Materials For Encapsulation of Food Ingredients
Materials For Encapsulation of Food Ingredients
Materials For Encapsulation of Food Ingredients
Materials for Encapsulation of Food Ingredients: Understanding the Properties to Find Practical Solutions
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The food industry is continuously developing new materials and formulations for the efficient encapsulation of food ingredients to make them easier to handle and providing added functionality. The material(s) that can be used include carbohydrates, proteins, lipids, gums and cellulose, and the choice depends on factors such as the nature of the core material, the expected requirements, for instance, oxidation and process stability and controlled flavour release, the process of encapsulation, labeling concerns and economics. Each type of material has its own particular strengths and complex structural designs may be required for optimal functionality. To help in the selection of the optimum system, this paper examines the properties that make materials, particularly carbohydrates, applicable for encapsulation of food ingredients in terms of the basic underlying physicochemical principles.
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In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
214
Introduction
Encapsulation is a technology for coating solids, liquids and gaseous materials into sealed capsules that preserve the substance in a finely divided state or as a whole ingredient and release their contents under certain conditions at specific rates. In the case of microencapsulation, the capsules may vary in size from several tenths of a micron to a few thousand micrometers. Nanocapsules and capsules produced by macrocoating are generally less than 2000 and greater than 5000 respectively (1). For each of these capsule classes, the technological challenges and type of coatings differ. Numerous techniques have been evaluated for the encapsulation of food ingredients (including spray drying, extrusion, fluidized bed coating, spray cooling/ chilling, freeze drying, spinning disk and centrifugal coextrusion, coacervation, co-crystallisation, liposome entrappment and molecular inclusion (2-6). The selection of an appropriate technique depends on the type of capsule required, the physico/chemical properties of the core and coating material and economics. In the food industry, spray drying is the most widely used technique as it provides the most economical and flexible way to encapsulate hydrophobic ingredients such as fats, oils, flavours and vitamins. It involves the formation of an emulsion or suspension of core and coating material and nebulizing this feed solution in hot air. Moisture evaporates quickly on contact with the hot air rendering free-flowing powder particles with the active core material entrapped inside a coating matrix. During spray drying, the temperature of the core is much lower (<100 C) than that of the hot air (3), enabling encapsulation of heatsensitive food ingredients. However, loss of low boiling core compounds may occur. In addition, core material may adhere to the surface of the capsule and be prone to oxidation by direct contact to the air. Not only the drying process but also the nature of the coating material, the distribution of particles in the feed solution, the viscosity of the feed solution and core loading affect the retention of core compounds. Extensively used coating materials in spray-dried encapsulation are hydrolyzed starches (7), because they are inexpensive, bland in flavour, easy to dissolve and exhibit low viscosity in solution, which is important in spray-drying applications. However, they lack emulsifying capacity and result in poor retention of organic compounds during drying (8). Therefore, in practice, they are combined with emulsifying polymers like gum arabic and whey protein or substituted with hydrophobic groups especially n-octenylsuccinic anhydride (n-OSA). In spray-dried powders, the coating material acts as a barrier for the release of core compounds through volatilization and diffusion, and minimizes the penetration of moisture, oxygen and other components in the environment. The extent and nature of protection provided by the coating material both during drying and storage varies with the chemical composition and the physical state of
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In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
215 the coating material. Knowledge on how different characteristics of coating material affect the stability of core material both during drying and storage can help the food developer in selecting the optimal system. Therefore, the properties of coating material that control the coating's protective nature in the microencapsulation of organic compounds have been investigated.
Molecular weight and viscosity Hydrolysed starches are traditionally characterized by their dextrose equivalent (DE), which is a measure of their reducing power as compared to that of glucose (dextrose). A n unhydrolysed starch has a D E value close to zero while glucose has a D E of 100. If the D E is less than 20, starch hydrolysates are called maltodextrins. Corn syrup solids have a D E of 20 or greater. Q i and X u (9) showed the molecular distribution of starch hydrolysates with different D E values and confirmed the data from Kenyon & Anderson (10) that the D E is roughly proportional to the reciprocal of the average degree of polymerization (Le. the average number of repeating glucose units in the carbohydrate molecules). However, by varying the type of hydrolyzing agent, it is possible to produce products with the same D E value but different carbohydrate profiles (). In agreement with earlier studies (12-14), Bangs & Reineccius (15) found that the D E of hydrolysed starch is inversely related to the retention of flavour compounds during spray drying at constant infeed solids content. This relation held true down to D E 15 for all of 12 combined aroma compounds and was most likely related to an increase in the rate at which an amorphous film was formed around droplets of the aroma compounds (16-18). Interestingly, Sheu & Rosenberg (19) found that this relation was of lesser importance in the presence of an emulsifier. Furthermore, Bangs & Reineccius (15) found that flavor retention decreased with D E values at DE<15,but this decrease was not statistically significant, and for certain aroma compounds, this decrease could not be observed. The viscosity and solubility characteristics of hydrolysed starches vary with the average molecular weight (11). The higher the D E , the lower the viscosity and consequently, the higher the concentration of starch that can be dissolved prior to spray-drying. Various studies (15, 20 & 21) have shown that increasing the solids content of the infeed allowed better performance not only in terms of economics but also in retaining flavours during drying. Our studies confirm this finding. For example, at an oil load of 20%, an increase from 30 to 55% solids increased the retention of oil from ca. 93% to full recovery (Table l).In addition, our studies show that the maximum level of oil
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
216 that could be retained at 55% solids was ca. 20% (Table 1). Increasing the oil load to levels above 20% led to losses of oil during drying.
Table I. Influence of infeed solids content and oil load on the retention of orange oil during spray drying. Carrier
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The importance of infeed solids content in retaining flavour during drying was related to an increase in the rate of film formation (22). Interestingly, Bangs & Reineccius (15) showed that the advantage of higher infeed solids content at higher D E values did not offset the improved film forming ability of higher molecular weight dextrins for flavours with a boiling point >160C. In agreement with later studies (21), infeed solids content influenced the more volatile components to a greater extent. The effectiveness of the matrix film in holding and protecting the core material is strongly depended on the physical state of the matrix material. The contribution of the molecular weight of hydrolyzed starches to this aspect of encapsulation has been further discussed below.
Amorphous state of the carbohydrate matrix The success of encapsulation depends to a large extent on the formation of a metastable amorphous structure, a glass, with a low permeability to organic compounds but will let water diffuse through (Karel & Langer, 1988). Starch hydrolysis products are particularly useful for the formation of such a structure with selected permeability. The faster the matrix material forms an amorphous film around the core material, the more organic compound will be retained and thus, the higher for the flavour retention (23 & 24). Hydrophilic amorphous matrices are formed when a low water activity has been reached upon rapid evaporation from droplet surfaces. The sudden water reduction increases the glass transition temperature of the matrix material. As long as the storage temperature remains below the glass transition temperature, the resulting matrix is believed to be in the amorphous state, which is characterised by a very low mobility of the carrier molecules. Because of this low mobility, permeability to organic compounds is strongly retarded and core material is released primarily by diffusion through the pores in the matrix (25 &
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
217 26). Consequently, release or retention of core material depends on factors such as the chemical composition of the matrix, pore size, molecular size (or DE), wall thickness and contact surface area. For the carbohydrate matrix to remain in the amorphous state, the glass transition temperature may not drop below the room temperature. Thus, processes reducing the glass transition temperature need to be controlled. For example, increased hydrolyses results in starches with a higher D E and consequently, a lower glass transition temperature (9 and 27). In addition, starches with a higher D E are usually more susceptible to hygroscopicity (10) and the increased uptake of moisture reduces the glass transition temperature. The relation between increased moisture uptake and glass transition temperature has been illustrated by the results in Figure 1 for a carrier comprising glucose syrup (DE 40) and modified starch (3:1, w/w). Initially, the glass transition temperature was in the range 60 to 70 C. Increasing the relative humidity to 60% increased the moisture content to 7% and reduced the glass transition temperature to well below room temperature. Thus, storage at low humidity (<50%) was required to keep the wall material of the powder in the amorphous state. The effectiveness of an amorphous carbohydrate matrix film to retain flavour and inhibit uptake of oxygen is directly related to D E . For example, Anandaraman & Reineccius (28) found improved oxygen-barrier properties in parallel with D E on encapsulation of orange peel oil. In addition, Whorton & Reineccius (29) observed increased volatile retention with an increase in D E when they examined encapsulated vegetable oils containing short chain aldehydes at increasing water activities. Our studies have also demonstrated the importance of D E on oxidation stability and flavour retention in the encapsulation of orange oil (Figure 2). After 25 days of storage, most of the flavour was still retained and practically no limonene, which is present as the major component in orange oil, was oxidized at D E 40. However, reducing the value of D E to 17 increased the production of limonene oxide substantially and at the same time, led to a rapid loss in flavour. In accordance with observations made by Benczedi (26), it may be speculated that at a higher D E , the increased concentration of low-molecular weight plasticizer led to a densification of the polymer followed by a reduction in permeability. On the other hand, a potential improvement in the viscoelastic properties of wall material may have played a role in reducing permeability. Sheu & Rosenberg (19 & 30) observed less dent formation and less cracks in wall material when the D E increased. It has been suggested that surface dents result from uneven shrinkage of the drying droplets during the early stages of drying. Subsequent thermal expansion of air or water vapours inside the drying particles can smooth them out to varying extents depending on the drying rate and on the viscoelastic properties of the wall matrix. Thus, differences in the viscoelastic properties of the carrier with a change in D E probably affected dent formation and cracking.
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In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
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20
15
10
40
60
80
100
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009. Relative humidity ( % )
Figure 1. Influence of relative humidity on equilibrium moisture content () and glass transition (A) of a carrier comprising glucose syrup DE 40 and n-OSA starch (3:1, w/w) in the encapsulation of orange oil (20%).
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Flavour retention ( % )
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Figure 2. Shelf life stability (flavour retention: A and limonene oxide: OA) at 50C of orange oil (20%) encapsulated in a matrix containing glucose syrup of different DE and n-OSA starch (3:1). Properties of the coating: DE = 40 and Tg = 60-70C () and DE = 17 andTg = 81-104C (A A).
220 Crystallisation of wall material ingredients Hydrolysed starch products don't usually crystallise but loose flowability and eventually cake (10). This phenomenon can be attributed to the glass transition properties of the hydrolysed starches (9). When the glass transition temperature drops below the storage temperature with increasing moisture content, a transition takes place from solid glass to a liquid-like rubbery state. The hydrogen bonds responsible for the main structural forces in the amorphous matrix are weakened and consequently, molecular mobility and hence diffusion increase (25). When the moisture content continues to increase, the polymer matrix collapses resulting in caking (10). This caking, or collapse, is caused by the inability of the carrier to support itself against gravity as viscosity decreases. Holes in the particle wall reduce, the surface matrix shrinks thereby forcing some or all of the core material to the surface and diffusion is yet again retarded, effectively by 're-encapsulating' the remaining organic compound (29, 31 & 32). This ability to release and reseal core material could be used to impart a desired level of release depending upon the degree to which the collapse is allowed to progress. Crystallization, like structural collapse, is promoted when the glass transition temperature drops below the storage temperature with increasing moisture content. It's a two-step process with the phase of initial nucleation and subsequent crystal growth. At a temperature above that of glass transition, particles have sufficient mobility to associate and form crystalline nucleus. Like collapse, crystallisation also leads to a reduction in pore size. As a result, core material is forced out from the crystallized matrix to the surface (27 & 31). Water may also be released from the crystallized areas into the amorphous regions, further plasticizing the wall material and decreasing the stability of the system (25). Trehalose is an interesting molecule because it possesses a high glass transition temperature and, unlike hydrolysed starch, crystallises. In addition, it crystallises mainly as trehalose dihydrate thus immobilizing water and keeping the water activity at a low level. These interesting properties of trehalose have lead to a study on the use of trehalose as wall material in the encapsulation of orange oil. Table 2 lists the results obtained shortly after spray drying for the moisture content and the glass transition and melting characteristics of two powders, one encapsulated with glucose syrup and n-OSA starch and the other with trehalose and n-OSA starch. Differences between the powders in moisture content were insignificant. In the presence of glucose syrup (DE 38), the wall material was fully amorphous with a glass transition range in the region 78-95 C. When trehalose replaced glucose syrup, the glass transition temperature was found to be slightly lower (70-82 C) and a melting transition was observed. The extent of crystallinity was, derived from the melting transition, only ca 8%. Thus, both powders were fully or almost fully amorphous.
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In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
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Table II. Moisture content and glass transition and melting characteristics of two spray-dried powders comprising orange oil (20%) and wall material of different compositions immediately after spray drying. Wall material Parameter
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Moisture (%) Glass transition temperature ( C ) onset peak end Melting temperature ( C ) Onset Peak Crystallinity (%)
b c a
Trehalose/n-OSA starch (3:1, w/w) 2.79 70.7 0.9 74.2 1 . 1 81.8 1.1 90.3 0.7 98.1 0 . 7 Ca. 8
Infra-red moisture balance (130C, 20 min); DSC program: Equilibrated at 20C and ramped from 20 to 130C (scan rate 5C/min). Average of 3 replicates; Calculated with A H (trehalose dehydrate) = 86.2J/g ()
m
Table III. Influence of low molecular weight carbohydrates on the retention of orange oil during spray drying. Carrier Glucose syrup D E 42/ n-OSA starch (3:1, w/w) Trehalose/ n-OSA starch (3:1, w/w) Trehalose/ n-OSA starch (3:1, w/w) Erythritol/n-OSA starch (3:1, w/w) Isomalt/n-OSA starch (3:1, w/w) Orange oil load (%) 20 20 20 20 20 Infeed solids (%) 55 55 55 55 55 Oil retention (%) 96.6 95.2 98.6 35.4 94.5
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
222 The extent of crystallinity in the orange oil powder encapsulated with trehalose was too small to affect the retention of orange oil during drying (Table 3). Similar results were obtained with isomalt (Table 3). However, erythritol resulted in a crystalline powder (extent of crystallinity was ca. 82%) with poor flavour oil retention (Table 3). Since no orange oil was lost with glucose syrup, trehalose or isomalt, these results suggest that for good flavour retention a matrix, which does not crystallise during processing, is required. In the amorphous state, Drusch, Serfert, van den Heuvel and Schwarz (33) found that trehalose was a better ingredient for encapsulation of fish oil than glucose syrup (DE 38) due to its ability to provide better protection against oxidation. These results were obtained at a very low relative humidity. Figure 3 demonstrates the moisture sorption properties of similar carriers but for the encapsulation of orange oil under conditions of increasing relative humidity. The powder encapsulated in the presence of glucose syrup exhibited a continuous increase in the uptake of moisture as the relative humidity increased. In contrast, a plateau was observed for the powder encapsulated in the presence of trehalose at relative humidities in the region of 53.3 to 85.0%. This plateau corresponded to complete crystallisation of trehalose (Table 4). At complete crystallisation, there was no significant increase in the uptake of moisture (Figure 3) and consequently, the glass transition temperature did not significantly decrease (Table 4). Collapse/caking was observed when the powder encapsulated with glucose syrup increased in relative humidity to 43% and at a relative humidity of 70%, this powder liquefied. Crystallisation of trehalose led to a hardening of the powder, limiting the range of applications to capsules requiring storage at low humidity. Drush, Serfert, van den Heuvel and Schwarz. (33) came to the same conclusion based on the observation that rapid oxidation followed crystallisation of trehalose.
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Emulsification capacity The retention of oil during spray drying has been found to improve on addition of an emulsifier. For example, Trubiano & Lacourse (34) showed that even though maltodextrins matched the viscosity of gum Arabic, they didn't encapsulate as much oil possibly due to lack of emulsifying properties (Table 5). Gum Arabic is a complex mixture of macromolecules comprising predominantly carbohydrate and a small proportion (2%) of protein. Concentrations of 12% or higher are required to stabilize 20% (w/w) orange oil-in-water emulsions. Under these conditions, Randall, Phillips and Williams (35) showed that only 1-2% of gum Arabic bound effectively at the oil droplet surface and this adsorbed material contained a high proportion of protein. It has been proposed that the
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
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20 40 50
30
60
70
80
90
100
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Figure 3. Moisture/sorption isotherms of two spray-dried powders comprising orange oil (20%) and wall material of different composition, Le. () glucose syrup DE 42/n-OSA starch (3:1, w/w) and (m) trehalose/n-OSA starch (3:1, w/w).
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Table IV. DSC Characteristics of two spray-dried powders comprising orange oil (20%) and wall material of different compositions at varying relative humidities Composition of wall material Trehalose/n-OSA starch (3:1, w/w) 43.0 58.0 80.5
Parameters
Glucose syrup DE 38/ n-OSA starch (3:1, w/w) 43.0 58.0 80.5
Glass transition temperature ( C ) - onset 35.3 19.7 -31.7 -22.7 -14.8 30.1 39.8 44.1 52.5
b
26.3 32.3
9.2 15.4
- peak
Crystallinity (%)
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
m
DSC program: Equilibrated at 20C and ramped from 20 to 130C (scan rate 5C/min). Average of 3 replicates; Calculated with A H (trehalose dehydrate) = 86.2J/g ()
225 protein component of gum Arabic embeds in the oil while the carbohydrate component extends into the water phase (36). The emulsifying properties inherent to gum Arabic are believed to be partially responsible for its ability to improve oil retention during drying. A stable emulsion of fine droplets of core material as infeed solution is critical to microencapsulation. Risch & Reineccius (37) demonstrated the importance of particle size in the encapsulation of organic compounds. A smaller particle size led to a better retention of citrus oil during drying and yielded spray-dried powders, which contained less extractable surface oil. These findings are in agreement with the results obtained from various studies and listed in Table 5. Surface oil may be critical to powder stability because oil droplets on the surface of powder particles are not protected against atmospheric oxygen. However, a reduction in extractable surface oil with smaller particle size did not result in better shelf stability or resistance to oxidation. The fact that surface oil is not critical to shelf stability has been confirmed by various studies (32, 34 & 38), which suggests that other factors such as matrix porosity may be more significant in determining the rate of oxidation of encapsulated core materials. As an alternative to gum Arabic, a chemically modified starch has been used successfully in the microencapsulation of organic compounds. The starch derivative is prepared by a standard esterification reaction using n-octenyl succinic anhydride (n-OSA). The substitution of a hydrophobic octenyl side chain is at a level of about 1 per 50-60 anhydrous glucose units, which corresponds to 3% n-OSA in weight, the maximum level approved for food use. To lower viscosity, n-OSA starches are hydrolyzed either by acid thinning, pyrodextrinization or enzyme hydrolyses. Enzymes that can be used are the aand -amylase or a combination of both. n-OSA Starches offer excellent emulsifying properties leading to good quality infeed solutions with average oil droplet sizes of less than one micron (Table 5: Cargill and 32). Compared to gum Arabic, n-OSA starch provides wall materials that have higher levels of retained core material and less extractable surface oil (Table 5:32 & 34). These improved properties result in a direct economic benefit to the manufacturer and user of the product. They did not, however, result in better oxidation stability. Both Trubiano & Lacourse (34) and Partanen , Yoshii, Kallio, Yang & Forssell (32) found that the oxidation resistance of wall material comprising n-OSA starch was similar, but not worse, to that of gum Arabic. In our studies, excellent results were obtained at an oil load of 20% and an infeed solids concentration of 55%. Retention of oil during spray drying was high (Table 1 and 5) and due to the high D E of the coating material, the spraydried powder displayed excellent stability against oxidation (Figure 2). In addition, Figure 4 illustrates that the spray-dried capsules had little surface indentations (Figure 4), which likely contributed to the excellent stability during storage.
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In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
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OS
Carrier
Reference
Core material (%) 30 30 30 Average diameter () <3 2-10 <2 Oil retention (%) 94.0 76.5 99.7 98.6 100 100 Surface oil (%) 16.5 25.6 1.0 0.63 0.8 4.4 20 30 30 52 52 55
34
0.2
Cargill
32 32.6
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Gum Arabic Dextrin n-OSA Starch Syrup DE42 / n-OSA starch (3:1) n-OSA Starch (DE 32-37) Dextrin D E 18.5/ Gum arabic (1:7)
227
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Figure 4. A SEM image of spray dried powders containing orange oil (20%) encapsulated with glucose syrup DE 42/n-OSA starch (3:1) at an average particle she of25-55 m
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
228 The emulsifying properties inherent to gum Arabic are due to the presence of proteins. Proteins in isolation can be good emulsifiers but under certain conditions, they can loose stability due to aggregation or precipitation. This instability is most pronounced at pH values close to the protein's isoelectric point. Ideally, proteins suitable for microencapsulation by spray drying should be soluble over a wide pH range, have good emulsifying properties and exhibit a low viscosity profile on dissolution in water. A promising group of proteins that fulfills these requirements are whey protein isolates. In combination with carbohydrates, Sheu & Rosenberg (19 & 30) showed that whey proteins provided good quality infeed solutions and improved the surface smoothness of carbohydrate-based microcapsules. Best results were obtained with blends of whey protein isolate and carbohydrates of high D E .
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Conclusion
Successful microencapsulation is the result of a judicial choice of wall material composition for a given core material. The basic principles governing the fonction of starch hydrolysis products in the microencapsulation of organic compounds are quite well understood. For example, low molecular carbohydrates are effective in providing protection against oxidation, possibly by increasing the density and improving the viscoelasticity of the wall matrix, but they lack emulsifying properties. Lower D E value maltodextrins accelerate film formation and lead to improved retention of core material during drying . However, this effect could not be confirmed in the presence of an emulsifier. Emulsifiers like gum Arabic, modified starches and proteins are added to provide a good quality infeed solution with properly sized oil droplets (<1 micron). A stable emulsion of fine oil droplets as infeed solution is critical to microencapsulation. In practice, the choice of wall materiall is determined by the requirements for optimal microencapsulation of a given core material in terms of (a) the infeed solids content, (b) particle size of the infeed solution, (c) D E , (d) ratio of emulsifier to low molecular weight carbohydrates and (e) hygroscopicity. Higher infeed solids content can be made with hydrolyzed starches of higher DE, hence lower viscosity. In the presence of less water, a film is formed faster around the core material leading to a better retention of core material and to less oil on the surface of the powder. A smaller particle size increases the rate of film formation and results in a better retention of core material in the spray-dried powder. In addition, the product is more stable upon reconstitution in beverage applications where viscosity cannot be increased to help stabilize the core material.
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
229 In the amorphous state, the effectiveness of a carbohydrate matrix film to retain core material and inhibit the uptake of oxygen is directly related to D E . From this it can be concluded that the use of low molecular weight carbohydrates with a higher D E is preferred. However, hydrolysed starches with a higher D E have a lower glass transition temperature. The D E should be selected at a value, which is not too high as to remain below the glass transition temperature. In addition, hydrolysed starches with a higher D E are usually more susceptible to hygroscopicity. Increased moisture uptake leads to a reduction in the glass transition temperature and consequently, controlled storage conditions may be required.
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Acknowledgement
The authors wish to express their sincere thanks to Daniele Karleskind and Pat Clarkin for their enthusiastic and invaluable support to this project, to Dirk Fonteyn, Annick van den Heuvel and Dounia Sahmaoui for their technical support and to Marline Moris and Myriam Marinoni for their contribution in searching the literature.
References
Jackson, L.S. & Lee, K. (1991). Microencapsulation in the food industry. Lebensmittel-Wissenschaft und Technologie, 24, 289-297. 2. Balassa, L.L. & Fanger, G.O. (1971). Microencapsulation in the food industry. CRC Critical Reviews in Food Technology 2 (2) 245-265. 3. Dziezak, J.D. (1988). Microencapsulation and encapsulated ingredients. Food Technology, 42, 136-151 4. Gibbs, B.F., Kermasha, S., Alli, I. & Mulligan, C.N. (1999) international Journal of Food Sciences and Nutrition 50, 213-224. 5. Gouin, S. (2004) Micro-encapsulation: Industial appraisal of existing technologies and trends. Trends in Food Science & Technology 15, 330347. 6. Desai, K.G.H. & Park, H.J. (2005) Recent developments in microencapsulation of food ingredients. Drying Technology 23 (7) 13611394. 7. Madene, ., Jacquot, M . , Scher, J. & Desobry, S. (2006) Flavour encapsulation and controlled release - a review. International Journal of Food Science and Technology 41, 1-21. 8. Reineccius, G.A. (1991) Carbohydrates for flavor encapsulation. Food Technology March, 144-146. 1.
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
230
9. 10.
11.
12. 13.
14. 15.
16.
17.
18.
19.
20.
21.
Qi, A.H. & Xu, A. (1999) Starch-based ingredients for flavor encapsulation. Cereal Foods World 44 (7): 460-465. Kenyon, M.M. & Anderson, R.J. (1988). Maltodextrins and low-dextrose-equivalence corn syrup solids: production and technology for the flavor industry. In: Flavor Encapsulation (edited by S.J. Risch & G.A. Reineccius). Pp. 7-12. Washington, DC: American Chemical Society Kenyon, M.M. (1995) Modified starch, maltodextrin, and corn syrup solids as wall materials for food encapsulation. In: Encapsulation and Controlled Release of Food Ingredients (edited by S.J. Risch & G.A. Reineccius). Pp. 43-50. ACS Symposium Series 590. Washington, DC: American Chemical Society Reinceccius, G. A. & Coulter, S.T. (1969) Flavor retention during drying. J. Dairy Sci. 52 (8): 1219-1223. Kerkhof, P.J.A.M. & Thijssen, H.A.C. (1975) Aroma Research, Proceedings of the International Symposium; Pudoc: Wageningen, The Netherlands. Pp 167-192. Voilley, A. & Simatos, D. (1980) Retention of aroma during freeze and air drying. "Food Process Engineering". Vol. 1. Appl. Sci. Pub. Ltd., London. Bangs, W.E. & Reineccius, G.A. (1981) Influence of dryer infeed matrices on retention of volatile flavor compounds during spray-drying. Journal of Food Science, 47, 254-259. Karel, M & Langer, R. (1988) Controlled release of food ingredients. In: "Flavor encapsulation" (Reineccius, G.A. & Risch, S.J., eds). ACS Symposium Series No. 370. American Chemical Society, Washington, D.C., 177-190. Bangs, W.E. & Reineccius, G.A. (1990) Characterization of selected materials for lemon oil encapsulation by spray drying. J. Food Sci. 55: 1356-1358 Goubet, I., Le Quere, J.L. & Voilley, A. (1998) Retention of aroma compounds by carbohydrates: influence of their physicochemical characteristics and of their physical state. Journal of Agricultural of Food Chemistry, 48, 1981-1990. Sheu, T.Y. & Rosenberg, M . (1995). Microencapsulation by spray-drying ethyl caprylate in whey protein and carbohydrate wall systems. Journal of Food Science, 60, 98-103. Leahy, M.M., Anandaraman, S., Bangs, W.E. & Reineccius, G.A. (1983) Spray drying of food flavors II. A comparison of encapsulating agents for the drying of artificial flavors. Perfumer & Flavorist 8: 49-56 Reineccius, G.A. & Bangs (1985) Spray drying of food flavors. III. Optimum infeed concentrations for the retention of artificial flavors. Perfumer & Flavorist 9: 27-29.
Downloaded by INST POLITEC NACIONAL IPN on October 23, 2009 | http://pubs.acs.org Publication Date: March 3, 2009 | doi: 10.1021/bk-2009-1007.ch014
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
231
22. Menting, L.C. & Hoogstad, B. J. (1967) Volatiles retention during the drying of aqueous carbohydrate solutions. Journal of Food Science 32: 8790. 23. Reineccius, G.A. (1988) Spray drying of food flavors. In: Flavor Encapsulation (edited by S.J. Risch & G.A. Reineccius). Pp. 55-64. Washington, DC: American Chemical Society. 24. Rosenberg, M , Kopelman, I.J. & Talmon, Y. (1990) Factors affecting retention in spray drying microencapsulation of volatiles materials. J. Agric. Food Chem, 38: 1288-1294. 25. Whorton, C, (1995) Factors influencing volatile release from encapsulation matrices. In: "Encapsulation and controlled release of food ingredients" (edited by S.J. Risch & G.A. Reineccius). Pp. 134-139.. Washington, DC: American Chemical Society 26. Benczedi, D. (2002) Flavour encapsulation using polymer-based delivery systems. In: "Food Flavour Technology" (edited by A.J. Taylor). Pp153166. Sheffield Academic Press Ltd., UK. 27. Roos, Y . & Karel, M . (1991). Water and molecular weight effects on glass transitions in amorphous carbohydrates and carbohydrate solutions. Journal of Food Science 56 (6) 1676-1681 28. Anandaraman, s. & Reineccius, G.A. (1986) Stability of encapsulated orange peel oil. Food Technology 40, 88-93. 29. Whorton, C. & Reineccius, G.A. (1995) Evaluation of the mechanisms associated with the release of encapsulated flavor materials from maltodextrin matrices. In: "Encapsulation and controlled release of food ingredients" (edited by S.J. Risch & G.A. Reineccius). Pp. 143-159. Washington, DC: American Chemical Society 30. Sheu, T.Y. & Rosenberg, M . (1998). Microstructure of microcapsules consisting of whey proteins and carbohydrates. Journal of Food Science, 63, 491-494. 31. Labrousse, S., Roos, Y. & Karel, M. (1992) Collapse and crystallization in amorphous matrixes with encapsulated compounds. Sci. Aliments 12: 757769 32. Partanen, R., Yoshii, H., Kallio, H., Yang, B. & Forssell, P. (2002) Encapsulation of sea buckthorn kernel oil in modified starches. Journal of the American Oil Chemists Society, 79 (3) 219-223 33. Drush, S., Serfert, Y., Heuvel van den, A. & Schwarz, K. (2006) Physicochemical characterization and oxidative stability of fish oil encapsulated in an amorphous matrix containing trehalose. Food Research International 39, 807-815. 34. Trubiano, P.C. & Lacourse, N.L. (1988) Emulsion-stabilized starches. In: Flavor Encapsulation (edited by S.J. Risch & G.A. Reineccius). Pp. 55-64. Washington, DC: American Chemical Society.
Downloaded by INST POLITEC NACIONAL IPN on October 23, 2009 | http://pubs.acs.org Publication Date: March 3, 2009 | doi: 10.1021/bk-2009-1007.ch014
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
232
Downloaded by INST POLITEC NACIONAL IPN on October 23, 2009 | http://pubs.acs.org Publication Date: March 3, 2009 | doi: 10.1021/bk-2009-1007.ch014
35. Randall, R.C., Phillips, G.O. & Williams, P.A. (1988) The role of the proteinaccous component on the emulsifying properties of gum arabic. Food Hydrocolloids, 2: 131-140. 36. Garti, N . (1999). Hydrocolloids as emulsifying agents for oil-in-water emulsions. Journal of Dispersion Science and Technology, 20: 327-355. 37. Risch, S.J. & Reineccius, G.A. (1988) Spray-dried orange oil. Effect of emulsion size on flavor retention and shelf stability. In: Flavor Encapsulation (edited by S.J. Risch & G.A. Reineccius). Pp. 67-77. Washington, DC: American Chemical Society. 38. Buffo, R. & Reineccius, G. (2000). Optimization of gum acacia/modified starch/maltodextrin blends for the spray drying of flavors. Perfermor and Flavorist, 25, 37-51.
In Micro/Nanoencapsulation of Active Food Ingredients; Huang, Q., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.