulated matter for food systems – safely and effectively.

* N. Garti. Delivery and controlled release of bioactives in foods and nutraceuticals. Chapter 18, pp 463, (2008)


Liquid-Liquid Systems based on emulsions

NameParticle

DiameterThermodynamic

StabilityAppearance

Surfactant to Oil Ratio

Example

0.1-100 Emulsion

0.1-100 microns

No Opaque <1:10 Milk

Liposome100 nm-microns

Yes Clear-Cloudy N/ALiposomal CoQ10

enzyme

Microemulsion 5-50 nm Yes Clear-Cloudy >1:1NutraLease Technology Products

Nanoemulsion 10-100 nm No Clear-Cloudy ~1:1High-Pressure homogenized

emulsions

10Food Technology, March 2006, 30-36.


Microemulsions

� Basics:

• Mixture of Oil, Water and Surfactant

• Oil in Water (Continuous Phase) mixture with surfactant at the interface of oil and water phase

• Swollen micelle system (Critical Micelle • Swollen micelle system (Critical Micelle Concentration, CMC)

• Thermodynamically stable

• Optically Transparent (Particle Size 5-50 nm)


Microemulsions

� How are they made?

• Energy input is needed, typically to mix two immiscible phases, viz., oil and water

• Mixing

− Gentle low shear mixing− Gentle low shear mixing

− High shear mixing

• Homogenization

− Low Pressure

− High Pressure

• Self emulsifying systems


Microemulsions

� Stability• Kinetic Stability: Stable during storage and

product use (environmental condition) − Gravitational separation

• Creaming or sedimentation

− Flocculation due to non-steric hindrance− Flocculation due to non-steric hindrance

− Coalescence or Oswald Ripening due to solubility of one phase into the other phase.

• Thermodynamic stability


Microemulsions characterization

� Particle Properties• Concentration• Mean particle size• Particle size distribution• Particle charge• Interfacial properties

� Product properties� Product properties• Optical clarity• Rheology (strong function of particle size, shape and

concentration)• Stability

� Product performance• Appearance• Flavor/ingredient stability• Texture


List of ingredients which can be solubilized by nanoparticulate encapsulates in two-phase liquid system

Alpha-lipoic acid

Alpha-tocopherol (Vitamin E)

Ascorbic Acid

Astaxanthin

Benzoic Acid

Omega-3 fish oil from fish and algae

Orange

Phytosterols

Rice bran oil

Rosemary Extract

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Beta-Carotene

Citric Acid

Coenzyme Q10

Flavor Oils

Flaxseed oil

Gama-tocopherol (Vitamin E)

Isofavone

Lutein

Lycopene

Mint

Rosemary Extract

Sorbic Acid

Unique Weight Management Solutions

Vitamin A Acetate and Palmitate

Vitamin B

Vitamin D

Vitamin D3

Vitamin E

Vitamin K

Vitmain A


Microemulsions in beverages

� Micelle based system, AQUANOVA AG and Zymes LLC

• Polysorbate (Tween), (AQUANOVA AG) and Polyoxyethanyl-a-tocopheryl sebacate (PTS), (Zymes LLC) surfactant based solubilization systems

• Micelles with <30 nm size solubilize lipophilic flavors and ingredients to form a transparent solution

• Stable at wide rage of pH, temperatures and mechanical shear.

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US Patent 6,048,566, http://www.aquanova.de, http://www.zymesllc.com© 2011 Institute of Food Technologists

Microemulsions in beverages

� Self Emulsifying system, NutraLease Technology based on Nano-sized Self-assembled Structured Liquids (NSSL) technology

• Micelle based system

• Self emulsification when ingredients are mixed• Self emulsification when ingredients are mixed

• Useful for solubilizing lipophilic flavors/ingredients

� Ingredients solubilized are• Omega-3 fish oil, vitamins, nutraceuticals,

phytosterols, flavors and others

17US patent 7,182,950 , http://www.nutralease.com


What is Nanoemulsion?

� 1-100 nm droplets dispersed in a continuous phase

� Metastable system (Thermodynamically Unstable System)

� Need high energy input to obtain nanoemulsion

� They do not form spontaneously

� Nanoemulsions are different from lyotropic liquid crystalline phases such as micelles, mesophases, which are equilibrium structuressuch as micelles, mesophases, which are equilibrium structures

� Physical properties can be different from microemulsions

� Potential benefits

� Higher surface area: much larger surface area to volume ratio

� Optically clear

� Reduction in viscosity

� Reduced amount of surfactant required

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J Phys.: Condens. Matter 18 (2006) R635-R666© 2011 Institute of Food Technologists

Nanoemulsions: How to make them?

� Use of high-pressure homogenizers

• The oil/water/surfactant/ingredient slurry is forced through microns size piston-gap under high pressure to create cavitation and turbulence leading to particle size reductionto particle size reduction

− Milk is homogenized at low pressures typically < 4000 psi

• For nanoemulsions, high pressures of the order of 10 to 20K psi are typically used to obtain nanoemulsions

• High-Pressure homogenizer manufactures are: Avestin, BEE International, Microfluidics Corporation, Niro-Soavi and Others


Stability of Nanoemulsion

� Nanoemulsions are kinetically stable systems.

� Mechanism of instability

• Coalescence: Avoid by steric hindrance or • Coalescence: Avoid by steric hindrance or repulsion due to electrostatic charges

• Ostwald Ripening: High solubility for dispersed phase in continuous phase. This can be avoided by using a film coating around the oil droplet


Nanoemulsion for delivery of Nutraceuticals

� Solubilization of phytochemicals, e.g., Curcumin, resveratrol, epigallocatchin gallate) and cartoenoids, e.g., lycopene, B-cartotene, lutein, zeaxanthin

� Improves bioavailability and solubility

� Factors affecting the bioavailability

• Size of the emulsion droplet

• Lipid components in the formulation

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Photographic images of curcumin nanoemulsions (A), nanodispersion (B), and water solution (C) (Food Chemistry, 119:669-74, 2010).

JOURNAL OF FOOD SCIENCE—Vol. 75, Nr. 1, 2010, R50-R57© 2011 Institute of Food Technologists

Taiyo Kagaku Co. Japan.

SolubilizationSolubilization of Hydrophobic Functional Ingredientsof Hydrophobic Functional Ingredients

• SunActive Fe is composed of micronized ferric pyrophosphate (~300nm), which is stabilized and protected with unique emulsifiers.

• Bioavailability confirmed in several clinical trials

• Delivery system based on emulsification technology

• High stability against heat and oxidation, masking the unpleasant taste, odor and color of nutrients, and protecting the gastrointestinal system, providing a non-irritating fortification with superior absorption properties and bioavailability

• Minerals, vitamins, functional oils

http://www.taiyointernational.com/NDS/NDS_Overview.asp22 © 2011 Institute of Food Technologists

Nanoemulsion for delivery of Antimicrobials

� Due to small size and large curvature, antimicrobials will have a better activity

� Some antimicrobials have surfactant like properties and can stabilize the nanoemulsion.

� Surface active antimicrobials are lysozyme, nisin and lauric arginate.

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Book: Global Issues in Food Science and Technology, 2009,Chapter 24-Nanostructured Encapsulation Systems: Food Antimicrobials, Pages 425-479, Jochen Weiss, Sylvia Gaysinsky, Michael Davidson, Julian McClements


Liposomes

� Spherical Particles formed from Polar Lipids

� Size: 100 nm-microns

� Good carrier for hydrophilic and lipophilic food actives

� Expensive to manufacture

24

J Sci Food Agric 86:2038–2045 (2006), DOI: 10.1002/jsfa

Courtsey: Mr. Charles Brain, Ingredients Innovation International (3i)© 2011 Institute of Food Technologists

Nanofiber based Flavor Encapsulation

� Why Nanofiber?� High surface to volume ratio, leading to very high surface

area, improvement in bioavailability of ingredient� Controlled release of flavor including stimuli responsive fast

dissolve or burst effect� Unique surface morphology may prove beneficial in

improving shelf life� Near room temperature process may work well for � Near room temperature process may work well for

encapsulation of thermally labile ingredients.

� How are they made?� Dissolve the polymer carrier in an organic solvent/water

mixture with the flavor/functional ingredient to form a suspension/solution.

� Electrospin the fiber using a very high DC voltage of upto 30kV

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Food Hydrocolloids 23 (2009) 1427-1432; US Patent Application US2006/0264130 A1


Electrospinning of Fibers

� Zein fibers were electrospun using this setup

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Journal of Food Science, 74 (2009) C233-C240.© 2011 Institute of Food Technologists

Electrospinning of Nanofibers, Case Study: Beta-Carotene encapsulated in Zein Nanofibers

Zein Nanofiber mat

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Zein with Beta-Carotene Nanofiber mat

Food Hydrocolloids 23 (2009) 1427-1432© 2011 Institute of Food Technologists

Electrospinning of Nanofibers, Case Study: Beta-Carotene encapsulated in Zein Nanofibers

� Beta-carotene is light sensitive, zein was able to protect Beta-carotene from light

� The B-carotene loading was 0.6-1.2% by weight

28Food Hydrocolloids 23 (2009) 1427-1432© 2011 Institute of Food Technologists

New Nanoencapsulation technologies� Double-layered nanocapsules based on layer-by layer

(LbL) electrostatic deposition method: Polyelectrolyte complexes

� Multi-assembled nanocapsule aggregates

29

Book: Global Issues in Food Science and Technology, 2009,Chapter 24-Nanostructured Encapsulation Systems: Food Antimicrobials, Pages 425-479, Jochen Weiss, Sylvia Gaysinsky, Michael Davidson, Julian McClements

Precision Particle Fabrication Technology based on vibrating nozzles (Orbis Biosciences)

� Minimum 2 micron size particles

� Core-shell morphology

� Monodisperse particle size distribution

� High Loading of the active

30Professor Cory Berkland, University of Kansas, Presentation from 14th

Industrial Microencapsulation Workshop, San Anotonio, TX© 2011 Institute of Food Technologists

Regulatory Considerations

� Questions to consider:

� What are the appropriate criteria for defining their specifications of identity and purity for determining safety?

� What types of toxicity testing protocols are appropriate for establishing safe conditions of use?

� Do existing authorizations cover these products?

� Concerns regarding safety of nanomaterials in general will result in required safety assessment of nanoencapsulated bioactives ;

� Additional research on toxicity of oral exposure to engineered nanomaterials must include:

� Characterization of nanomaterials,

� Established protocols and/or validated in vitro assays.

31

Annette M. McCarthy, Ph.D., Office of Food Additive Safety, Center for Food Safety and Applied Nutrition (CFSAN), USFDA. Presentation at IFT 2009 Nanotechnology preconference workshopBerna Magnuson, Ph.D., Cantox Health Sciences International, Presentation at 14th

Industrial Microencapsulation Workshop, San Antonio, March 2011 © 2011 Institute of Food Technologists

Summary

� The nanoparticulate formulations for food and flavor ingredient encapsulation offer distinct benefits:

� Improved active retention

�Reduction in surface oils

� Increase in solubility leading to higher bioavailability� Increase in solubility leading to higher bioavailability

� Improved shelf stability

�Controlled release of actives

� Nanoencapsulation is an emerging area for food ingredients and should be used to enable distinct benefits.


Useful Citations on Nanoencapsulation in Food� Design of Nano-Laminated Coatings to Control Bioavailability of Lipophilic Food Components,

David Julian McClements, JOURNAL OF FOOD SCIENCE—Vol. 75, Nr. 1, 2010, R30-R42

� Book: Global Issues in Food Science and Technology, 2009 Elsevier, Inc., Chapter 24, Nanostructured Encapsulation Systems: Food Antimicrobials., pp. 425-479.

� Nanoscale materials development – a food industry perspective, P. Sanguansri and M.A. Augustin, Trends in Food Science & Technology, 17 (2006) 547-556.

� Nanoemulsions: formation, structure and physical properties, T.G. Mason, N.N. Wilking, K. Meleson, C.B. Chang and S.M. Graves, J. Phys.: Condens. Matter 18 (2006) R635-R666.

� Encapsulation efficiency of food flavors and oils during spray drying S.M. Jafari, E. Assadpoor, Y. He, and B. Bhandari, Drying Technology, 26 (2008) 816-835.Y. He, and B. Bhandari, Drying Technology, 26 (2008) 816-835.

� Structural design principles for delivery of bioactive components in nutraceuticals and functional foods, D.J. McClements, E.A. Decker, Y. Park and J. Weiss, Critical Reviews in Food Science and Nutrition, 49 (2009) 577-606.

� Bioavailability and delivery of nutraceuticals using nanotechnology, Q. Huang, H. Yu and Q. Ru, Journal of Food Science, 75 (2010) R50-R57

� Book: Global Issues in Food Science and Technology, 2009 Elsevier, Inc., Chapter 23, Nanotechnology for foods: Delivery Systems, E. Shimoni, pp 411-424.

� Nanostructured materials in the food industry, MA. Augustin and P. Sanguansri, Advances in Food and Nutrition Research, 58 (2009) 183-213.

� Food nanotechnology – an overview, B.S. Sekhon, Nanotechnology, Science and Applications 2010:3 1-15.


Thank You!

Questions?


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