micro- and nano-encapsulation technologies -...

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


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


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)



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



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 & 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.


Dairy-based encapsulants used with hydrophilic cores – Example 2

10 |


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



Dairy-based encapsulants used for probiotics –Example 3

11 |


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


Plant protein-based micro- and nanoparticles for food ingredient Delivery - 1


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


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


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


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


Nanotechnology – Applications across Agrifood


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


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


New materials based on Nanotechnology



Approaches for Control of Size and Assembly of Materials


Top down and bottom up approaches


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™


http://pubs.acs.org/journals/mdd/about.html

http://pubs.acs.org/journals/mdd/about.html

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

http://www.avestin.com/c5page.html

http://www.avestin.com/c5page.html

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


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)


Forster & Konrad, J. Material Chemistry, 13, 2671, 2003

Self-Assembled Nanoparticle of Common Food Constituents That Carries a Sparingly Soluble Small Molecule


Bhopatkar et al., JAFC 2015, 63 (17), pp 4312–4319


Applications in the Food Industry


Nanotechnology in the Food Industry

Moraru et al., 2003. Food Technology, Vol 57(12), 24


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


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


Bacterial detection in drinking water based on gold nanoparticle–enzyme complexes


• 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


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


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




Nanocomposites used as antimicrobial films for food packaging based on metallic silver


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

http://apps.webofknowledge.com/full_record.do?product=UA&search_mode=GeneralSearch&qid=12&SID=W1xug7lYTivM8qS8SYs&page=9&doc=84&cacheurlFromRightClick=no

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


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


Nanoparticles for delivery of bioactives


McClements (2015) Journal of Food Science, 80(7), N1602-N1611,


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)


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


Thank youCSIRO Food & NutritionMary Ann AugustinResearch Group Leadert +61 3 9731 3486e [email protected]

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