Micro- and Nano-encapsulation Technologies
CSIRO FOOD AND NUTRITION
Mary Ann Augustin & Luz Sanguansri
Short Course on Micro- and Nano-encapsulation of Functional Ingredients in Food ProductsWorld Congress on Oils & Fats and 31st Lectureship Series31st Oct – 4th November 2015, Rosario, Argentina
Outline
• Encapsulation Technology• Applications in the Food Industry
• Nanotechnology & Nanoencapsulation• Approaches for Control of Size and Assembly of Materials• Applications in the Food Industry
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri2 |
Encapsulation Technology
Applications in the Food Industry
3 | Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Role of Microencapsulation in the Food Industry
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri4 |
Adapted from Perez & Gaonakar, Microencapsulation in the Food Industry, 2014, 543-549
Health & Wellness
ENCAPSULATION HAS AN IMPORTANT ROLE IN THE FOOD INDUSTY
Flavour & Taste
Interactive Foods &
Packaging
CONSUMERS ARE DEMANDING MORE
PRODUCT ATTRIBUTES
Convenience& Cost-
effectiveness
Food Safety & Stability
THE FOOD INDUSTRY IS LOOKING FOR SUPERIOR INGREDIENT
Improved shelf life
and product attributes
What are some of the things to think about?Desired functionality of encapsulated ingredients in selected applicationsApplication Purpose Desired functionality of encapsulant matrix
Flavours Protection Provide protection against environment and undesirable ingredient
interactions
Controlled release Release flavour in the mouth in response to the desired trigger (e.g. shear
due to chewing for flavour burst, dissolution when in contact with saliva)
Bioactives Protection Provide protection against environment and undesirable ingredient
interactions
Decrease flavour
release
Slow the release of undesirable flavours (e.g. bitterness of some nutrients,
chalky taste of calcium salts)
Site-specific
delivery
Protect against gastrointestinal tract conditions until targeted release site
(e.g. protect probiotics and bioactive peptides against stomach conditions)
Controlled release Control rate of release (e.g. decrease size of microcapsules to improve bio-
accessibility or tailor the thickness of the wall material to increase resistance
to gastric/intestinal enzymes)
Leavening Controlled release Leavening control during baking
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri5 |
Perez & Gaonakar, Microencapsulation in the Food Industry, 2014, 543-549
Microencapsulation for Food & Beverage Industry
Industry Segment Ingredient FunctionReady to Eat Meat Organic acids (et lactate) Improve shelf life
Increase resistance to bacteria (Listeria monocytogenes, Clostridia, Salmonella)
Bakery Flavours Fat barrier stabilises flavours in ready-to-bake doughs (eg Flavourshure - Balchem)
Gums and candies Volatile anti-odour or anti-microbial or taste-masking formulations
Minimize loss of volatile active components(eg TheraBreth (cinnamic aldehyde) – Wrigley;Trident (menthol) – Mondolez;
Instant coffee Thiols, unsaturated aldehydes, ketones
Flavour components
Dairy desserts Probioitics and vitamins Improve nutritional value
Range of dairy and food products
Omega-3 fatty acids / oil Improve nutritional value
Beverages Gas Gas-infusing or turbulence-inducing microparticles to produce froth or foams (eg instant cappuccino)
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri6 |
Perez & Gaonakar, Microencapsulation in the Food Industry, 2014, 543-549
Microencapsulation for Food & Beverage IndustryIngredient Encapsulation
MechanismFunction Commercial
Application Flavour compounds (eg thiols in coffee and esters in fruit)
Heat resistant coatingIsoelectric precipitation
Flavour enhancement Tea, coffee, juice
Omega-3 fatty acids, probiotics, prebiotics
Heat and moisture-tolerant coating, isoelectric precipitation
Flavor/odor masking and protection from moisture and heat
Beverage, nutritional bar, cereal
Mint flavours Coacervates Flavour release and long lasting
Chewing gum
Cheese ripening enzymes Enzyme immobilisation Cheese ripening Cheese products
Probiotics Biopolymer matrix Stabilisation during storage and protection through stomach
Dairy products
Carbonate, pressurised air Gas inclusion system / biopolymers/ cyclodextrin
Foaming Beverages
Spoilage by-productreacting agent
Nanocomposite / Microencapsulation
Colour change to indicatefood safety
Interactive and intelligentpackaging
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri7 |
Perez & Gaonakar, Microencapsulation in the Food Industry, 2014, 543-549
Selected Examples from the Literature
- Dairy encapsulants for hydrophobic, hydrophilic and probiotic cores
- Plant protein-based micro- and nano-particles
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri8 |
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Dairy-based encapsulants used with hydrophobic cores – Example 1
9 |
Encapsulated component
Dairy encapsulant Encapsulation technique
Benefit(s) of encapsulation
Reference
Orange oil WPI Spray drying Protection against oxidation
Kim & Morr, 1996
Soy oil Sodium caseinate Spray drying High encapsulation efficiency (89%)
Hogan et al., 2001a
CLA WPC Spray drying Protection against oxidation
Jimenez et al., 2004; 2006
Flaxseed oil WPI Spray drying Protection against oxidation
Partanen, Raula, Seppānen, Buchert, Kauppinen, & Forssell, 2008
AMF WPI Spray drying Protection against oxidation during storage
Moreau & Rosenberg, 1996
AMF WPI, WPC-50, WPC-75
Spray drying High encapsulation efficiency (> 90%)
Young et al., 1993a
Retinol WPI Emulsification/Cold gelation /Air drying
Gastroresistance and protection against oxidation
Beaulieu et al., 2002
Oregano, citronella and marjoram flavours
SMP or WPC Spray drying Improved retention of flavours during spray drying
Baranauskienė et al., 2006
Augustin, M.A. and Oliver C.M..(2014) IN The Art and Science of Microencapsulation: An Application Handbook for the Food Industry. (Eds. Anilkumar Gaonkar, Niraj Vasisht, Atul Khare, Robert Sobel), Academic Press, Chap 19, 211-226.
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Dairy-based encapsulants used with hydrophilic cores – Example 2
10 |
Encapsulated component
Dairy encapsulant Encapsulation technique
Benefit(s) of encapsulation Reference
3-methylbutyr-aldehyde
WPC and sodium caseinate or SMP as secondary emulsifier
Double emulsification/Spray drying
Improved retention of aldehyde during storage
Brückner et al., 2007
Sumac concentrate
Whey powder or SMP
Spray drying Improved retention of flavour during spray drying
Bayram et al., 2008
Ascorbic acid Lactose Co-crystallisation Improved retention of ascorbic acid during co-crystallization
Kim et al., 2001
Citric acid Casein Co-crystallisation Development of a novel, efficient and cost-effective microwave encapsulation technique that provided high encapsulation efficiency (100%)
Abbasi & Rahimi, 2008
IgY WPC as secondary emulsifier
Double emulsion /Gelation/Air drying
Protected IgY from highly acidic conditions and heat treatment processes
Cho et al., 2005
Protease enzymes
High melting milkfat fraction
Gel beads Increased rate of proteolysis during cheese ripening
Kailasapathy & Lam, 2005
Caffeine WPC Hydrogels/Air drying
Controlled release of caffeine
Gunasekaran et al., 2006
Augustin, M.A. and Oliver C.M..(2014) IN The Art and Science of Microencapsulation: An Application Handbook for the Food Industry. (Eds. Anilkumar Gaonkar, Niraj Vasisht, Atul Khare, Robert Sobel), Academic Press, Chap 19, 211-226.
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Dairy-based encapsulants used for probiotics –Example 3
11 |
Encapsulated component
Dairy encapsulant
Encapsulation technique
Benefit(s) of encapsulation
Reference
Lactobacillus sp Milkfat and/or denatured WPI
Emulsification/Spray drying
Improved cell viability in yogurt and after exposure to simulated gastrointestinal fluids
Picot & Lacroix, 2003; 2004
Lactobacillus sp WPI Freeze drying Improved cell viability during storage and in yogurt
Kailasapathy & Sureeta, 2004
Bifidobacterium sp WPI Freeze drying Improved cell viability in simulated gastrointestinal fluids
Reid et al., 2005
WPI Freeze drying Improved cell viability during the production and storage of biscuits, and improved pH stability
Reid et al., 2007
Milkfat Spray coating Improved cell viability during storage
Champagne et al., 1995
Augustin, M.A. and Oliver C.M..(2014) IN The Art and Science of Microencapsulation: An Application Handbook for the Food Industry. (Eds. Anilkumar Gaonkar, Niraj Vasisht, Atul Khare, Robert Sobel), Academic Press, Chap 19, 211-226.
Plant protein-based micro- and nanoparticles for food ingredient Delivery - 1
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri12 |
Type of particle Method Core
Zein microparticles Spray drying or supercritical anti-solvent method
Food grade antimicrobials: lysozyme, thymol, nisin
Spray or freeze drying Flax oil
Zein nanoparticles Liquid–liquid dispersion method
Polyphenols: curcumin, quercetin, tangeretin, cranberryprocyanidins
Phase separation or liquid–liquid
Essential oils: oregano, red thyme, cassia and carvacrol
Liquid–liquid dispersion method or electrospraying
Bioactive lipids: fish oil, DHA, Food coloring agents: curcumin, indigocarmine
Zein-chitosan complex nanoparticles
Low-energy phase separation method
Vitamin D3
SPI-zein complex microparticles / SPI nanoparticles
Ca2+-induced cold gelation method
Riboflavin / Vitamin B12
Wan et al. (2015) Food & Function 6, 2876 – 2889
Plant protein-based micro- and nanoparticles for food ingredient Delivery - 2
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri13 |
Type of particle Method Core
SPI/FA-conjugated SPI Ethanol solvation method Curcumin
SPI-CMCS complex nanoparticles
Ca2+ induced co-gelation method
Vitamin D3
Soy protein-soy polysaccharide complex nanogels
High-pressure homogenization and heating
Folic acid
Soy lipophilic protein Ultrasonic treatment Conjugated linoleic acid
Gliadin nanoparticles Antisolvent precipitation method
All-trans-retinoic acid, vitamin E
Barley protein microparticles
Pre-emulsifying process followed by microfluidizing
Fish oil, β-carotene
Barley protein nanoparticles High pressure homogenization
β-Carotene
Soy protein nanocomplex Ligand binding properties Vitamin B12, cranberry polyphenols, curcumin, RES and grape polyphenol
Wan et al. (2015) Food & Function 6, 2876 – 2889
Nanotechnology and Nanoencapsulation
14 | Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Nanotechnology
Nanotechnology is the ability to work at the atomic, molecular and supramolecular level (in the order of 1-100nm) in order to understand, create and use material structures, devices and systems with fundamentally new properties and functions resulting from their small structures
15 |
Roco, Current Opinion in Biotechnology 2003, 14:337
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Relevance of the concept of scale to food materials – Link to Nanotechnology Concepts
Leser et al., IN Food colloids, biopolymers and materials (Eds Dickinson and van Vliet, 2003), pp3-13
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri16 |
Nanotechnology – Applications across Agrifood
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri17 |
http://www.bing.com/images/search?q=nanotechnology+in+food&view=detailv2&&id=B6E9F703FECEF1068BC82C8DFE20233396618D39&selectedIndex=0&ccid=8LqON4nK&simid=608000695069049234&thid=OIP.Mf0ba8e3789ca59ba3e7f3eeadf1d949bH0&ajaxhist=0
Concept of Size and Its Implications for Food Materials, Processes and Products
Size relates to functionality in terms of the physical properties of food materials
• Smaller size means bigger surface area for the purposes of water absorption (solubility), chemical reaction (e.g. oxidation, digestion), catalyst/enzyme activity, flavour release, bioavailability etc
Controlling the size and assembly of food components provides opportunities for designing new food products
• Link b/w nanoscale and food microstructure• Effects on nutritional and physiological functionality
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri18 |
Nanoencapsulated particles
Nanoemulsions and Nanoparticles- Developed using a range of materials- Co-block polymer micelles, polyelectrolyte capsules, colloidosomes,
polymersomes, gelled macromolecules
Target release- In response to environment (eg pH, salt concentration, ultrasound)
Target distribution- Control of surface properties of polymers- Control interaction between particle and cells in body
19 | Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
New materials based on Nanotechnology
20 | Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Nanotechnology and Nanoencapsulation
Approaches for Control of Size and Assembly of Materials
21 | Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Top down and bottom up approaches
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri22 |
Scientific Approaches for Modification of Materials in Nanotechnology
• Top-down approach
• Nanostructures are produced by breaking up bulk materials
with large structures into smaller ones
• Physical machining of materials to nanometre range by
grinding, milling, precision engineering, homogenisation
and lithography
• Bottom-up approach
• Nanostructures are built-up from individual atoms or
molecules that are capable of self-assembling
BioSilicon™
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri23 |
Top-Down Approach for Size reduction of food
• Ball Milling and Jet Milling
• High Pressure Homogenisation
• Microfluidisation
• Ultrasound Emulsification
• Membrane Emulsification
Materials_ Microencapsulation | Augustin & Sanguansri
Solid Lipid Nanoparticles (SLNs)
Materials_ Microencapsulation | Augustin & Sanguansri25 |
SLNs are particles consisting of a matrix made of solid lipid shell Weiss et al. (2008) Food Biophysics, 3, 146-154
Emulsions – How the components assemble will affect its functional properties
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri26 |
Bottom-up Approach in NanotechnologyBuilding up products by assembly of molecules [Molecule-by-
molecule formation of hierarchical structures]• Biomimetic Approach (Mimics strategy used by biological systems for
structuring of molecules)– Nanometre scale self-assembly by autonomous organisation of components into
structures and patterns without human intervention– Organisation of nanometre scale molecular assemblies into larger structures from
10 nm to sub-micrometre range)
A) Self-assembled polymer structures block co-polymer micellesB) Polyelectrolyte capsulesC) Colloidosomes D) Block co-polymer vesicles (polymersomes)
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri27 |
Forster & Konrad, J. Material Chemistry, 13, 2671, 2003
Self-Assembled Nanoparticle of Common Food Constituents That Carries a Sparingly Soluble Small Molecule
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri28 |
Bhopatkar et al., JAFC 2015, 63 (17), pp 4312–4319
Nanotechnology and Nanoencapsulation
Applications in the Food Industry
29 | Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Nanotechnology in the Food Industry
Moraru et al., 2003. Food Technology, Vol 57(12), 24
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri30 |
Potential benefits of nanotechnology in Food
• Food safety and shelf life extension
• Enhancement of taste, flavour and texture
• Improvements in processing
• Improvement in absorption ratio of nutrients
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri31 |
Nanotechnology in Food SafetySensing for safetyCreation of new materials and novel methods and devices for
sensing, diagnosis and analysis of pathogens and single molecules for ensuring safety, quality and security of the food supply in real time
• Interactions between biomolecules and molecular assemblies with electronic structures or materials for nano- and microfabrication of devices for improved methods and sensors for detecting pathogens and improved diagnostics for food allergens
• Formation of nanoparticles and quantum dots for biotagging or barcoding within biological systems to design products with electronic functionality in materials for use in intelligent packaging of food materials and tracking food quality in supply chains
• Silver Nanoparticles embedded in plastic that line storage bins – Ag nanoparticles kill bacteria
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri32 |
Bacterial detection in drinking water based on gold nanoparticle–enzyme complexes
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri33 |
• Gold nanoparticles functionalized with positively charged quaternary amine headgroups bind to enzymes ⇒ inhibition of enzymatic activity
• In the presence of bacteria, the nanoparticles were released from the enzymes and preferentially bound to the bacteria
⇓Increase in enzyme activity, releasing a redox-active phenol from the substrate
Sensing of Escherichia coli and Staphylococcus aureus, resulting in a rapid detection (<1 h) with high sensitivity (102 CFU mL−1)
Chen et al. Analyst, 140, 4991-4996
Nanoencapsulation of essential oils to enhance their antimicrobial activity in foods
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri34 |
Brightfield (a and c) and fluorescence micrographs (b and d) of S. cerevisiae cells exposed to nanoemulsion Terpene-Soy lecithin captured by fluorescence microscopy after 5 min (a and b) and 24 h (c and d).
Donsi et al (2011) LWT - Food Sci Tech, 44,1908–1914
• Under a fluorescent light, the nanoemulsion droplets cannot be distinguished when they are dispersed in an aqueous system due to their nanometric size
• When the nanoemulsion droplets accumulate in the cell membrane as well as the intracellular space, the yeast cells became fluorescent and can be observed
Inactivation curve of L. delbrueckii suspended in juice with terpenes nanoemulsion
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri35 |
Donsi et al (2011) LWT - Food Sci Tech, 44,1908–1914
(a) orange juice treated with terpenes nanoemulsion
(b) pear juice treated with terpenes nanoemulsion
Control
Control
1g/L terpene mixture
1g/L terpene mixture
10g/L terpene mixture
10g/L terpene mixture
Nanocomposites used as antimicrobial films for food packaging based on metallic silver
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri36 |
Nanoparticle release from nano-silver antimicrobial food containers Echegoyen & Nerin (2103)FOOD AND CHEMICAL TOXICOLOGY, 62, 16-22
• In all cases the total Ag migration is far below the maximum migration limits stated by the European legislation
Canadian penny-based silver nano-structure was synthesized as SERS-active substrate for determination of CAP in food matrices
⇓Detects trace level of chemical hazards in food systems within 15 min
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Detection and Quantification of Chloramphenicol in Milk and Honey Using Molecularly Imprinted Polymers: Canadian Penny-Based SERS (Surface-enhanced Raman Spectroscopy) Nano-Biosensor
37 |
Gao et al (2014) JFS, 79(12) N2542-N2549
Template molecule (CAP), functional monomer (acrylamide), cross-linking agent (ethylene glycol dimethacrylate), initiator (2,2’-azobis(isobutyronitrile)), and porogen (methanol) were employed to form MIPs via “dummy” precipitation polymerization
Nanotechnology for healthy foodsDevelopment of healthier foodsHealthy foods and diets may be devised to promote health of consumers and the understanding between genetic pre-dispositions, nutrition and diet may be used to design diets for target populations
• New nanoscale technologies for the fabrication of materials, manufacture and control of microencapsulated products have potential for improving the quality of functional foods and target delivery of bioactives and desired molecules
• Nanotechnology may be directed towards the manipulation of food surface structure on a molecular scale to improve the metabolic consequences of consuming processed foods
• Biotransformation for production of high value nutritional components and food ingredients
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri38 |
Nanoparticles for delivery of bioactives
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri39 |
McClements (2015) Journal of Food Science, 80(7), N1602-N1611,
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Stability of Bioactive in SLN & crystal structure of fat
40 |
• Crystallization behavior of SLN depended on the bioactive and surfactant type
• Oxidative stability of bioactives depended on the crystal structure
• Delivery systems need to be designed specifically for each bioactive compound
Salminen et al. Food Chem (2016), 928-937
Nanotechnology encapsulation platforms used in food applications
Chitosan hydrogels Whey protein nanostructures
Examples:• Novasol® range: ready to use liquid formulations
by Aquanova AG• NutraLease®: nanosized self assembled liquid
structures (NSSL)
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri41 |
Market drivers & trends - Encapsulation
5395.2 5788.7 6222.69070.5
3776.1 4049.14347.1
6307.8
2807.23025.8
3267.7
4872.7
1619.11717.3
1823.9
2493.2
$0
$5,000
$10,000
$15,000
$20,000
$25,000
2007 2008 2009 2014
MacroencapsulationHybrid TechnologiesNano-encapsulationMicroencapsulation
GLOBAL FOOD ENCAPSULATION MARKET BY TECHNOLOGY2007 – 2014 ($MILLIONS)
Source: Global food encapsulation market, MarketsandMarkets, 2009** Global Business Insights – Innovations in delivery methods for nutraceutical food and drinks, 2011
CAGR 7.8%
CAGR 7.7%
CAGR 8.3%
CAGR 6.5%
CAGR 2009-14
Mmarket: $23 billion by the year 2014Europe - CAGR of 9.1% North America - largest market share - 41% in 2014
Target Groups/Markets:Infant, functional and health food segments Ageing populationFoods with disease prevention benefits.
Concerns – Nanoencapsulation:“Whilst this is in part due to potential and unknown toxicity relating to nanoparticles, it is also the case that nanoencapsulation is rarely the best solution”**
$ M
illio
ns
Year
Micro and Nanoencapsulation Technologies | Augustin & Sanguansri
Thank youCSIRO Food & NutritionMary Ann AugustinResearch Group Leadert +61 3 9731 3486e [email protected]