11 Nanoencapsulation in Food

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

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
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Outline
Introduction Examples of Nanoencapsulated systems Liquid-Liquid System Solid System Emerging Nanoencapsulation forms Regulatory Update Summary

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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 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
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
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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) Viruses (10-300 nm) Formation of nanoparticles Size Reduction (Communition), Top down approach Particle formation (Precipitation), Bottoms up approach

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Technical difficulty, today

Nanotechnology Roadmap
Nano-devices

Nano-systems

Nano-materials + Tools

2000

2005
Nanoparticles

2010

2015

2020
Nanocomposites

Time, yrs

Nanodispersions

-Metal, metal oxides -Films/Coatings/ -Ceramic powders Nanolaminates -Carbon tubes and -Microemulsions spheres -Micellar solutions -Ferrofluids -Quatum dots -Liquid crystals -Dendrimers Liposomes -Porous supports -Capsules, fibers
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-Fabrics -Optical components -Orthopedic material -Polymers

Multidisciplinary Approach is Required

1.
Polysaccharides Proteins

Control physical stability (lower energy state) Low energy processing (controlled selfassembly)Effectiveness of ingredient delivery (controlled release) Improved control of food properties (e.g. flavor perception, texture)

2.

Water

Lipids

Air

3.

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Many potential applications for food, but overall tech is at very early stage Food Processing
fast-good-low costsafe food processing at nanoscale

Food Engineering
pleasant-nutritive-high quality organoleptic properties, and functional food Ingredient encapsulation Leverage intrinsic nanostructure of food stuff and food additives

Food Packaging
Cost, sustainability, convenience, safety and quality value added packaging Functionality: barrier, thermal, mechanical, biodegradable

Driver Nanomaterial s 2000(FACTS) Nanodevices 2010(NEAR REALITY) Nanosystems 2018(FICTION ?)

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Molecular filters Nanofiltration

Microreactors Portable sensors

Target delivery and control release Novel food matrixes

Sensors for diagnostic RFID Active packaging

Molecular Manufacturing

Bio-mimetic materials

Intelligent/Active Packaging

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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), (SolidLiquid), (Solid-Solid) Generally Water is the main component If liquid form required Filtration and/or pasteurization step or other sterilization step
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If dry form required

Removal of water to form a dry encapsulated powder form. Drying can be done by spray drying, freeze drying or other unit operations

Structured Food Systems, and Advance Delivery Technologies* = Edible Nano sized delivery systems
Micro/mini-emulsions (droplet size < 1m) Surfactant micelles- Reverse micelles Emulsion bilayers multilamellar, multivesicular, unilamellar Colloidosomes Association colloids Nanotubes Nanocochelates Solid Lipid Nanoparticles Biopolymer Nanoparticles - (e.g. porous starch granules, casein micelles) Functional Interfacial Nanolayers biopolymers, surfactants, lipids
* N. Garti. Delivery and controlled release of bioactives in foods and nutraceuticals. Chapter 18, pp 463, (2008)

Goal: Maximize protection, trigger and control the release pattern of 2011 Institute 2010 of Institute Food Technologists of Food Technologists 9 9encapsulated matter for food systems safely and effectively.

Liquid-Liquid Systems based on emulsions

Name

Particle Diameter 0.1-100 microns 100 nmmicrons

Thermodynamic Stability No

Appearance

Surfactant to Oil Ratio <1:10

Example

Emulsion

Opaque

Milk Liposomal CoQ10 enzyme NutraLease Technology Products High-Pressure homogenized emulsions

Liposome

Yes

Clear-Cloudy

N/A

Microemulsion

5-50 nm

Yes

Clear-Cloudy

>1:1

Nanoemulsion

10-100 nm

No

Clear-Cloudy

~1:1

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Food 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 Concentration, CMC) Thermodynamically stable Optically Transparent (Particle Size 5-50 nm)

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Microemulsions How are they made?

Energy input is needed, typically to mix two

immiscible phases, viz., oil and water Mixing

Gentle low shear mixing High shear mixing

Homogenization Low Pressure High Pressure Self emulsifying systems

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Microemulsions Stability
Kinetic Stability: Stable during storage and

product use (environmental condition)

Gravitational separation
Creaming or sedimentation

Flocculation due to non-steric hindrance Coalescence or Oswald Ripening due to solubility of one phase into the other phase.

Thermodynamic stability

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Microemulsions characterization
Particle Properties

Concentration Mean particle size Particle size distribution Particle charge Interfacial properties

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

concentration) Stability

Product performance
Appearance Flavor/ingredient stability Texture

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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 Rosemary Extract Beta-Carotene Sorbic Acid Citric Acid Unique Weight Management Solutions Coenzyme Q10 Flavor Oils Flaxseed oil Gama-tocopherol (Vitamin E) Isofavone Lutein Lycopene Mint
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Omega-3 fish oil from fish and algae Orange Phytosterols Rice bran oil

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.

US Patent 6,048,566, http://www.aquanova.de, http://www.zymesllc.com

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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 Useful for solubilizing lipophilic flavors/ingredients

Ingredients solubilized are

Omega-3 fish oil, vitamins, nutraceuticals,

phytosterols, flavors and others

US patent 7,182,950 , http://www.nutralease.com
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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 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 J Phys.: Condens. Matter 18 (2006) R635-R666
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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 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

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Stability of Nanoemulsion
Nanoemulsions are kinetically stable systems. Mechanism of instability 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

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Nanoemulsion for delivery of Nutraceuticals

Solubilization of phytochemicals, e.g., Curcumin, resveratrol, epigallocatchin gallate) and cartoenoids, e.g., lycopene, Bcartotene, lutein, zeaxanthin Improves bioavailability and solubility Factors affecting the bioavailability
Size of the emulsion droplet Lipid components in the formulation
Photographic images of curcumin nanoemulsions (A), nanodispersion (B), and water solution (C) (Food Chemistry, 119:669-74, 2010).

JOURNAL OF FOOD SCIENCEVol. 75, Nr. 1, 2010, R50-R57

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Solubilization of Hydrophobic Functional Ingredients Taiyo Kagaku Co. Japan.

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

J Sci Food Agric 86:20382045 (2006), DOI: 10.1002/jsfa Courtsey: Mr. Charles Brain, Ingredients Innovation International (3i)
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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 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
Food Hydrocolloids 23 (2009) 1427-1432; US Patent Application US2006/0264130 A1
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Electrospinning of Fibers
Zein fibers were electrospun using this setup

Journal of Food Science, 74 (2009) C233-C240.

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

Zein Nanofiber mat Zein with Beta-Carotene Nanofiber mat Food Hydrocolloids 23 (2009) 1427-1432
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Electrospinning of Nanofibers, Case Study: Beta-Carotene encapsulated in Zein Nanofibers

Beta-carotene is light sensitive, zein was able to protect Betacarotene from light The B-carotene loading was 0.61.2% by weight

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Food Hydrocolloids 23 (2009) 1427-1432

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New Nanoencapsulation technologies

Double-layered nanocapsules based on layer-by layer (LbL) electrostatic deposition method: Polyelectrolyte complexes Multi-assembled nanocapsule aggregates

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Book: Global Issues in Food Science and Technology, 2009,Chapter 24Nanostructured 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

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Professor Cory Berkland, University of Kansas, Presentation from 14th 2011 Institute of Food Technologists Industrial Microencapsulation Workshop, San Anotonio, TX

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.
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 workshop BernaMagnuson, Ph.D., Cantox Health Sciences International, Presentation at 14th 2011 Institute of Food Technologists Industrial Microencapsulation Workshop, San Antonio, March 2011

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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 Improved shelf stability Controlled release of actives Nanoencapsulation is an emerging area for food ingredients and should be used to enable distinct benefits.

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Useful Citations on Nanoencapsulation in Food

Design of Nano-Laminated Coatings to Control Bioavailability of Lipophilic Food Components, David Julian McClements, JOURNAL OF FOOD SCIENCEVol. 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. 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.
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Thank You!

Questions?

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