Drying Technology, 23: 13611394, 2005 Copyright Q 2005 Taylor & Francis, Inc.

ISSN: 0737-3937 print/1532-2300 online DOI: 10.1081/DRT-200063478

Recent Developments in Microencapsulation of Food Ingredients

Kashappa Goud H. Desai and Hyun Jin Park*
Graduate School of Biotechnology, Korea University, Sungbuk-ku, Seoul, South Korea

Abstract: Microencapsulation involves the incorporation of food ingredients, enzymes, cells, or other materials in small capsules. Microcapsules offer food processors a means with which to protect sensitive food components, ensure against nutritional loss, utilize otherwise sensitive ingredients, incorporate unusual or time-release mechanisms into the formulation, mask or preserve flavors and aromas, and transform liquids into easily handled solid ingredients. Various techniques are employed to form microcapsules, including spray drying, spray chilling or spray cooling, extrusion coating, fluidized-bed coating, liposome entrapment, coacervation, inclusion complexation, centrifugal extrusion, and rotational suspension separation. Recent developments in each of these techniques are discussed in this review. Controlled release of food ingredients at the right place and the right time is a key functionality that can be provided by microencapsulation. A timely and targeted release improves the effectiveness of food additives, broadens the application range of food ingredients, and ensures optimal dosage, thereby improving the cost effectiveness for the food manufacturer. Reactive, sensitive, or volatile additives (vitamins, cultures, flavors, etc.) can be turned into stable ingredients through microencapsulation. With carefully fine-tuned controlled-release properties, microencapsulation is no longer just an added-value technique, but the source of totally new ingredients with matchless properties.
Keywords: Microencapsulation; Food ingredients; Controlled release; Spray drying; Microcapsules

INTRODUCTION Microencapsulation is defined as a technology of packaging solids, liquids, or gaseous materials in miniature, sealed capsules that can release
Correspondence: Hyun Jin Park, Graduate School of Biotechnology, Korea University, 1, 5-Ka, Anam-Dong, Sungbuk-ku, Seoul 136701, South Korea; Tel.: 82-2-3290-3450; Fax: 82-2-953-5892; E-mail: hjpark@korea.ac.kr

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their contents at controlled rates under specific conditions.[16] The microencapsulation technology has been used by the food industry for more than 60 years. In a broad sense, encapsulation technology in food processing includes the coating of minute particles of ingredients (e.g., acidulants, fats, and flavors) as well as whole ingredients (e.g., raisins, nuts, and confectionary products), which may be accomplished by microencapsulation and macro-coating techniques, respectively.[7] More specifically, the microcapsule has the ability to preserve a substance in the finely divided state and to release it as occasion demands.[8] These microcapsules may range from submicrometer to several millimeters in size and have a multitude of different shapes, depending on the materials and methods used to prepare them. The food industry applies microencapsulation process for a variety of reasons: (1) encapsulation= entrapment can protect the core material from degradation by reducing its reactivity to its outside environment (e.g., heat, moisture, air, and light), (2) evaporation or transfer rate of the core material to the outside environment is decreased=retarded, (3) the physical characteristics of the original material can be modified and made easier to handle, (4) the product can be tailor to either release slowly over time or at a certain point (i.e., to control the release of the core material to achieve the property delay until the right stimulus), (5) the flavor of the core material can be masked, (6) the core material can be diluted when only very small amounts are required, yet still achieve a uniform dispersion in the host material, and (7) it can be employed to separate components within a mixture that would otherwise react with one another.[914] Various properties of microcapsules that may be changed to suit specific ingredient applications include composition, mechanism of release, particle size, final physical form, and cost. The architecture of microcapsules is generally divided into several arbitrary and overlapping classifications (Fig. 1). One such classification is known matrix encapsulation. This is the simplest structure, in which a sphere is surrounded by a wall or membrane of uniform thickness resembling that of a hens egg. In this design, the core material is buried to varying depths inside the shell. This microcapsule has been termed a single-particle structure (Fig. 1A). It is also possible to design microcapsules that have several distinct cores within the same microcapsule or, more commonly, number numerous core particles embedded in a continuous matrix of wall material. This type of design is termed the aggregate structure (Fig. 1B). In order to improve the properties of food ingredients, immobilization of food ingredients onto a suitable polymer or addition of antimicrobial agents are common practices in the food industres.[1517] For example, an important bacteria used in the food industry, lactic acid bacteria, was first immobilized in 1975 on Berl saddles and Lactobacillus lactis was encapsulated in alginate gel beads years later.[18] Seiss and Davis suggested that immobilized lactic acid bacteria could be used to

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Figure 1. Schematic diagram of two representative types of microcapsules.

continuously produce yogurt.[19] However, the alginate gel beads leaked large quantities of cells. The use of microencapsulated food ingredients allows food ingredients to be carefully tailored to the specific release site through the choice and microencapsulation variables, specifically, the method and food ingredients-polymer ratio.[7] The total amount of ingestion and the kinetics of release are variables that can be manipulated to achieve the desired result.[7,9,14] Using innovative microencapsulation technologies, and varying the copolymer ratio, molecular weight of the polymer, etc., microcapsules can be developed into an optimal food ingredient device.[7] Microcapsule-based systems increases the life span of food ingredients and control the release of food ingredients. Various properties of microcapsules that may be changed to suit specific ingredient applications include composition, mechanism of release, particle size, final physical form, and cost. Before considering the properties desired in encapsulated products, the purpose of encapsulation must be clear. In designing the encapsulation process, the following questions are taken into consideration: 1. What functionality should the encapsulated ingredients provide the final product? 2. What kind of coating material should be selected? 3. What processing conditions must the encapsulated ingredient survive before releasing its content? 4. What is optimal concentration of the active ingredient in the microcapsule? 5. By what mechanism the ingredient be released from the microcapsules? 6. What are the particle size, density, and stability requirements for the encapsulated ingredient? 7. What are the cost constraints of the encapsulated ingredient?

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Controlled release may be defined as a method by which one or more active agents or ingredients are made available at a desired site and time at a specific rate. With the emergence of controlled-release technology, some heat-, temperature-, or pH-sensitive additives can be used very conveniently in food systems. Such additives are introduced into the food system mostly in the form of microcapsules. The additive present in the microcapsule is released under the influence of a specific stimulus at a specified stage. For example, flavors and nutrients may be released upon consumption, whereas sweeteners that are susceptible to heat may be released toward the end of baking, thus preventing undesirable caramelization in the baked product.[2030] Although quite a number of reviews are published on the microencapsulation of food ingredients, we have made an attempt here to update the recent developments in the microencapsulation of food ingredients. MICROENCAPSULATION TECHNIQUES Encapsulation of food ingredients into coating materials can be achieved by several methods. The selection of the microencapsulation process is governed by the properties (physical and chemical) of core and coating materials and the intended application of food ingredients. However, the microencapsulation processes that are used to encapsulate food ingredients are given in Table 1, which outlines various methods used for the preparation of microencapsulated food systems. Sophisticated shell materials and technologies have been developed and an extremely wide variety of functionalities can now be achieved through microencapsulation. Any kind of trigger can be used to prompt the release of the encapsulated ingredient, such as pH change (enteric and anti-enteric coating), mechanical stress, temperature, enzymatic activity, time, osmotic force, etc. However, cost considerations in the food industry are much more stringent than in, for instance, the pharmaceutical or cosmetic industries. The selection of microencapsulation method and coating materials are interdependent. Based on the coating material or method applied, the appropriate method or coating material is selected. Coating materials, which are basically film-forming materials, can be selected from a wide variety of natural or synthetic polymers, depending on the material to be coated and characteristics desired in the final microcapsules. The composition of the coating material is the main determinant of the functional properties of the microcapsule and of how it may be used to improve the performance of a particular ingredient. An ideal coating material should exhibit the following characteristics: 1. Good rheological properties at high concentration and easy workability during encapsulation. 2. The ability to disperse or emulsify the active material and stabilize the emulsion produced.

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Table 1. Various microencapsulation techniques and the processes involved in each technique No 1 Microencapsulation technique Spray-drying Major steps in encapsulation a. Preparation of the dispersion b. Homogenization of the dispersion c. Atomization of the infeed dispersion d. Dehydration of the atomized particles a. Preparation of the dispersion b. Homogenization of the dispersion c. Atomization of the infeed dispersion a. Preparation of the dispersion b. Homogenization of the dispersion c. Atomization of the infeed dispersion a. Preparation of coating solution b. Fluidization of core particles. c. Coating of core particles a. Preparation of molten coating solution b. Dispersion of core into molten polymer c. Cooling or passing of core-coat mixture through dehydrating liquid a. Preparation of core solution b. Preparation of coating material solution c. Co-extrusion of core and coat solution through nozzles a. Mixing of core in a coating solution b. Freeze-drying of the mixture a. Formation of a three-immiscible chemical phases b. Deposition of the coating c. Solidification of the coating a. Mixing of core in a coating material b. Pour the mixture over a rotating disc to obtain encapsulated tiny particles c. Drying a. Preparation of supersaturated sucrose solution b. Adding of core into supersaturated solution c. Emission of substantial heat after solution reaches the sucrose crystallization temperature (Continued)

Spray-cooling

Spray-chilling

Fluidized-bed coating

Extrusion

Centrifugal extrusion

7 8

Lyophilization Coacervation

Centrifugal suspension separation

10

Cocrystallization

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Table 1. (Continued) No 11 Microencapsulation technique Liposome entrapment Major steps in encapsulation a. Microfluidization b. Ultrasonication c. Reverse-phase evaporation Preparation of complexes by mixing or grinding or spray-drying

12

Inclusion complexation

3. Nonreactivity with the material to be encapsulated both during processing and on prolonged storage. 4. The ability to seal and hold the active material within its structure during processing or storage. 5. The ability to completely release the solvent or other materials used during the process of encapsulation under drying or other desolventization conditions. 6. The ability to provide maximum protection to the active material against environmental conditions (e.g., oxygen, heat, light, humidity). 7. Solubility in solvents acceptable in the food industry (e.g., water, ethanol). 8. Chemical nonreactivity with the active core materials. 9. Inexpensive, food-grade status. Because no single coating material can meet all of the criteria listed above, in practice either coating materials are employed in combinations or modifiers such as oxygen scavengers, antioxidants, chelating agents, and surfactants are added. Some commonly used biocompatible and food-grade coating materials are listed in Table 2. However, chemical modifications of the existing coating materials to manipulate their properties are also being considered. Those modified coating materials exhibit better physical and mechanical properties when compared to individual coating materials. Spray-Drying Spray-drying encapsulation has been used in the food industry since the late 1950s to provide flavor oils with some protection against degradation=oxidation and to convert liquids to powders. Spray-drying is the most widely used microencapsulation technique in the food industry and is typically used for the preparation of dry, stable food additives and flavors. The process is economical; flexible, in that it offers substantial variation in microencapsulation matrix; adaptable to commonly used processing equipment; and produces particles of good quality. In fact,

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Table 2. Coating materials for microencapsulation of functional food additives Widely used methods Spray- and freeze-drying, extrusion, coacervation, inclusion complexation Coacervation, spray-drying, and edible films

Category

Coating materials

References 2024

Carbohydrate Starch,maltodextrins, chitosan, corn syrup solids, dextran, modified starch, cyclodextrins Cellulose

Gum Lipids Protein

Carboxymethylcellulose, methyl cellulose, ethylcellulose, celluloseacetate-phthalate, celluloseacetatebutylate-phthalate Gum acacia, agar, sodium Spray-drying, syringe alginate, carrageenan method (gel beads) Wax, paraffin, beeswax, Emulsion, liposomes, diacylglyerols, oils, fats film formation Gluten, casein, gelatin, Emulsion, spray-drying albumin, peptides

2526

27 2829 30

spray-drying production costs are lower than those associated with most other methods of encapsulation. One limitation of the spray-drying technology is the limited number of shell materials available. Since almost all spray-drying processes in the food industry are carried out from aqueous feed formulations, the shell material must be soluble in water at an acceptable level. Typical shell materials include gum acacia, maltodextrins, hydrophobically modified starch, and mixtures thereof. Other polysaccharides (alginate, carboxymethylcellulose, guar gum) and proteins (whey proteins, soy proteins, sodium caseinate) can be used as the wall material in spray-drying, but their usage becomes very tedious and expensive because of their low solubility in water: the amount of water in the feed to be evaporated is much larger due to the lower dry matter content and the amount of active ingredient in the feed must be reduced accordingly. In this method, the material for encapsulation is homogenized with the carrier material at a different ratio. The mixture is then fed into a spray dryer and atomized with a nozzle or spinning wheel. Water is evaporated by the hot air contacting the atomized material. The microcapsules are then collected after they fall to the bottom of the drier.[31] Rosenberg and Sheu demonstrated the use of whey protein isolate as a wall material for encapsulation of volatiles.[32] They encapsulated ethyl butyrate and ethyl caprylate in whey protein isolate and 1:1 mixture of

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whey protein isolate and lactose. Retention of volatiles was significantly affected by wall solids concentration (1030%, w=w), initial ester load (1075%, w=w, of wall solids), and by ester and wall type. Ester retention in whey protein isolate=lactose was higher than in whey protein isolate. Spray-drying is a food manufacturerfriendly technique because it allows the food processor to manipulate the preparation process to improve the quality of the final product. Recently, Shiga et al. prepared flavorinclusion powder by a spray-drying technique using the combined encapsulation method of inclusion by b-cyclodextrin and emulsified by gum arabic where d-limonene and ethyl n-hexanoate were used as model flavors.[33] The effective film-forming property and inclusion complex were achieved by applying high pressure to the mixture of flavors and b-cyclodextrin slurry using a microfluidizer. It is reported that flavor retention during spray-drying increased due to blending of gum arabic and b-cyclodextrin in the feed liquid. The release rate of flavors was manipulated by the blending of maltodextrin in the feed liquid. In order to evaluate the release kinetics of flavors, the release data were fitted to Avramis equation (Eq. 1). R expktn 1

where R is the retention of flavors during release, t is time, n is a parameter representing the release mechanism, and k is the release rate constant. Eq. (1) was originally developed the crystal growth of polymers, and has been recently used to represent the time-dependent protein inactivation in amorphous sugar matrices.[34] In Eq. (1), n 1 represents the first-order reaction, and n 0.54 represents the diffusion-limiting reaction kinetics.[35] Taking a logarithm of both sides of Eq. (1) twice yields Eq. (2): lnln R n ln k n ln t 2

From Eq. (2) one can find the parameter n as a slope by plotting ln( ln R) vs. ln t, and the release rate constant k from the interception at ln t 0. It is important to protect the flavor loss during drying, because high-temperature air is commonly used in spray-drying. Generally, the retention of flavor in microcapsules is manipulated by varying the spray-drying conditions and compositions of wall material. Recently, Liu et al. adopted new technique where they used emulsified liquid flavor for spray-drying.[36] Nearly 100% of d-limonene was retained during spray-drying, independent of the composition of the feed liquid. However, the stability of emulsion droplets markedly affected the retention of flavors. d-Limonene emulsion was quite stable independent of the emulsifier, while the emulsion of ethyl butyrate was unstable with gum arabic as the emulsifier. The use of a mixture of gum arabic and soluble soybean polysaccharide as the emulsifier improved oiliness, and adjusting

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density of ethyl butyrate and adding gelatin increased the retention of ethyl butyrate during spray-drying. In recent years, new wall materials for use in spray-drying microencapsulation have not really emerged. A few exceptions are noteworthy, though. The investigations of other natural gums and their emulsification and shell properties have been reported. Mesquite gum, for instance, has been shown to give a better stability of the o=w emulsions and higher encapsulation efficiency compared to gum acacia.[37,38] Augustin et al. proposed the use of Maillard reaction products (MRPs) obtained by the reaction at high temperature between protein and carbohydrate to encapsulate oxidation-sensitive nutrients such as fish oils.[39] The MRPs are known to exhibit antioxidant properties and form a stable and robust shell around the oil phase. The stability of the oil against oxidation was greatly improved compared to nonencapsulated spray-dried samples in ordinary shell material. More interesting is the recent development of complex shell formulations for spray-drying encapsulation. For instance, aqueous two-phase systems (ATPSs), which result from the phase separation of a mixture of soluble polymers in a common solvent due to the low entropy of mixing (DSmix) of polymer mixtures, can be used to design double-encapsulated ingredients in a single spray-drying step. MillqvistFureby et al. encapsulated Enterococcus fcium in a mixture of polyvinylpyrrolidone (PVP) and dextran.[40] While proteins exhibit partitioning between the two phases, whole cells tend to concentrate in one of the polymer phases, which make them ideal candidates for ATPS spray-drying. The structure of the microcapsule, whether PVP is the outer layer and dextran the inner core or vice versa, can be controlled by adjusting the ratio and concentration of the two polymers. Encapsulated E. fcium in spraydried ATPS showed a survival rate of up to 45% after 4 weeks at room temperature. Another example is the preparation and spray-drying of multiple emulsions, which results a in a double-layered microcapsule, providing better protection to sensitive materials such as oxidation-probe flavor oils. Edris and Bergmtahl have encapsulated orange oil by first preparing a triple emulsion o=w=o=w and then evaporating the outer continuous aqueous phase, which contains sodium caseinate and lactose as shell material, by spray-drying.[41] The process leads to a dry free-flowing powder constituting of a double o=w=o, in which the inner orange oil phase is dispersed in an aqueous phase, which is itself dispersed in an oil phase encapsulated in sodium caseinate and lactose. This double emulsion process is not practically more complex than a typical spray-drying process that requires an emulsion step anyway. However, preparing a second emulsion implies a dilution of the flavor oil, and the much lower payload in the microcapsule (510%) is a drawback compared to typical spray-dried flavor oils, which have payloads of around 2025%. The unique protection and delayedrelease properties obtained with two layers might compensate for the lower payload, but this has still to be demonstrated.

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Chitosan is a hydrophilic, biocompatible, and biodegradable, polysaccharide of low toxicity. In recent years, it has been used for development of oral controlled drug delivery systems. It is also a well-known dietary food additive. Therefore, our research team demonstrated the cross-linked chitosan as a wall material for the encapsulation of vitamin C by a spray-drying technique. Vitamin C, a representative water-soluble vitamin, has a variety of biological, pharmaceutical, and dermatological functions. Vitamin C is widely used in various types of foods as a vitamin supplement and as an antioxidant. Hence, in previous studies, sustainedrelease carriers of vitamin C have been prepared by using cross-linked chitosan as a wall material by spray-drying technique.[4244] The process of the preparation of vitamin Cencapsulated chitosan microcapsules is shown in Fig. 2. Chitosan was cross-linked with nontoxic cross-linking agent, i.e., tripolyphosphate. Vitamin Cencapsulated chitosan microspheres of different size, surface morphology, loading efficiency, and zeta potential with controlled-release property could be obtained by varying the manufacturing parameters (inlet temperature, flow rate) and using the different molecular weight and concentration of chitosan. Vitamin Cencapsulated chitosan microcapsules were spherical in shape with a smooth surface as observed by scanning electron microscopy (Fig. 3). Microencapsulation of vitamin C improves and broadens its applications in the food industry.

Figure 2. Procedure of preparation of vitamin Cencapsulated chitosan microspheres by spray-drying.

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Figure 3. Scanning electronic microscopic picture of the vitamin C-encapsulated microcapsule.

Numerous materials have been used as flavor-encapsulating agents using a spray-drying technique. These include proteins, gums, and modified starches.[45] An area of research of increasing interest is the development of alternative and inexpensive polymers that may be considered natural, like gum arabic, and that could encapsulate flavors with the same efficiency as gum arabic.[46] Mesquite gum has been reported as a very good encapsulating agent.[47,48] Beristain and Vernon-Carter noted that a blend of 60% gum arabic and 40% mesquite gum encapsulated 93.5% of orange peel oil.[49] More recently, Beristain et al. reported that a mixture consisting of 40% mesquite gum and 60% maltodextrins was able to encapsulate 84.6% of the starting oil.[50] Cardamom-based oil microcapsules were successfully produced by spray-drying using mesquite gum.[38] The stability against drop coalescence of the emulsions was elevated for all the gum:oil ratios studied. High flavor retention (83.6%) was attained during microencapsulation by spray-drying when a proportion of 4:1 gum:oil was used. This confirmed the interesting emulsifying properties and good flavor-encapsulation ability that qualify mesquite gum as an important alternative encapsulating medium. The microcapsules can be readily used as a food ingredient. Recent developments have been in the use of new carrier materials and a newly designed spray dryer. Colloides Naturels and TIC Gums

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have developed new combinations of gum arabic starches to increase the retention of volatiles and shelf life of microcapsules.[51,52] Risch and Reineccius enhanced the retention of orange oil and decreased oxidation by using gum arabic.[53] Bhandari et al. showed that a new type of dryer called the Leaflish spray dryer, which uses a high air velocity with a temperature of 300 to 400C, was effective for encapsulating citral and linalyl acetate without degradation.[54] A disadvantage is that a separate agglomeration step is required to prevent separation or to render the obtained powder soluble. A chief advantage is that this technique can be used for heat-labile materials. Recently, studies on the modification of spray-drying chamber configurations and atomization along applications of computational fluid dynamic model have been reported to broaden the applications range of spray-drying methods.[5560] Spray-Chilling or Spray-Cooling In spray-chilling and spray-cooling, the core and wall mixtures are atomized into the cooled or chilled air, which causes the wall to solidify around the core. Unlike spray-drying, spray-chilling or spray-cooling does not involve evaporation of water. In spray-cooling, the coating material is typically some form of vegetable oil or its derivatives. However, a wide range of other encapsulating materials may be employed. These include fat and stearin with melting points of 45122C, as well as hard mono- and diacylglycerols with melting points of 4565C.[31] In spray-chilling, the coating material is typically a fractionated or hydrogenated vegetable oil with a melting point in the range of 3242C.[61] In spray-chilling, there is no mass transfer (i.e., evaporation from the atomized droplets); therefore these solidify into almost perfect spheres to give free-flowing powders. Atomization gives an enormous surface area and an immediate as well as intimate mixing of these droplets with the cooling medium. Microcapsules prepared by spray-chilling and spraycooling are insoluble in water due to the lipid coating. Consequently, these techniques tend to be utilized for encapsulating water-soluble core materials such as minerals, water-soluble vitamins, enzymes, acidulants, and some flavors.[62] Fluidized-Bed Coating Originally developed as a pharmaceutical technique, fluidized-bed coating is now increasingly being applied in the food industry to fine-tune the effect of functional ingredients and additives. The main benefits of such miniature packages, called microcapsules, include increased shelf life, taste masking, ease of handling, controlled release, and improved aesthetics, taste, and color. Fluidized-bed coating increasingly supplies

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the food industry with a wide variety of encapsulated versions of food ingredients and additives.[63] Compared to pharmaceutical fluidized-bed coating, food industry fluidized-bed coating is more obliged to cut production costs and, therefore, should adopt a somewhat different approach to this rather expensive technology. Solid particles are suspended in a temperature and humidity-controlled chamber of highvelocity air where the coating material is atomized.[64,65] Typical food processing applications of fluidization include freezing and cooling, drying, puffing, freeze-drying, spray-drying, agglomeration and granulation, classification, and blanching and cooking.[66] Great variations in available wall materials exist. Cellulose derivatives, dextrins, emulsifiers, lipids, protein derivatives, and starch derivatives are examples of typical coating systems, and they may be used in a molten state or dissolved in an evaporable solvent. This technique is applicable for hot-melt coatings such as hydrogenated vegetable oil, stearines, fatty acids, emulsifiers, and waxes, or solvent-based coatings such as starches, gums, maltodextrins. For hot melts, cool air is used to harden the carrier, whereas for solvent-based coatings, hot air is used to evaporate the solvent. Hot-melt ingredients release their contents by increasing the temperature or physical breakage, whereas water-soluble coatings release their contents when water is added. Fluidized-bed encapsulation can be used to isolate iron from ascorbic acid in multivitamins and in small tablets such as childrens vitamins. Many fortified foods, nutritional mixes, and dry mixes, contain fluidized-bedencapsulated ingredients. Citric acid, lactic acid, sorbic acid, vitamin C, sodium bicarbonate in baked goods, and salt added to pretzels and meats are all encapsulated. Nowadays, the applicability and the utility of fluidized-bed coating and other microencapsulation techniques in the food industry is well recognized, as presented in several reviews.[6670] There are, however, important factors to be considered in fluidized-bed coating of food ingredients and additives. Fluidized-bed coating was first developed by D.E. Wurster in the 1950s; hence, the term Wurster process.[70] Today, the fluidized-bed coating method is being modified by changing the position of the nozzle to be used for coating the solid particles. The different fluidized-bed coating methods are: (1) top-spray, (2) bottom-spray, and (3) tangentialspray. The conventional top-spray method is shown in Fig. 4. The air is passed through a bed of core particles to suspend them in air and coating solution is sprayed countercurrently onto the randomly fluidized particles. The coated particles travel through the coating zone into the expansion chamber, and then they fall back into the product container and continue cycling throughout the process.[71] The top-spray system has successfully been used to coat materials as small as 100 mm.[71] However, Thiel and Nguyen demonstrated the possibility of encapsulating very fine particles (25 mm) by adsorbing them on a coarser carrier, which is encapsulated by means of conventional fluidized-bed equipment.[72] In

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Figure 4. Top-spray fluidized-bed coating.

the top-spray configuration, controlling the distance the droplets travel before contacting the substrate is impossible, and coating imperfections can occur due to premature droplet evaporation. The bottom-spray method known as the Wurster system (Fig. 5) is widely used for coating particles as small as 100 mm. In this method, the particles are recycled through the coating zone at a faster rate and the fluidization pattern is much more controlled than the top-spray method.[73] The typical advantage of this method is that, the path of the droplets concurrently toward the core particles is extremely short,

Figure 5. Bottom-spray fluidized-bed coating.

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so that premature droplet evaporation is almost absent. In addition, coating solution can spread out at the lowest viscosity, producing a very dense film with a superior physical strength. In contrary, Wesdyk et al. reported that particles coated in the bottom spray mode did not display a uniform film thickness with respect to particle size; larger beads displayed thicker films compared with smaller beads. The film thickness variation could be explained by differences in fluidization patterns. This phenomenon did not occur in other configurations.[74] Recently, a fascinating advancement in fluidized-bed coating technique was reported by Matsuda et al. for the fluidization and coating of very fine particles.[75] In conventional fluidized-bed coating, whether it is top-spray, Wurster, or rotational, the basic concept of fluidization relies on the compensation of the gravitational force experienced by the particles by an upward moving air flow, which ensures complete fluidization of the particles. Typical fluidized-bed apparatus can efficiently process particles from 100 mm to a few millimeters. However, for very small particles, other forces, such as electrostatic forces, start to play a major role in the movement of the particles in the fluidization chamber and prevent adequate fluidization. Colloidal particles have been used with some success to reduce electrostatic force, but are not much help in the fluidization of very small (submicron) particles in a conventional fluidized-bed apparatus. In this innovative process (Fig. 6), however, the gravitational force is multiplied through the use of a rotating perforated drum that contains the particle. The air flow is then applied tangentially to the rotation of the drum as compensation for the gravitational force, now a multiple (up to 37 g) of the normal gravitational force. The conventional top-spray method remains unique and widely used technique in food industry. This is due to its high versatility, relatively high batch size, and relative simplicity.[75] Recently, continuous fluidized-bed

Figure 6. Tangential-spray fluidized-bed coating.

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coaters have been developed.[76] With such a continuous fluidized-bed coating process, manufacturers can adapt the system to their own specific requirements while maintaining the flexibility needed for a large material throughput and wide product ranges, and while providing the coating quality demanded in the food industry. The efficiency of fluidized-bed techniques is governed by process variables, ambient variables, and thermodynamic factors (Table 3). Appropriate modification or combinations of these variables will yield the desired results. The use of melted fats, waxes, or emulsifiers as shell materials is a relatively new but very promising and interesting concept. From an industrial point of view, the inherent advantage of hot-melt fluidizedbed coating lies in the fact that the coating formulation is concentrated (no solvent, as in aqueous-based coating formulation), which means dramatically shorter processing times. The energy input is also much lower than with aqueous-based formulation since no evaporation needs to be done. Very few reports have been published on hot-melt coating by fluidized beds since Jozwiakowsksi et al. described the coating of sucrose particles with partially hydrogenated cottonseed oil and analyzed the optimal processing parameters by modified central composite design.[77] A number of patent applications, very similar in processing designs, have been published using fats and emulsifiers of various melting points and have developed an innovative fluidized-bed process for coating particles with fats and waxes using supercritical carbon dioxide as the solvent for the coating formulation.[7880] Here, again, minimal energy input is needed to evaporate the solvent and the process might lead to lower cost-in-use encapsulated ingredients.

Table 3. Different variables influencing fluidized-bed operation No 1 Variables Process variables 1. Inlet air temperature 2. Inlet air velocity 3. Spray rate 4. Solution temperature 5. Solution dry matter content 6. Atomization pressure Ambient variables 1. Ambient air temperature 2. Ambient air relative humidity Thermodynamic 1. Outlet air temperature 2. Outlet air relative humidity

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APPLICATION OF FLUIDIZED-BED TECHNIQUE IN FOOD INDUSTRY This technique is used to encapsulate nutritional substances such as vitamin C, B vitamins, ferrous sulfate, ferrous fumarate, sodium ascorbate, potassium chloride, and a variety of vitamin=mineral premixes. These encapsulated products are used as nutritional supplements.[81] In the case of bakery products, it is also used to encapsulate the leavening system ingredients, as well as vitamin C, acetic acid, lactic acid, potassium sorbate, sorbic acid, calcium propionate, and salt.[81,82] In the meat industry, several food acids have been fluid-bed encapsulated to develop color and flavor systems. They are also used to achieve a reproducible pH in cured meat products and to shorten their processing time. Fluid-bed encapsulated salt is used in meats to prevent development of rancidity, as well as premature set due to myofibrilar binding.[81]

Extrusion Encapsulation of food ingredients by extrusion is a relatively new process compared to spray-drying. Extrusion used in this context is not same as extrusion used for cooking and texturizing of cereal-based products. Actually, extrusion, as applied to flavor encapsulation, is a relatively lowtemperature entrapping method, which involves forcing a core material in a molten carbohydrate mass through a series of dies into a bath of dehydrating liquid. The pressure and temperature employed are typically <100 psi and seldom 115C.[23] The coating material hardens on contacting the liquids, forming an encapsulating matrix to entrap the core material. Then the extruded filaments are separated from the liquid bath, dried, and sized.[12] The carrier used may be composed of more than one ingredient, such as sucrose, maltodextrin, glucose syrup, glycerine, and glucose.[70] Schultz et al. were pioneers in the extrusion=encapsulation processes.[83] They emulsified orange peel oil in a molten dextrose mass, poured it on stainless steel sheets, and let it cool. The pulverized product exhibited good stability and flavor retention over a 6-month period. Combining the basic formulation of Schultz et al. with extrusion, Swisher created a novel encapsulating processes that is similar to the one currently used today in the flavor industry.[84] The primary benefit claimed was the maintenance of fresh flavor in encapsulated citrus oils, which otherwise would readily oxidize and yield objectionable off-flavors during storage. He conducted an accelerated shelf life test on encapsulated orange peel oil that contained an antioxidant and found that its shelf life was about one year. Figure 7 shows the key steps for the flavor encapsulation by extrusion. The advantage of this method is that the material is completely surrounded by the wall material (true encapsulation), and any residual oil or

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Figure 7. Flow diagram of encapsulation of food flavors by extrusion method.

core material is removed from the surface in an alcohol bath.[14,51,71,81] This provides an excellent stability against oxidation and therefore prolongs the shelf life. The product can be kept for 12 years without any substantial quality degradation.[71,81] This technique can be classified as a glass encapsulation system or a controlled-release system, depending on the polymeric materials used. The polymer matrices and the plasticizers used can be modified to produce the capsules for controlled release in food application.[85] However, microcapsules produced from this method are commonly designed to be soluble in water by the use of high-molecular-weight hydrophilic polymer. Thus, this encapsulation technique is considered unsuitable for subsequent extrusion processing because the water in the extruder melt can dissolve the capsules.[86]

Centrifugal Extrusion Centrifugal extrusion is another encapsulation technique that has been investigated and used by some manufacturers. A number of food-approved

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coating systems have been formulated to encapsulate products such as flavorings, seasonings, and vitamins. These wall materials include gelatin, sodium alginate, carrageenan, starches, cellulose derivatives, gum acacia, fats=fatty acids, waxes, and polyethylene glycol. Centrifugal extrusion is a liquid coextrusion process utilizing nozzles consisting of concentric orifice located on the outer circumference of a rotating cylinder (i.e., head). The encapsulating cylinder or head consists of a concentric feed tube through which coating and core materials are pumped separately to the many nozzles mounted on the outer surface of the device. While the core material passes through the center tube, coating material flows through the outer tube. The entire device is attached to a rotating shaft such that the head rotates around its vertical axis. As the head rotates, the core and coating materials are co-extruded through the concentric orifices of the nozzles as a fluid rod of the core sheathed in coating material. Centrifugal force impels the rod outward, causing it to break into tiny particles. By the action of surface tension, the coating material envelops the core material, thus accomplishing encapsulation. The microcapsules are collected on a moving bed of fine-grained starch, which cushions their impact and absorbs unwanted coating moisture. Particles produced by this method have diameter ranging from 150 to 2000 mm.[87]

Lyophilization Lyophilization, or freeze-drying, is a process used for the dehydration of almost all heat-sensitive materials and aromas. It has been used to encapsulate water-soluble essences and natural aromas as well as drugs. Except for the long dehydration period required (commonly 20 h), freeze-drying is a simple technique, which is particularly suitable for the encapsulation of aromatic materials. The retention of volatile compounds during the lyophilization is dependent upon the chemical nature of the system.[88]

Coacervation Coacervation involves the separation of a liquid phase of coating material from a polymeric solution followed by the coating of that phase as a uniform layer around suspended core particles. The coating is then solidified. In general, the batch-type coacervation processes consist of three steps and are carried out under continuous agitation. 1. Formation of a three-immiscible chemical phase 2. Deposition of the coating 3. Solidification of the coating

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In the first step, a three-phase system consisting of a liquid manufacturing vehicle phase, a core material phase, and a coating material phase is formed by either a direct addition or in situ separation technique. In the direct addition approach, the coating-insoluble waxes, immiscible solutions, and insoluble liquid polymers are added directly to the liquid-manufacturing vehicle, provided that it is immiscible with the other two phases and is capable of being liquefied. In the in situ separation technique, a monomer is dissolved in the liquid vehicle and is then subsequently polymerized at the interface. Deposition of the liquid polymer coating around the core material is accomplished by controlled physical mixing of the coating material (while liquid) and the core material in the manufacturing vehicle in the liquid phase; this sorption phenomenon is a prerequisite to effective coating. Continued deposition of the coating is prompted by a reduction in the total free interfacial energy of the system brought about by a decrease of the coating material surface area during coalescence of the liquid polymer droplets. Finally, solidification of the coating is achieved by thermal, cross-linking, or desolventization techniques and forms a self-sustaining microcapsule. The microcapsules are usually collected by filtration or centrifugation, washed with an appropriate solvent, and subsequently dried by standard techniques such as spray- or fluidized-bed drying to yield free-flowing, discrete particles.[7] A large numbers of coating materials have been evaluated for coacervation microencapsulation but the most studied and well understood coating system is probably the gelatin=gum acacia system. However, other coating systems such as gliadin, heparin=gelatin, carrageenan, chitosan, soy protein, polyvinyl alcohol, gelatin=carboxymethylcellulose, B-lactoglobulin=gum acacia, and guar gum=dextran are also studied.[89] In recent years, modified coacervation processes have also been developed that can overcome some of the problems encountered during a typical gelatin=gum acacia complex coacervation process, especially when dealing with food ingredients; for example, a room-temperature process for the encapsulation of heat-sensitive ingredients such as volatile flavor oils.[90] In this process, the coating materials are mixed and then phase separation (coacervation) is achieved by adjusting the pH. The newly formed coacervate phase is allowed to separate and sediment, most of the supernatant water is removed, and the flavor oil is then added to the mixture kept at 50C and emulsified rapidly. The initial volume of water is restored with room temperature water, causing a quick drop in the temperature, which means that the flavor oils experience a high temperature for only a few minutes, compared to several hours for a typical coacervation process. Another process involves the formation of a multilayered coacervated microcapsule.[91] This process consists of multiple coacervation stages in which an additional layer of wall material is applied to the microcapsule at each passage and the final shell layer can reach a thickness up to 100 mm.

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The coacervation method has some drawbacks. This process is very expensive and rather complex, and cross-linking of the wall material usually involves glutaraldehyde, which must be carefully used according to the countrys legislation. The problems related to harmful chemical cross-linkers could eventually be solved by using enzymatic cross-linkers instead. Soper and Thomas, for instance, described a process in which a transglutaminase is used to cross-link the proteins in the shell material. The enzyme is added to the microencapsulation tank at 10C and pH 7 and the reaction is carried out over 16 h, after which a hardened shell of coacervate is formed around the flavor oil droplets.[92] Centrifugal Suspension Separation Centrifugal suspension is more recent microencapsulation process. The process in principle involves mixing the core and wall materials and then adding to a rotating disk. The core materials then leave the disk with a coating of residual liquid. The microcapsules are then dried or chilled after removal from the disk. The whole process can take between a few seconds to minutes. Solids, liquids, or suspensions of 30 mm to 2 mm can be encapsulated in this manner. Coatings can be 1200 mm in thickness and include fats, polyethylene glycol (PEG), diglycerides, and other meltable substances. Since this is a continuous, high-speed method that can coat particles, it is highly suitable for foods. One application is to protect foods that are sensitive to or readily absorb moisture, such as aspartame, vitamins, or methionine.[93] The preparation process of encapsulated particles by centrifugal suspension separation is illustrated in Fig. 8. Cocrystallization Cocrystallization is a new encapsulation process utilizing sucrose as a matrix for the incorporation of core materials. The sucrose syrup is concentrated to the supersaturated state and maintained at a temperature high enough to prevent crystallization. A predetermined amount of core material is then added to the concentrated syrup with vigorous mechanical agitation, thus providing nucleation for the sucrose=ingredient mixture to crystallize. As the syrup reaches the temperature at which transformation and crystallization begin, a substantial amount of heat is emitted. Agitation is continued in order to promote and extend transformation= crystallization until the agglomerates are discharged from the vessel. The encapsulated products are then dried to the desired moisture (if necessary) and screened to a uniform size. It is very important to properly control the rates of nucleation and crystallization as well as the thermal balance during the various phases.[94]

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Figure 8. Representation of rotational suspension separation (A: establishing particle size for pure coating, and B: encapsulation by suspension separation).

The advantages of this technique include: (1) It can be employed to achieve particle drying. By means of this process, core materials in a liquid form can be converted to a dry powdered form without additional drying. (2) Products offer direct tableting characteristics because of their agglomerated structure and thus offer significant advantages to the candy and pharmaceutical industries. Recently, Beristain et al. encapsulated orange peel oil by a cocrystallization technique.[95] In their study, encapsulation capacity of sucrose syrups was found to be greater than 90% for a range of 100 to 250 g oil=kg of sugar. Surface oil, a measurement of encapsulation efficiency, varied from 3350 to 8880 mg oil=kg solids. Moisture content of the crystals was lower than 10 g=kg, and bulk density was greater than 670 kg=m3 for all the cocrystallizates prepared. Sensory evaluation showed that all of the panelists were able to detect oxidized flavors in oils without antioxidant added after storage at 35C for one day. When butylated hydroxyanisole was added to the oil prior to cocrystallization, no signs of oxidized flavors were detected after 2 months of storage at ambient temperature. Liposome Entrapment Liposomes consist of an aqueous phase that is completely surrounded by a phospholipid-based membrane. When phospholipids, such as lecithin,

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are dispersed in an aqueous phase, the liposomes form spontaneously. One can have either aqueous or lipid-soluble material enclosed in the liposome. They have been used for delivery of vaccines, hormones, enzymes, and vitamins.[96] They consist of one or more layers of lipids and thus are nontoxic and acceptable for foods. Permeability, stability, surface activity, and affinity can be varied through size and lipid composition variations. They can range from 25 nm to several microns in diameter, are easy to make, and can be stored by freeze-drying. Kirby and Gregoriadis have devised a method to encapsulate at high efficiency, which is easy to scale-up and uses mild conditions appropriate for enzymes.[97] It is important to reiterate that large unilamellar vesicles (LUV) are the most appropriate liposomes for the food industry because of their high encapsulation efficiency, their simple production methods, and their good stability over time. The great advantage of liposomes over other microencapsulation technologies is the stability liposomes impart to water-soluble material in high water activity application: spray-dryers, extruders, and fluidized beds impart great stability to food ingredients in the dry state but release their content readily in high water activity application, giving up all protection properties. Another unique property of liposomes is the targeted delivery of their content in specific parts of the foodstuff. For example, it has been shown that liposome-encapsulated enzymes concentrate preferably in the curd during cheese formation, whereas nonencapsulated enzymes are usually distributed evenly in the whole milk mixture, which leads to very low (24%) retention of the flavor-producing enzymes in the curd. They have prepared bromelainloaded liposomes for use as meat-tenderizer to improve stability of the enzyme during the processing of the food and subsequently improve the availability of the enzyme.[98] Benech Kheadr et al. showed that liposome-entrapped nisin retained higher activity against Listeria innocua and had improved stability in cheese production, proving a powerful tool to inhibit the growth of Listeria I in cheese while not preventing the detrimental effect of nisin on the actual cheese-ripening process.[99] Kirby et al. have developed a process to stabilize vitamin C in the aqueous inner core of liposomes.[100] Encapsulation of vitamin C gave significant improvements in shelf life (from a few days to up to 2 months), especially in the presence of common food components that would normally speed up decomposition, such as copper ions, ascorbate oxidase, and lysine. Liposomes can also be used to deliver the encapsulated ingredient at a specific and well-defined temperature: the liposome bilayer is instantly broken down at the transition temperature of the phospholipids, typically around 50C, at which temperature the content is immediately released. The most common phospholipid in lectin, phosphatidyl choline, is insoluble in water and is inexpensively isolated from soy or egg yolk. The composition of the phospholipids and the process used determine

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if a single layer or multiple layers are formed. Fatty acids also make up liposomes and their degree of saturation is dependent on the source. Animal sources provide more saturated fatty acids. They influence the transition temperature, which is the conversion from a gel to the more leaky liquid form. The main issues in liposome encapsulation for the food industry are (1) the scaling up of the microencapsulation process at acceptable cost-in-use levels and (2) the delivery form of the liposomeencapsulated ingredients. The development of a cost-effective drying method for liposome microcapsules and development of a dry liposome formulation that readily reconstitutes upon rehydration would ensure a promising future to liposome encapsulation of food ingredients. The recent advances in liposome technology have most probably solved the first issue: microfluidization has been shown to be an effective, cost-effective, and solvent-free continuous method for the production of liposomes with high encapsulation efficiency. The method can process a few hundred liters per hour of aqueous liposomes on a continuous basis.[101,102] The other issue concerns the aqueous form in which the liposomes are usually delivered. Most of the time, if not always, liposome formulations are kept in relatively dilute aqueous suspensions and this might be a very serious drawback for the large-scale production, storage, and shipping of encapsulated food ingredients.

Inclusion Complexation Molecular inclusion is another means of achieving encapsulation. Unlike other processes discussed to this point, this technique takes place at a molecular level; b-cyclodextrin is typically used as the encapsulating medium. b-Cyclodextrin is a cyclic derivative of starch made up of seven glucopyranose units. They are prepared from partially hydrolyzed starch (maltodextrin) by an enzymatic process. The external part of the cyclodextrin molecule is hydrophilic, whereas the internal part is hydrophobic. The guest molecules, which are apolar, can be entrapped into the apolar internal cavity through a hydrophobic interaction.[103] This internal cavity of about 0.65 nm diameter permits the inclusion of essential oil compounds and can take up one or more flavor volatile molecules.[13] In this method, the flavor compounds are entrapped inside the hollow center of a b-cyclodextrin molecule. The chemical structure and geometry of b-cyclodextrin are shown in Fig. 9. b-Cyclodextrin molecules form inclusion complexes with compounds that can fit dimensionally into their central cavity. These complexes are formed in a reaction that takes place only in the presence of water. Molecules that are less polar than water (i.e., most flavor substances) and have suitable molecular dimensions to fit inside the cyclodextrin interior can be incorporated into the molecule. There are three methods to produce

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Figure 9. Molecular structure and microstructure of b-cyclodextrin.[79]

the flavor-b-cyclodextrin complex. In the first method, b-cyclodextrin is dissolved in water to form an aqueous solution, and the flavors are added to form an inclusion complex in crystalline form. The crystal obtained is then separated and dried. In the second method, b-cyclodextrin is dissolved in a lesser amount of water than in the first method to form a concentrated suspension, and the flavors are mixed to form an inclusion complex in crystalline form. The complex then must be separated and dried. In the third method, b-cyclodextrin is dissolved in a much lower water content to form a paste, and the flavors are mixed during kneading to form an inclusion complex. This method is superior to the former two because it does not require further separation and drying.[103] A cyclodextrin-complexation method has been patented using a ball mill with a charge of cyclodextrin and a guest molecule. This process needs little water, preferably 2560% moisture by weight. The inclusion capacity of 1 g of b-cyclodextrin is not more than 97 mg of lemon oil. Among all existing microencapsulation methods, molecular inclusion of flavor volatiles in b-cyclodextrin molecules is the most effective for protecting the aromas. Encapsulating flavors in this way can provide better protection from volatilization during extrusion. However, the use of b-cyclodextrin for food application is very limited, possibly due to regulatory requirements in a number of countries.[86]

1386 Preferred mode of encapsulation Fluidized-bed coating, extrusion Applications Inclusion complexation, extrusion, centrifugal extrusion, spray-drying 1. Used to assist in the development of color and flavor in meat emulsions, dry sausage products, uncooked processed meats, and meat containing products. 2. 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. 1. To transform liquid flavorings into stable and free flowing powders, which are easier to handle and incorporate into a dry food system.

Table 4. Encapsulated food ingredients and their application in food industry

No.

Category of food ingredients

Examples

Acidulants

Lactic acid, glucono-d-lactone, vitamin C, acetic acid, potassium sorbate, sorbic acid, calcium propionate, and sodium chloride

Flavoring agents

Citrus oil, mint oils, onion oils, garlic oils, spice oleoresins

Sweeteners

Cocrystallization, fluidized-bed coating Extrusion, emulsion

Colorants

Sugars, nutritive or artificial sugars: aspartame Annatto, b-carotene, turmeric

Lipids

Spray-drying, freeze-drying, vacuum-drying

1. To reduce the hygroscopicity, improve flowability, and prolong sweetness perception. 1. Encapsulated colors are easier to handle and offer improved solubility, stability to oxidation, and control over stratification from dry blends. 1. To prevent oxidative degradation during processing and storage.

6 Coacervation, inclusion complexation, spray-drying, liposome entrapment

Vitamins and minerals

Enzymes and microorganisms

Fish oil, linolenic acid, rice brain oil, egg white powder, sardine oil, palmitic acid, seal blubber oil Fat-soluble: vitamin A, D, E, and K. Water-soluble: vitamin C, vitamin B1, vitamin B2, vitamin B6, vitamin B12, niacin, folic acid Lipase, invertase, Brevibacterium linens, Penicillium roqueforti Coacervation, spray method, liposome entrapment

1. To reduce off-flavors. 2. To permit time-release of nutrients. 3. To enhance the stability to extremes in temperature and moisture. 4. To reduce each nutrient interaction other ingredients. 1. To improve the stability. 2. To reduce the ripening time.

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ENCAPSULATED INGREDIENTS AND APPLICATIONS Microencapsulation can potentially offer numerous benefits to the materials being encapsulated. Various properties of active agents may be changed by encapsulation. For example, handling and flow properties can be improved by converting liquid to a solid encapsulated from. Hygroscopic materials can be protected from moisture. Some of the encapsulated food ingredients and their applications are summarized in Table 4. CONCLUSIONS The use of microencapsulated food ingredients for controlled-release applications is a promising alternative to solve the major problem of food ingredients faced by food industries. The challenges are to select the appropriate microencapsulation technique and encapsulating material. Despite the wide range of encapsulated products that have been developed, manufactured, and successfully marketed in the pharmaceutical and cosmetic industries, microencapsulation has found a comparatively much smaller market in the food industry. The technology is still far from being fully developed and has yet to become a conventional tool in the food technologists repertoire for several reasons. First of all, the development time is rather long and requires multidisciplinary cooperation. Secondly, the low margins typically achieved in food ingredients and the relative inertia of well-established corporations are an effective deterrent to the development and implementation of novel technologies that could result in truly unique food products, whether for more effective production, food fortification, neutraceuticals, improved organoleptic properties, or development of novelty food products. However, the most important aspect of R&D, from the very first lab-bench tests, is an understanding of the industrial constraints and requirements to make a microencapsulation process viable, from the transition to full-scale production to the marketing of the final product. ACKNOWLEDGEMENT This study was supported by a grant of the Korea Health 21 R and D Project, Ministry of Health and Welfare, Republic of Korea (A050376). REFERENCES
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