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MICROENCAPSULATION OF FLAVOUR
PREETHI RAMACHANDRAN (H D)
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FOOD FLAVOUR ???
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WHAT IS FLAVOUR ? Mixture of taste and odour.
Principally perceived by taste receptors in mouth and the aroma receptors in nose. Flavour compound into divided into two classes: Compounds responsible for taste. Compounds responsible for odour.
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Perception of flavour in mouth:
Compound arousing taste perception must dissolve in saliva before they can be perceived. As a result, they interact with taste receptors located in taste buds on the tongue. Flavour responsible for odour are volatile compounds which are perceived by odour receptor sites of the smell organ such as olfactory tissues of nasal cavity. Flavour Volatile Non volatile
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FOOD FLAVOUR Essence of food.
Important role in consumer satisfaction and influence the further consumption of food. Stability of flavour in food-important…… because of its relationship with the quality and acceptability of food. Most food flavour are volatile and chemically unstable in presence of air, light, moisture and high temperature.
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FLAVOUR STABILITY Factors linked to aroma affecting the quality of the food. Cause of Modification in overall flavour that reduce aroma compound intensity or produce off-flavour in food Physico-chemical properties. Concentration and interaction of volatile aroma molecules with food components Manufacturing and storage process. Packaging material. Ingredients in food.
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PHYSICO-CHEMICAL PROPERTIES OF FLAVOUR
Depends of nature of food and flavour compounds. Flavour delivery depends on the availability of the flavour compound in the gas phase. Properties of flavour compound determining the interaction with the food components are: Molecular size, Functional group, Shape and Volatility. Volatility of compound under static condition is determined by properties; Molecular weight, Vapour pressure, Boiling point, Octanol water partion cofficient.
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FOOD-FLAVOUR INTERACTION
Defining the major parameter that influence the release of flavour compound from food would provide information to control the flavour response of food product. Food matrix components can bind, entrap or encapsulate volatile and non volatile flavour compounds. The interaction results in reduced rate of flavour release and also affects the flavor intensity and quality of food.
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MECHANISM OF FOOD FLAVOUR INTERACTION
Binding Binding means the inclusion, adsorption, absorption and retention of flavour compounds onto nonvolatile substrates. Partitioning Partitioning means the distribution of flavour compound between phase such as oil, water and gas phases. Release Release means the availability of flavour compounds from the bulk food into the gas phase for sensory perception.
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Main groups of flavour compound interaction in food matrices compounds
Irreversible bonding such as interaction between aldehyde or ketones group and amino groups of protein. Covalent binding Occurs between the polar or volatile alcohol and heteroatom (N, S, O) of food components Hydrogen bonding Weak and irreversible bonding such as van der waals bond between apolar compound and fat molecules. Hydrophobic bonds For example inclusion complexes, which occurs between flavour compound or starch derivatives. Physical binding
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Need of flavour encapsulation
To guard against either light induced reactions or oxidation To retain volatile aroma compound in food product during storage To protect the constituents from undesirable interaction with food To provide liquid flavouring free flowing powder properties To minimise flavour/flavour interaction To effect the controlled release of flavour and other volatile bioactive compounds COST865 spring 2009 meeting
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MICRO-ENCAPSULATION TECHNIQUE
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MICROENCAPSULATION…??? Defined as process to entrap one substance within another substance, thereby producing particles within diameter of few nanometer to few micrometers. Products obtained by this process are called microparticles, microcapsules and microspheres which differentiate in morphology and internal structure.
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KEY TERMS: Substance encapsulated: core material, the active agent, fill, internal phase, or payload phase. Substance encapsulating: coating, membrane, shell, carrier material, wall material, external phase, or matrix. The carrier material used in food products or processes should be food grade and able to form barrier for active agent and its surrounding.
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TYPES OF ENCAPSULATES:
Can be classified on three basic categories according to their morphology. Mononuclear Polynuclear Matrix type Mononuclear and polynuclear is also known as reservior type. Mononuclear are called capsules, single-core, mono-core or core-shell type. Whereas polynuclear are called poly- or multi-core type of encapsulates. Another types of encapsulate is coated matrix type.
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Mechanisms for the release of encapsulated core materials:
Disruption of the coating by pressure, shear, or abrasion forces. Enzymatic degradation of the coating where permeability changes. Diffusion or leaching of core materials. The rate of release of core material is a function of : the permeability of the coating to core material. the dissolution rate of the core materials the coating thickness the concentration gradient existing across the coating membrane.
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REASONS FOR ENCAPSULATION
Protect reactive substances from the environment. Convert liquid active components into a dry free flowing solid system. Separate incompatible components for functional reasons. Mask undesired properties of the active components. Protection of active compounds from immediate environment. Controlled release of active compounds. Targeted release of encapsulated materials.
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MATERIAL FOR ENCAPSULATION
Preparation of microspheres requires understanding of the general properties of microcapsules, such as: Nature of core and coating materials, Stability and release characteristics of coated materials and Microencapsulating methods. Coating material Core material Film forming material, natural or synthetic polymer. Characteristic of ideal coating material: Good rheological properties. Ability to disperse or emulsify the active material and stabilize the emulsion produced. Nonreactive Ability to seal and hold active material. Maximum protection to active material. Ability to completely release the solvent. Inexpensive, food-grade status. Chemical nonreactive. Solubility in solvent acceptable in food industry. Liquid or solid in nature. Composition of the core material. Liquids core can include dispersed and/or dissolved material. solid core can be a mixture of active constituents, stabilizers, diluents, recipients and release-rate retardants or accelerators.
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(Madene et al., 2006)
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APPLICATION OF ENCAPSULATION
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ENCAPSULATED FOOD INGREDIENTS AND THEIR APPLICATION
No. Category of food ingredients Examples Applications 1. Acidulants Lactic acid, vitamin C, acetic acid, potassium sorbate, sorbic acid, calcium propionate and sodium chloride. Development of colour and flavour in meat emulsion, dry sausage products, uncooked processed meat and meat containing materials. Baking industry use stable acids and baking soda in wet and dry mixes to control the release of carbon dioxide during processing and subsequent baking. 2. Flavoring agents Citrus oil, mint oil, onion oil, garlic oil, spice oleoresins To transform liquid flavorings into stable and free flowing powders, which are easier to handle and incorporate into a dry food system. 3. Sweeteners Sugars (nutritive or artificial sugars) To reduce the hygroscopicity, improve flowability, and prolong sweetness perception.
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Category of food ingredients
No. Category of food ingredients Examples Applications 4. Colourants Annatto, β-carotene, turmeric Encapsulated colors are easier to handle and offer improved solubility, stability to oxidation, and control over stratification from dry blends. 5. Lipids Fish oil, linolenic acid, rice brain oil, egg white powder, sardine oil, palmitic acid, seal blubber oil To prevent oxidative degradation during processing and storage. 6. Vitamins and minerals Fat-soluble: vitamin A, D, E, and K. Water-soluble: vitamin C, vitamin B1, vitamin B2, vitamin B6, vitamin B12,niacin, folic acid To reduce off-flavors. To permit time-release of nutrients. To enhance the stability to extremes in temperature and moisture. To reduce each nutrient interaction other ingredients. 7. Enzymes and microorgnism Lipase, invertase, Brevibacterium linens, Penicillium roqueforti To improve the stability. To reduce the ripening time.
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BENEFITS OF MICROENCAPSULATION
Protects core compounds from the environments (heat, moisture, oxygen and light. Reduces loss due to vaporization. Modulates intact properties of compounds for easy control during processing. Superior handling of active agents. Adjustable properties of active compounds. Immobility of active agents. Improved safety. Improved stability in final product and during processing. Off-flavour masking. Controlled release.
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HURDLES DURING ENCAPSULATION:
Additional cost Increased complexity of production process and/or supply chain. Undesirable consumer notice of encapsulated in food products. Stability challenges of encapsulates during processing and storage of food products. Encapsulates facilitates formulation of food products that are healthier, tastier and convenient.
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ENCAPSULATION METHODOLOGIES
Physical processes Spray drying Spray chilling Fluid bed coating Pan coating Air suspension coating Centrifugal extrusion Stationary nozzel extrusion Submerged nozzel extrusion. Physiochemical processes Simple coacervatin Complex coacervation Entrapment into liposomes Chemical processes Interfacial polymerization Molecular inclusion Matrix polymerization In-situ polymerization Solvent extraction Solvent evaporation
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MICROENCAPSULATION TECHNIQUES
Spray-drying Extrusion Spray-cooling Coacervation Spray-chilling Microencapsulation techniques Liposome entrapment Fluidised bed coating Inclusion complexation Centrifugal extrusion Lyophilization cryocrystallization Centrifugal suspesion separation
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SPRAY DRYING ENCAPSULATION
Used in food industry since late 1950s:, To provide flavor oil with protection against degradation/oxidation. To convert liquid to powders. Used in encapsulation for preparation of dry, stable food additives and flavours. Low-cost commercial process, widely used for encapsulation of encapsulation of fragrances, oil and flavours. Economical; flexible (offers substantial variation in microencapsulation matrix). Limitation: limited number of shell material are available.
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Shell material must be soluble in water.
Shell material includes gum acacia, maltodextrin, hydrophobically modified starch. Material to encapsulate is homogenized with the carrier material Mixture is fed into spray drier Atomized with nozzle or spinning wheel Water is evaporated by the hot air contacting the atomized material. Microcapsules are then collected after they fall to the bottom of the drier.
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Spray chilling/spray cooling
Core and wall mixture are atomized into cool or chilled air, which causes the wall to solidify around the core. Does not involve evaporation of water. In spray cooling, coating material is vegetable oil or its derivatives, whereas in spray chilling its is fractionated or hydrogenated vegetable oil. Insoluble in water due to lipid coating. Used for coating water soluble core material such as minerals, water soluble vitamins, enzymes, acidulates and some flavours.
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FLUID BED COATING Developed by D. E. Wurster in 1950s.
The liquid coating is sprayed onto the particles and the rapid evaporation helps in the formation of an outer layer on the particle. Coating material must have Acceptable viscosity, Thermally stable, Should be able to form a film over a particle surface. 5-50% coating is applied, depending on the particle size of the material. Coating material might be aqueous solution of cellulose derivatives, dextrin, proteins, gums and starch derivatives.
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Different type of fluid-bed coaters are: Top spray Bottom spray
Tangential spray Schematics of a fluid-bed coater. (a) Top spray; (b) bottom spray; (c) tangential spray. (Redrawn from Ghosh 2).
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EXTRUSION Relative low temperature entrapping method, which involves forcing a core material in molten carbohydrate mass through a series of dies into a bath of dehydrating liquid. Pressure and temperature employed are more than <100 psi and 115˚C. Coating material hardens on contacting the liquids, forming an encapsulating matrix to entrap the core material. The extruded filaments are separated from liquid bath, dried, and sized. Carrier used are more than one ingredients such as sucrose, maltodextrin, glucose syrup, glycerine and glucose.
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Scheme of a melt extruder
Scheme of a melt extruder. Most often, extruders with two screws are preferred. Each section can be temperature controlled. The carrier material is commonly added via a twin screw feeder in the first section, and water and active can be added simultaneously or later.
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Flow diagram of encapsulation of food flavors by extrusion method.
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Centrifugal extrustion
Encapsulating head consist of a concentric feed tube. Coating material flows through the outer tube. Centrifugal force impels the rod outward, causing it to break into tiny particles. During surface tension, the coating material envelops the core material. Entire device is attached to a rotating shaft. Through the head coating and core material are pumped separately Core material passes through the center tube Head rotates , the core and coating materials are co-extruded through the concentric orifice. ENCAPSULATION Used in encapsulation of products such as flavorings, seasoning, and vitamins. Wall material includes gelatin, sodium alginate, starches, cellulose derivatives, fats/fatty acids, waxes and polyethylene glycol. Is a liquid co-extrustion process utilizing nozzles consisting of concentric orifice located on the outer circumference of a rotating cylinder.
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Lyphilization Used for dehydration of almost all heat sensitive material and aromas. Used in encapsulation of water soluble essences and natural aroma. Retention of volatile compound during the lyophilization is dependent upon the chemical nature of the system.
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Emulsification Dispersed emulsion droplets may be turned into microcapsules. First, dispersing an oil phase (containing the active compound to encapsulate) in a polymer solution, and then including the precipitation of the polymer at the interface of the droplets. Water soluble food active agent encapsulated in w/o emulsions or double emulsion of the type w/o/w. o/w emulsion affects the taste by changing the aqueous phase volume and thus the concentration of taste molecule in water and by suppressing contact of salt with taste receptors.
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Coacervation Core material dispersion in solution of shell polymer separationof coacervate from solution; Liquid-liquid phase separation mechanism of an aqueous solution into a polymer rich phase (known as coacervates) and a polymer-poor phase. Involves separation process of liquid phase of coating material from polymeric solution followed by coating of that phase as uniform layer around suspended core particle. Shell composed of gum arabic and gelatin. Batch type process consist of three steps and are carried out under continuous agitation: coalescence of coacervate to form continuous shellaround core particles. coating of core material by microdroplets of coacervate; Formation of three immiscible chemical phase Deposition of the coating Solidification of coating material
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Complex coacervates are made from
o/w emulsion with gelatin and gum arabic at 1:1 w/w ratio at 2-4% w/w of each polymer dissolved in the water phase via adjusting the pH from neutral to about 4 under turbulent condition. Temperature above 35˚C, temperature above gelation temperature of gelatin. Creates three immiscible phases (oil, polymer-rich, and polymer-poor phase) Polymer-rich phase droplets will deposit on the emulsion surface Oil is emulsified in 8-11% (w/w) gelatin solution Addition of gum arabic dilution water Cooling below 35˚C Deposited gelatin and shell solidify (Gouin, 2004; Lemetter et al. 2009) Thies , 2007; Lemetter et al. 2009)
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LIPOSOME ENTRAPMENT Consist of an aqueous phase that is completely surrounded by phospholipids-based membrane. Phospholipids when dissolved in aqueous phase, and exposed to high shear rates by using collidal mill, forms liposomes. Liposome consist of atleast one closed vesicle composed of bilayer membranes which are made of lipid molecules. Mechanism for formation: hydrophillic-hydrophobic interaction between phospholipids and water molecules.
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Advantage: Liposome impart stability to water soluble material in high water activity application. Targeted delivery of the content in specific part of the food stuff.
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Factors effecting encapsulation:
(Yeo and Park, 2004)
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Global research activities in encapsulation of food and flavours:
Key words No. of records Microencapsulation and food 223 Microencapsulation and oil 496 Microencapsulation and fatty acid 78 Microencapsulation and vitamins 43 Microencapsulation and antioxidant 41 Microencapsulation and oleoresin 17 Microencapsulation and volatile Microencapsulation and flavour 25 Microencapsulation and essential oil 30 Microencapsulation and aroma 22 (COST865 spring 2009)
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Characteristic of the wall material used for encapsulation flavours
(Madene et al., 2006)
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Controlled flavour release
Defined as method by which one or more active agents or ingredients are made available at a desired site and time and at specific rate. (Pothakamury et al., 1995) Mechanism provides controlled, sustained and targetted release of core material. Release of core material-one or combination of stimuli. Factors affecting release: Nature of core and coating material Capsule size Diffusion of volatile compound through matrix Degradation of matrix material
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Mechanism of flavour release
Release of flavour by diffusion Controlled by solubility of a compound in the matrix and the permeability. Important in food because it is the dominant mechanism in controlled release from encapsulation matrix Steps in release of flavour are: Diffusion of the active agent to the surface of matrix Partition of volatile component between the matrix and the surrounding food Transport away from the matrix surface. Release of flavour by degradation Release of an active compound from matrix type delivery system may be controlled by diffusion, erosion and combination. Homogeneous and heterogeneous erosion Release of flavour by swelling Controlled by swelling the flavour dissolved or dispersed in a polymeric matrix is unable to diffuse to any significant extent within the matrix. When the matrix polymer is placed in thermodynamically compatible medium, the polymer swells because of absorption of fluid from the medium. The aroma in the swollen part of matrix then diffuses out. Release of flavour by melting Involves the melting of walls of capsule to release the active material.
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Release characteristic of allyl isothiocynate
Effects of temperature and relative humidity on the release of AITC from the inclusion complexes The maximum inclusion ratios of various flavors in modified (Takeshi, 2007)
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Release characteristics of complexed flavors prepared by freeze drying and spray drying
(Takeshi, 2007)
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Aroma retention and flavour release of peppermint essential oil encapsulated by spray-drying into food starch based matrices (Baranauskiene et al., 2007)
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Average flavour release from cheese containing limonene capsule
Larger capsule, blank pH 7 Large capsule, WP/GA pH 4; not cross-linked Small capsule, WP/GA pH 4; not cross-linked Small capsule, blank pH 7 Small capsule, WP/GA pH 4; cross-linked Large capsule, WP/GA pH 4; cross-linked (Weinbreck et al., 2004)
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Concentration of 3-methyibutyraldehyde released from different microcapsules after minutes lipase treatment (Bruckner et al., 2007)
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Release concentration of 3-methylbutyraldehyde from hydrated as a function of carrier material and dry mass in second aqueous phase at 90˚C (Bruckner et al., 2007)
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RETENTION OF FLAVOURS IN MICROCAPSULES
Factors affecting the flavour retention Properties of volatile compounds: Molecular weight Vapour pressure Solubility Properties of emulsion/feed solution: Solid concentration Viscosity Emulsion size Emulsion stability Concentration of flavor in the emulsion Additive materials Infeed temperature Type of capsule wall material Mono- and disaccharides - Mono- and disaccharides- Hydrolyzed starches Chemically modified starches Chemically modified starches Gums- Proteins (soybean) Blend of Gum arabic and hydrolyzed starch- Blend of modified starches and maltodextrin- Blend of hydrolyzed starches with proteins and lipids
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Encapsulation efficiency of flaxseed oil microencapsulated by spray drying using different combinations of wall materials The encapsulation efficiency of samples was significantly influenced by the type of wall material used, since emulsions prepared with Hi-Cap resulted in particles with considerably lower surface oil than those prepared with the other ones. The encapsulation efficiency values varied from 62.3% to 95.7%, being the lowest value obtained for MD:WPC. (Helena et al., 2013)
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Microencapsulation Of Peppermint Oil By Spray Drying
Effect of Carrier: oil ratio on the retention Properties of powder encapsulated peppermint oil (Total oil, Surface oil, Moisture content and Bulk density) (Badee et al., 2012)
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Encapsulation Efficiency of Food Flavours and Oils during Spray Drying
a. Effect of emulsion viscosity through addition of sodium alginateon the retention of ethyl caproate and Allylguaiacol during spray-drying microencapsulation. c. Influence of emulsion droplet size on the retention of flavors during spray-drying encapsulation b. Effect of initial solids concentration on the retention of different flavors during spray drying encapsulation . d. Influence of the difference between the emulsion droplet size and the particle size of dried microcapsules on the volatile retention. (Jafari et al., 2008)
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Flavour retention as a function of carrier material and time
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Flavour retention in alginate gel beads during baking of crackers
Effect of flavour encapsulation Effect of moisture content (De Roos, 1999)
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Effect of capsule type on flavour retention during the baking of crackers
The relatively high retention of volatile compounds by the alginate gel beads is due to their bigger size (about 1mm versus 250 mm for the coacervate microcapsules Effect of encapsulation on flavour release from sugar based stick gum measured as percentage released after 5 min of chewing (De Roos, 2003)
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STABILITY OF ENCAPSULATED FLAVOUR
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Oxidative stability of garlic oil-containing coacervates during storage
Peroxide value (PV) of the unencapsulated garlic oil significantly increased at day 4 in type A or type B gelatin-gum acacia based coacervates (p≤ 0.05) indicating the primary oxidation products started to appear in the unencapsulated garlic oil. Type A or B gelatin-gum acacia coacervates were found to be similarly effective against primary oxidation as the PV were similar throughout the study.
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Oxidative stability of encapsulated flaxseed oil evaluated by peroxide value method
The samples encapsulated with MD:Hi- Cap and MD:GA presented higher peroxide concentration afterone week, reaching values of 22.6 and 24.8 meq peroxide/kg oil, respectively. Samples encapsulated with Hi-Cap, GA or Capsul with maltodextrin suffered a significant increase in oxidation a the third week of storage. Between the third and fourth weeks, samples continued to oxidize and in the fourth week, MD:GA and MD:Capsul did not differ from each other.
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Influence of encapsulation method on storage stability of limonene
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Stability of entrapped aromas in microencapsulated cardomom oleoresin
gum arabic– maltodextrin gum arabic– modified starch A 4/6,1/6,1/6 blend of GA:MD:MS offered a protection, better than GA as seen from the t1/2, time required for a constituent to reduce to 50% of its initial value. gum arabic– Maltodextrin modcified starch (Krishnan et al., 2005)
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Shelf-life of encapsulated orange oil samples, as measured by limonene oxide formation at 37˚C.
Presence of small oligosaccharides (high DE) may promote oxidative stability by forming a more effective oxygen barrier. One would predict a shelf-life of about 7 months at 700 F for the worst product (amylomaize) and at least 14 months for the better products (corn, wheat, rice, waxy corn, and cassava).
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Aroma profile of the encapsulated meat-like process flavouring during storage for 6 months.
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ASSESSMENT OF MICROENCAPSULATED FLAVOURS
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Profile of original and microencapsulated sweet orange oil
(X. Jun-xia et al., 2011)
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SEM micrographs of microencapsulated sweet orange oil
SEM micrographs of microencapsulated sweet orange oil. (a and b): representatives of complete microcapsules; (c and d): representatives of incomplete microcapsules. The microcapsules were obtained in the sucrose/SPI ratio 1:1 and core material load 10%.
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Scanning electron microscope micrographs of coacervates containing garlic oil.
(a): coacervates made from Type A gelatin-gum acacia 419 produced at pH 4.5, gelatin-to-gum acacia ratio at 1:1 and core-to-wall ratio at 6:1 at magnification of 30×. (b): surface morphology of Type A 420 gelatin-gum acacia coacervates at magnification of 400×. (c): coacervates made from Type B gelatin-gum acacia produced at pH 3.5, gelatin-to-421 gum acacia ratio at 1:1 and core-to-wall ratio at 6:1 at magnification of 40×. (d) surface morphology of Type B gelatin-gum acacia coacervates at 422 magnification of 400× and 500× respectively. (Siow et al., 2013)
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Composition of the main constituents of fennel before and after encapsulation (mg/100g product)
When natural flavorings are encapsulated in the different matrixes it is important to know the changes in the composition taking place during emulsification and especially freeze-drying. Such knowledge is useful in designing preparations with a specified flavoring. (Charikleia Chranioti & Constantina Tzia )
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SEM micrographs of spray-dried inclusion complex powders.
Solid content of CD in feed liquid: 10 wt%, ture: 160 °C, Inlet air temperaand incubation time: 0, 1, and 24 h. Yamamoto et al.
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SEM micrographs of spray-dried powders with the mixrure wall materials of α-CD and HBCD. The percentage of α-CD was changed from 0 to 100 wt% at an interval of 20 wt%.
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Internal structures of spray-dried powders with the mixture wall materials of α-CD and HBCD. The percentage of α-CD was changed from 0 to 100 wt% at an interval of 20 wt%.
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Inclusion efficiency (IE) and retention degree (R%) of crude coriander EO in β-CD
(Dima et al., 2014)
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SEM images of the encapsulated coriander essential oil in β-cyclodextrin matrix
a)unloaded β-CD b) coriander EO/β-CD complex in 10:90 ratio c) coriander EO/β-CD complex in 15:85 ratio
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CONCLUSION Numerous development have been made in the field of flavour encapsulation because of its flavourable properties. Choice of techniques used depends on Properties of flavour Degree of stability during storage Processing Properties of food component Release properties required Maximum obtainable flavour load in the powder Cost production Microencapsulation of flavour using spray dry is most economical and commonly used method.
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Fluid bed coating is also becoming promising technique for large scale production of flavour powder microcapsules. Comprehensive technology of encapsulation enables: Satisfy relevant product requirement Tailoring food properties Easy product handling Improved shelf life Controlled release Important aspect for research and development- To understand how industrial constrain and requirement to make microencapsulation technology viable Modeling at laboratory scale so as to undertake the transition to full scale production and marketting of final product.
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