CA2821122A1 - Delivery of functional compounds - Google Patents

Abstract

Functional ingredients including a modified portion are microencapsulated in an enteric matrix. The modified functional ingredient portion increases the microencapsulation efficiency and reduces undesired organoleptic properties of the microencapsulated material while providing a desired release rate. The process includes forming an emulsion in water and titrating the emulsion with a precipitating agent to produce a particulate precipitate.

Description

DELIVERY OF FUNCTIONAL COMPOUNDS
CROSS-REFERENCE TO RELATED APPLICATIONS
[00011 This application claims benefit of United States Provisional Application Number 61/422,439, filed December 13, 2010, and is a continuation-in-part of United States Patent Application Number 12/479,444, filed June 5, 2009, both of which are hereby incorporated by reference in their entirety herein.
FIELD
100021 This application relates to a modified functional ingredient which is micro-encapsulated by an enteric matrix and methods for making the same. More particularly, the modified functional ingredient is rnicroencapsulated in an aqueous environment which is substantially free of organic solvents.
BACKGROUND
[00031 Enteric delivery of functional materials in food applications has been limited.
Enteric delivery systems are commonly utilized when the functional materials or medicaments are known to be sensitive to certain conditions such that they become less effective or if the functional materials cause problems for the user, such as stomach problems with aspirin.
Generally, enteric delivery, as most common in pharmaceutical practice, is accomplished using coated tablets and gel capsules. However, those particular delivery methods are not well suited for food applications. In particular, neither tablets nor capsules are sized to be integrated into most existing food products.
100041 An alternative process for enteric delivery is microencapsulation.
Micro-encapsulation is generally performed using specialized equipment or in an environment including organic solvents. These methods require additional capital expenditures and the use of additional materials, such as the organic solvents, which may or may not be usable in subsequent microencapsulation cycles. As a result, the process of microencapsulation requires investments in both equipment and organic solvent procurement and disposal.
100051 One issue with microencapsulation is the recovery rate, or microencapsulation efficiency of the process. Generally, a certain significant percentage of the material to be microencapsulated is not captured. The uncaptured material may be recovered for reuse, recycled, or a percentage of the uncaptured material remains adhered to the outer surface of the microencapsulated particulates.
[00061 As a result, the product tends to have a taste profile associated with the uncaptured material, which is often undesirable. This is particularly true when the uncaptured material includes oxidizable triglycerides such as unsaturated and polyunsaturated lipids, oxidizable flavors and essential oils, or other organic compounds that may naturally have undesirable taste and/or flavor.
SUMMARY
[00071 The composition includes a functional ingredient microencapsulated in an enteric matrix, such as described in US. Patent Application Serial No. 12/479,454, which is incorporated by reference in its entirety herein. The enteric matrix includes one or more food grade polymer(s), and the functional ingredient includes a modified functional ingredient [00081 In one embodiment, the functional ingredient is homogeneously dispersed throughout the enteric matrix material. In another embodiment, the functional ingredient includes at least about 30 percent modified compounds. In one form, the modified compound includes at least one of a salt, glycoside, complex or ester of an essential oil, such as linalool and thymol.
100091 In one aspect, a method of microencapsulating a modified active or functional ingredient is provided. The method includes agitating or mixing water, an enteric matrix material, and an emulsifier to form a combination at a pH that maintains complete dissolution of the enteric matrix material being utilind. In one approach, the combination is substantially free of organic solvents. A functional ingredient including a modified portion is added to the combination and homogenized to create a fine, stable emulsion. The emulsion is then treated with an acid and/or other cross-linking or precipitating agents, depending on the enteric matrix material being used, such as calcium, under controlled mixing conditions and in an amount and at a rate effective to form a particulate precipitate. Further, the functional ingredient is homogeneously dispersed throughout the precipitate and with an improved microencapsulation efficiency of the functional ingredient.

BRIET DESCRIPTION OF THE DRAWINGS
[0010] FIG. I illustrates a method for microencapsulating a functional ingredient;
[0011] FIG. 2 is a chart comparing the microencapsulation efficiency between two experiments, with one experiment including a functional ingredient that does not contain at least 30 percent esters, the second experiment including a functional ingredient that includes at least 30 percent esters of linalool and thymol;
[0012] FIG. 3 is a table showing the known empirical formula, solubility in water, vapor pressure, partition coefficient and a ratio comparing the affinity for oil to water ratio of various esters;
[00131 FIG. 4 is a graph illustrating the percentage release of the various components of a functional ingredient which does not include esters with an enteric matrix comprised of 95 percent shellac and 5 percent zein;
10014] FIG. 5 is a graph illustrating the percentage release of the various components of a functional ingredient including esters with an enteric matrix comprised of 95 percent shellac and 5 percent zein;
[0015] FIG. 6 is a graph illustrating the percentage release of the various components of a functional ingredient comprising linalyl acetate within an alginate/ shellac enteric matrix in a digestion model simulating stomach and small intestine conditions; and [00161 FIG. 7 is a graph illustrating the percentage release of the various components of a functional ingredient comprising linalyl butyrate within an alginate/ shellac enteric matrix in a digestion model simulating stomach and small intestine conditions.
DETAILED DESCRIFI __________________________ ION
[00171 Disclosed is a method of microencapsulating a modified functional ingredient and a non.-active carrier(s) in an enteric matrix that minimizes release of the functional ingredient prior to dissolution in the intestine. Further, the funchonal ingredients can have undesirable taste or flavor profiles. In some cases, modifying the functional ingredient can mask or change the undesirable tastes and/or flavors while retaining the proper ratios of the functional ingredients ensuring bioavailability and efficacy.

100181 In one form, the functional ingredient to be microencapsulated can include modified forms of essential oils, such as thymol and linalool. Modifications to the functional ingredient may include a variety of forms that modify the perceived taste and/or organoleptic properties of the functional ingredient. For example, the modification may cause a change to the flavor and/or taste threshold of the functional ingredient. In one form, the modification causes a change to the volatility and/or vapor pressure of the modified functional ingredient with respect to the non-modified, parent form of the functional ingredient. In particular, the organoleptic properties of the modified form may include a higher taste threshold. As a result, in some cases a modified functional ingredient on the surface of the enteric matrix may produce a less undesirable flavor profile than the presence of unmodified functional ingredients.
Further, the modifications may include salt, glycoside, complex and/or esterification of the functional ingredient.
[00191 When ingested and released in the intestinal tract, the modified form of the functional ingredient reverts back, at least in part, into the parent form and provides the same functional benefits as if the parent functional ingredient was microencapsulated and consumed.
In one form, the modified functional ingredient hydrolyzes from the modified form back into the parent, non-modified form of the functional ingredient during digestion.
Further, the modified forms of the functional ingredient can provide additional benefits as will be discussed further below.
[00201 The modified form may make up varying percents of the overall functional ingredient composition. For example, the modified form comprises at least 10%
of the functional ingredient composition. In another example, the modified form comprises at least 30% of the functional ingredient composition. In yet another example, the modified form comprises at least 50% of the functional ingredient composition.
[00211 Further, where the modified functional group includes an ester, other benefits are realized. Esters are generally known to produce less undesirable flavors, and therefore any flavors produced would not result in a wholly undesirable organoleptic flavor profile. Further, due to the low water solubility and/or increased hydrophobicity of the modified functional ingredients including an ester, particularly in reference to the parent non-esterified functional ingredients, the below described method can result in a higher microencapsulation efficiency, as can be shown by a higher payload and retention rate, than has been recognized in the absence of e.sterified functional ingredients.
[00221 Examples of the use of the product created by the methods described herein are aimed at delivery in a powdered soft drink (P5D) beverage. Other exemplary uses of the product include other food products, such as biscuits, bars, ice cream, snacks, instant meals and the like.
[0023] A method for microencapsulating a functional ingredient is generally described in FIG, 1. Enteric delivery within a food matrix is achieved by the formation of matrix particles with the dispersed portion being that of the functional ingredient, such as an essential oil blend with diluent triglycerides, and the matrix portion is that of food grade enteric polymers, such as shellac, zein, calcium alginate, denatured whey protein, caseinate and any and all food-grade enteric polymers.
[0024] As shown in FIG, 1, water, an enteric matrix material and an emulsifier are mixed or agitated until the enteric matrix material and emulsifier are fully dispersed in the water 1.00.
Generally, the emulsifier and enteric matrix material can be added to the water together or separately, with either being added first. The pH is maintained at a level sufficient that allows for complete solubilization of the enteric material. As an example, for use of shellac, zein or combinations thereof, the pH of the dispersion is generally between about 7.2 and 9,0. In some embodiments, a basic material, such as sodium, potassium or ammonium hydroxide, can be added to the dispersion to raise the pH, such as within a range from about 7.2 to about 1.2.0, preferably 8.0 to 11.3, to guarantee and maintain complete dissolution of the enteric polymers without the use of organic solvents, [0025] As used herein, "agitation" or "agitated" refers to the use of a top entering mixer with impeller or a rotor/stator mixing device operating at a speed of less than 10,000 RPM.
100261 As used herein, "substantially free of organic solvent" refers to an amount of added organic solvent, such as isopropanol or ethanol or any other organic solvent less than the amount required to enable solubility of the enteric material under the processing conditions. In.
one approach, the amount of added organic solvent is less than about 0,1 percent by weight of the combination of water, emulsifier and enteric material.
-.5.

[00271 In one embodiment, the water is deionized water.
[00281 The enteric matrix material used herein is any food grade enteric polymer, or a combination of two or more food grade enteric polymers. Preferably, the enteric matrix material is shellac, zein, calcium alginate, caseinate or combinations thereof. Other food grade enteric polymers include denatured whey protein. In one approach, the prepared enteric matrix material does not contain any organic solvents.
[00291 The emulsifier described herein may be any food grade emulsifier. In preferred embodiments, the emulsifier is polysorbate, polyglycerol ester, sucrose stearate, sucrose esters, proteins, lecithins or combinations thereof. More particularly, the emulsifier is preferably a sucrose ester due to the creation of the smaller and most uniformly dispersed oil droplets within the later created emulsion.
[00301 Generally, water comprises about 50 percent to about 95 percent of the dispersion by weight and preferably from about 70 to about 95 percent, and more preferably from about 80 to about 90 percent. The emulsifier generally comprises less than about 5 percent of the dispersion by weight, preferably from about 0.01 to about 1 percent by weight, and more preferably about 0.01 to about 0.1 percent by weight of the dispersion. In one approach, the enteric matrix material ranges from about 1 percent to about 10 percent by weight, in other approaches from about 4 to about 7 percent, and yet in other approaches from about 5 percent to 6 percent by weight of the dispersion.
[00311 Upon forming the dispersion, a functional ingredient, having at least a portion thereof modified, and a non-active carrier is added 200 and agitated 300 to provide a coarse emulsion having a droplet size of more than about 10 micrometers. After the coarse emulsion is formed, the coarse emulsion is homogenized 300 to create a fine, stable emulsion. In one approach, the fine, stable emulsion has a droplet size of less than about 10 micrometers. Within the fine emulsion, the functional ingredient and non-active carrier are homogeneously dispersed in the form of fine droplets throughout. In one approach, the combination of the functional ingredient and non-active carrier is added in amount ranging from about 2 to about 7 percent of the emulsion by weight. In other approaches, the combination of the functional ingredient and non-active carrier is added in an amount ranging from about 3 to about 6 percent of the emulsion by weight. The emulsion includes from about 60 to about 95 percent water.
[00321 As used herein, "homogenization" or "homogenized" refers to mixing at a speed greater than about 10,000 RPM, such as the use of a rotor/stator mixing device or at a lower mixing speed of an elevated pressure, such as a valve homogenizer operating at a pressure of about 500 psi to about 10,000 psi.
[00331 In one approach, the functional ingredient may include chemically modified compounds of essential oils. As an example, the functional ingredient includes chemically modified compounds of thyrnol and linalool. For example, glycosides, salts and/or complexes of thymol and/or linalool may be used. In one form, thymyl and linalyl acetate may be used.
Further, other fatty acid esters may be used, such as octanoate. Other acceptable chemically modified compounds can be used, such as butyrates, lactates, cin.namates and pyruvates. In another example, the functional ingredient includes alpha-pinene, para-cymene, thymyl esters or salts and linaly1 esters or salts. As discussed in the examples below, one exemplary blend includes, by weight, about 18 percent canola oil, about 8 percent alpha-pinene, about 39 percent para-cymene, about 5 percent linalool acetate and about 27 percent thymyl acetate.
[00341 The modified functional ingredient portion can comprise from about 1 to about 99 percent of the functional ingredient by weight. In some approaches, the modified functional ingredient can include from at least about 10 percent of the functional ingredient by weight and, in other approaches, about 30 percent by weight. In another embodiment, the modified functional ingredient can include from about 25 to about 65 percent of the functional ingredient by weight.
[00351 In one embodiment, the blend of non-active carrier and functional ingredient can include, by weight, about 15 to about 30 percent canola oil, about 1 to about 10 percent alpha-pinene, about 5 to about 25 percent para-cymene, about 5 to about 20 percent linalyl ester and about 20 to about 60 percent thymyl ester. In other approaches, the blend of non-active carrier and functional ingredient can include, by weight, about 20 to about 25 percent canola oil, about 2 to about 7 percent alpha-pinene, about 10 to about 20 percent para-cymene, about 7 to about 15 percent linalyi ester and about 35 to about 50 percent thymyl ester.
-I..

[0036] Generally, and in one approach, an esterified form of a functional ingredient, such as thymol and linalool, can be used regardless of the chemical or biochemical reaction approach for its preparation. For example, any ester formed between the hydroxyl group(s) of a terpene and an organic or inorganic oxoacid (containing single or multiple oxoacid groups) may be used as the functional ingredient. The volatility and vapor pressure of the modified functional ingredient can impact the perception of the ingredient. For example, the size of the ester group may be modified to provide a desired volatility. In one approach, the ester linakage is at least an ethyl ester. It should be noted that larger ester groups may also be used.
100371 By one approach, the selected esterified form may have increased functionality due to an increased rate of hydrolysis over the parent form after ingestion and release from the enteric matrix in an intestinal tract. Esters may be obtained from natural sources or synthesized using any suitable chemical or biochemical reactions between functional ingredients, such as thymol and linalool, and organic or inorganic oxoacids that yield esters.
Suitable oxoacids may include carboxylic acid, amino acids, phosphoric acid, sulfuric acid, and nitric acid. The hydroxyl group can be derived from a homogenous source (e.g. thymol) or mixed source (thymol and linalool). Exemplary monocarboxylic acids include, but are not limited to, acetic, propionic, butyric, pentanoic, hexanoic, decanoic, stearic, lactic, cinnamic, pyruvk, benzoic, and gluconic acids. Exemplary dicarboxylk acids include, but are not limited to, oxalic, malonic, maleic, fumaric, tartaric, succinic, glutaric, glucaric, adipic, pimelic, suberic, azelaic, and sebacic acids. Exemplary tricarboxylic acids, include, but are not limited to, citric and isocibic acids.
Other exemplary esters that may be formed by reactions of terpenes with oxoacids include dithymol succinate, dithymol adipate, and dithymol sebacate.
[0038] in another form, the modified functional ingredient can include an ester formed, regardless of chemical or biochemical reaction approach for its preparation, between terpene esters and other esters. In particular, the functional group can be formed using transesterification. For example, the functional group can include an ester formed by reacting thymol acetate with methyl octanoate or tripalmitin.
10039] Alternatively, it is anticipated that the functional ingredient can include other modified compounds. In one form, the modified functional group can include any glycoside formed by chemical or biochemical reaction between the hydroxyl group(s) of a terpene and a single sugar group (monosaccharide) or several sugar groups (oligosaccharide).
For example, thymol and/or linalool glycosides can be the modified functional ingredient.
The sugar group can include any glycoside with the glycone portion composed of mono-, di- tri-, and/or polysaccharides of any kind and the aglycone portion being any hydroxy-terpene (e.g. thymol, linalool). The sugar group can also include reducing sugars and/or non-reducing sugars.
Exemplary sugars include, but are not limited to, glucose, fructose, galactose, ribose, sucrose, mannose, maltose, lactose, and cellobiose.
100401 In another form, it is anticipated that the functional group can include any ionic or nonionic salt or complex formed involving a hydroxy-terpene and another chemical species.
For example, thymol and linalool salts or complexes can be the modified functional ingredient.
One example may be sodium and/or potassium chloride. In another form, the modified functional ingredient may include thymol salts that do not have fixed stoichiometries. For example, thymol salts may be prepared as partial or mixed salts having different ratios of cations and thymol comprising one or more specific cations (Na+, K+, Mg++, etc.) to prepare solid complexes. The solidified complexes may or may not be obtained in crystalline form. The salt or complex may be formed by any suitable method, but in some cases is formed by a chemical reaction or association between one or more hydroxy-terpene and one or more alkaline reagent. Exemplary alkaline reagents may include, but are not limited to, alkaline hydroxide, oxide, or carbonate. The salt or complex can include any alkali metal, alkaline earth metal, or transition metal element, or combination thereof. Suitable salts or complex for use in foods may include sodium, potassium, lithium, calcium, magnesium, iron, manganese, zinc, and aluminum. Other exemplary salts include any mono-, di-, or trivalent salt of thymol, including sodium thymolate (e.g. sodium thymoxide) and any mono-, di-, or trivalent salt of phenol, including calcium phenoxide.
100411 Furthermore, the functional ingredient may include various forms of modification that are combined. For example, a portion of the modified functional ingredient composition may include one or more of salts, glycosides, complexes and esterified forms of one or more essential oils.
[00421 In some approaches, the functional ingredient may include a mixture of any essential oils as described herein. Further, the functional ingredient can be selected to include materials which are desired to be released enterically. As an example, the functional ingredient can include compositions described in U.S. Patent Publication No. 2008/0145462 to Enan. For example, the functional ingredient includes about 25 to about 35 percent by weight para-cymene, about 1 to about 10 percent by weight linalool, about 1 to about 10 percent by weight alpha-pinene, about 35 to about 45 percent by weight thymol, and about 20 to about 30 percent by weight soybean oil.
[00431 In some approaches, the functional ingredient described herein can include compounds which possess functional properties, such as anti-parasitic, anti-protozoan, and anti-fungal. In one embodiment, the organic compounds further include alpha-pinene and para-cymene.
[0044] In another embodiment, organic compounds are blended with a non-active carrier such as a lipid, fatty acid, triglyceride or food grade oil, such as soybean oil or canola oil.
[0045] The volatile nature of some of the functional ingredients leads to a very low threshold value for olfactory perception, resulting in an undesirable flavor/taste in the existing beverage/food. In an effort to mask the flavor of the functional ingredients, the process described herein includes the inclusion of a far less water soluble form of a functional ingredient, such as an esterified form or other modified form of the functional ingredient (e.g.
esterified forms of thymol and linalool) as well as processes to remove unencapsulated material from the final ingredient. For example, esters generally have a less negative impact on the taste/flavor of the food system than their respective parent compounds.
Additionally, complexes, glycosides and salts of essential oils have a less negative impact on the taste/flavor of the food system than their respective parent compounds.
[0046] Due to the low water solubility and/or increased hydrophobicity, an ester may have higher microencapsulation efficiency, such as described above, than non-esterified parent compounds, such as thymol and linalool. Preferably, the efficiency increases about 50 to about 200 percent over the efficiency observed when using non-esterffied functional ingredients, more preferably about 100 to about 150 percent. Further, esters have a higher olfactory perception threshold than the parent compounds, such that amount of esters necessary to be perceived is more than the amount of non-esterified thymol and linalool.

[00471 Turning back to the method of FIG. I, the emulsion is then precipitated by titration with an acid or with a cross-linking or precipitating agent 400. During precipitation, the emulsion can be subjected to agitation. In one embodiment, the emulsion is titratecl with a solution of about 1 to about 5 percent calcium chloride and about 1 to about 5 percent citric acid.
In another embodimentõ the emulsion is titrated with acid in an amount effective to decrease the pH down to the isoelectric point of the polymer present in the emulsion, such as a pH of about 7, causing phase separation and inducing precipitation of the enteric matrix out of solution with the functional ingredient being microencapsuiated therein, thus creating a slurry of an aqueous solution and precipitate. The precipitated slurry has a particle size from about 1 to about 1000 micrometers, in some cases about 10 to about 500,0 micrometers, and more preferably from about 75 to about 250 micrometers. In other approaches, precipitation occurs at a pH ranging from about 3 to about 6, or further between a pH ranging from about 3.8 to about 4.6.
100481 While not wishing to be limited by theory, it is believed that as the pH of the emulsion drops down to the isoelectric point, the particles of enteric materialõ such as shellac and Zei11, may cross-link to like particles or to one another to form a matrix, the functional ingredient and non-active carrier being microencapsulated within the matrix.
As a result, of the cross-linking, the functional ingredient is homogenously dispersed throughout the matrix. The matrix further provides a seal for the functional ingredient. As a result, the impact of the functional ingredient on the organoleptic qualities of the finished powder is correlated to any functional ingredient remaining adhered to the outer surface of the enteric matrix.
[00491 The acid used can include any food grade acid. In one embodiment, the acid is citric acid.
[0050] As noted above, the composition of the enteric matrix material affects the dissolution rate and the protection provided by the enteric matrix.
[00511 To reclaim the precipitate, the slurry is filtered 500, washed 600 and dried 700. In one embodiment, the slurry is filtered, the resultant slurry cake is then washed and refiltered prior to drying.
-[00521 In some instances, there will remain at least marginal unencapsulated material on the outer surface of particulate precipitate. With the desire to mask compounds with low perception thresholds, the u.nencapsulated material generally is reduced to levels below perception in the final product matrix and/or solution. In some cases, the functional ingredient on the outer surface of the particulate precipitate is less than about 1 percent by weight of the final product.
[00531 In some cases, a surface oil remover is added to the slurry after filtering to aid in removing residual surface oil from the precipitate, as described in U.S, Patent Application Serial No, 12/479,433, which is incorporated by reference in its entirety herein.
Further, the surface oil remover can also be added prior to the refiltering step.
100541 After the precipitate has been filtered and washed, the precipitate is dried 700 to form a powder. Drying can be conducted. such that the powder has a moisture.
content of less than about 10 percent, in other approaches to a moisture content of about 2 to about 6 percent, and in yet other approaches to about 3 to about 5 percent.
[00551 Further, the powder can be pulverized to reduce the particle size of the powder precipitate, and then further dried to a moisture content of less than about 5 percent, such as with a fluidized bed dryer. The resultant particles have a particle size ranging from about 1 to about 1000 micrometers, in some cases from about 10 to about 500 micrometers, and in other cases from about 75 to about 250 micrometers.
[00561 When drying the powder, the temperature should be maintained between about 25 C to about 70 C, and in some cases about 35 C to about 65 C. During other processing steps, it may be suitable to maintain the temperature between about 4 C to about 40 C, in other cases about 4 C to about 30 C, and in yet other cases from about 15 C to about 28 C, 100571 As will be discussed further below, and as shown in FIG. 2, the inclusion of modified functional ingredients, such as thymyl and linaly1 esters, may result in an increased payload of the functional ingredients in the final product. The payload refers to the weight percentage of the functional ingredients in relation to the final product. Therefore, an increase in payload corresponds to an increase in functional ingredient per a given amount of enteric matrix. In some cases, the payload of the functional ingredients ranges from about 5 to about 50 percent.

The increased payload can be attributed, at least in part, to the decreased water solubility and/or increased hydrophobicity of a functional ingredient including modified functional ingredients, such as esters, in comparison to a functional ingredient which is not modified.
Further, in some cases, large volumes of water may be used in the disclosed process. A
modified functional ingredient, such as esters of thymol and linalool, would reduce leaching of the functional ingredient due to the decreased water solubility and/or increased hydrophobicity. The ability to limit losses during processing allows for control over the final ratio of functional compounds in the food system, as shown to be important in US. Patent Application Publication No. US 2008/0145462 Al, (Enan, E. et al.) Additionally, some functional ingredients, such as thymol, are crystalline solids at room temperature (about 20 to about 25 C). The substitution with a modified functional ingredient, such as thymyl acetate, which is a liquid at room temperature (about 20 to about 25 C) would allow for easier processing since a crystalline solid ingredient would no longer have to be solubilized in a liquid organic solvent, such as by dissolving thymol or other solid ingredient in triglyceride oil, ethanol, or other liquid, before preparation of the emulsion.
100581 Advantages and embodiments of the methods described herein are further illustrated by the following Examples. However, the particular conditions, processing schemes, materials, and amounts thereof recited in these Examples, as well as other conditions and details, should not be contrasted to unduly limit this method. All percentages are by weight unless otherwise indicated.
100591 Example 1: The Evaluation and Selection of Emulsifiers [00601 Various emulsifiers were combined with deionized water at about 60 C
to produce about 2% solutions. The resulting solutions were combined with an essential oil blend composition (about 4% alpha-pinene, about 30% para-cymene, about 7% linalool, about 35%
thymol and about 24% soybean oil) in a 50:50 weight ratio with deionind water to create an oil-in-water emulsion. The emulsifiers evaluated were Glycosperse 5-20 KFG (Lonza;
Fairlawn, NJ), Polyaldo 10-1-0 KFG (Lanza; Fairlawn, NJ), Aldosperse MS-20 KFG (Loma;
Fairlawn, NJ), Polyaldo 10-2-P KFG (Lonza; Fairlawn, NJ), Ryoto sugar ester (5-1570, Mitsubishi-Kagaku Food Corp.; Tokyo, Japan), Precept 8120 (Central Soya; Fort Wayne, IN) and sodium caseinate (Alanate-180, New Zealand Dairy Board; Wellington, New Zealand). The sucrose ester (5-1570) was identified as a good emulsifier due to the creation of the smallest and most uniformly dispersed oil droplets within the emulsion. The emulsion created with the sucrose ester also showed good stability after 24 hours storage at room temperature (about 20 to about 25"C).
[0061] Example 2: Microencapsulation of a Functional ingredient Containing Some Esterified Components in an About 75% Shellac / About 25% Zein Matrix [00621 About 2400 g of distilled, deionized water (D.I.H20) was added to a beaker mixed using StedFast Stirrer SL1200 (Yarnato Scientific; Tokyo, Japan) with a 4-pronged impeller blade at speed setting between 5 and 6. About 37.5 g of Jet Milled zein (F4000, Freeman Industries;
Tuckahoeõ NY) powder was added to the beaker and mixed until uniformly dispersed. Next, about 10% NaOH aqueous solution was added until the pH reached about 11.3. The zein-water mixture was agitated until the zein powder was completely dissolved and the solution was translucent. Next, about 450 g of the pre-made shellac (Temuss #594; Ajax, Ontario, Canada) in ammonium hydroxide solution (25% solids) was added and mixed for about 5 to about minutes. Finally, about 1.4 g of sucrose ste.arate, 5-1570 (Mitsubishi-Kagaku Food Corp.;
Tokyo, Japan) was added while mixing, such as for about 5 to about 10 minutes until homogeneous mixing has occurred.
[00631 Nextõ about 80 g of the essential oil blend (about 18.8% canola oil, about 8.6% alpha-pinene, about 39.8% para-cymene, about 5.4% !Maly' acetate and about 27.4%
thymyl acetate) was added and mixed for about 5 to about 10 minutes. Using the PowerGen 7001) (Thermo Fisher Scientific; Waltham, MA), the mixture was homogenized by blending for about 4 minutes at about 15,000 rpm, and then at about 20,000 rpm for about an additional minute to create the stable emulsion. Acid titration of the emulsion using about 3% citric acid solution followed using Master Flex pump (Barnan.t Corp.; Barrington, IL) at the highest speed setting with moderate overhead mixing until the pH reached about 3.8, thereby creating a slurry.
[00641 About 10 g of 5i02 AB-D (PPG Industries; Pittsburg, PA) was added to the slurry and continued to be mixed for about 20 to about 30 minutes. The mixture was filtered using a #200 mesh (75 micrometer) screen to produce a cake. In a separate, clean 4000 ml plastic beaker, about 2000 g of D.1. H2O and about 2.5 g of Si 02 AB-D was mixed to create a solution. The cake was resuspended in this solution and mixed for about 3 to about 5 minutes. The mixture was filtered using a #200 mesh screen to produce a second cake.

10065] In a separate, clean 4000 ml plastic beaker, about 2000 g of DJ. H20 and. about 2,5 g of 5102 AB-.D was mixed to create another solution. The second cake was resuspended again and mixed for about 3 to about 5 minutes. The filtrate was pressed using cheese cloth to remove the extra moisture. The filtrate was then spread evenly on large tray on top of a cookie sheet for overnight drying, uncovered and at room temperature (about 20 to about 25 C).
[00661 The dried filtrate particles were ground using a Magic Bullet MB1001 (Sino Link International Trading Co.; Zhejiang, China). Particles between about 75 to about 250 micro-meters were separated using #60 and #200 mesh sieves. The moisture content was measured using the CEM Smart System 5 (CEM Corp,; Matthews, NC). To reduce the moisture content to less than about 6 percent, the filtrate was dried in a Uni-Glatt fluid bed dryer (Glatt Air Techniques; Ramsey, NJ) at about 40 C, checking about every 5 minutes. As a result, the final product had a moisture content of less than about 6 percent. The fraction was sifted by passing through a #60 mesh screen and collected on a #200 mesh screen, thereby producing particles having a size of less than about 250 micrometers and greater than about 75 micrometers, The composition, payload, and surface oil of the resultant product are illustrated in the table below.
alpha- para-. Unalyl. Thyinyl Cancila Essential , Pinene Cymene Linalool Acetate Thymol Acetate Oil Oil Total . , ' wt % wt % wt % wt % wt % wt % wt % wt % wt %
Payload 057, , 1.3 <0.1 ' 1.8 0.12, 9.5 5.0 13.4 18.4 Surface oils 0.09 0.31 <0.001 0.34 <0.002 1,6 3,0 2.3 5.3 100671 Example 3: Microencapsulation of a Functional Ingredient Containing Some Esterified Components in an About 75% Shellac / About 25% Zein Matrix at a Pilot Plant Scale [0068] About 12 kg of water and about 7.5 g of sucrose stearate (S4570, Mitsubishi-Kagaku Food Corp.; Tokyo, japan) was added to a mixing tank and mixed for about Ito about 2 minutes. Then about 2,25 kg of pre-made shellac solution (Temuss #594; Ajax, Ontario, Canada) in ammonium hydroxide solution (about 25% solids) was added, followed by about 187,5 g zein powder (F4000, Freeman Industries; Tuckahoe, NY). About 10%
sodium hydroxide solution was metered in until pH reached about 11.3 (to solubilize the zein).
Once the zeth and shellac are completely in solution, about 400 g of essential oil blend (about 13% canola oil, about 10% alpha-pinene, about 25% para-cymeneõ about 12% linaly1 acetate., and about 40% thymyl acetate) was added. The mix was agitated for about 5 minutes to create an emulsion.
[0069] The emulsion was titrated with about 3 percent citric acid solution until the pH
reached about 3.9. About 75 g of Si02 AB-D (PPG industries; Pittsburg, PA) was added and mixed for about 20 to about 30 minutes. The slurry was then filtered using a 200 mesh (75 micrometer) screen. The filter cake on top of the screen was suspended in about 9.1 kg of water with about 50 g Si02 AB-D and mixed for approximately 5 minutes, and then re-filtered on the #200 mesh screen. The rinsing was repeated one more time, and the final filter cake was spread on a tray for drying overnight at room temperature (about 20 to about 250C). The following day, the product was pulverized in a Waring blender (Waring Lab Science;
Torrington, CT), and dried in a UniGlatt fluid bed (Glatt Air Techniques;
Ramsey, NI) at 40 C, and sieved to a desired size (about 75 - about 250 micrometers), The payload and surface oil of the resultant product are illustrated in the table below.
Essential Oil Total Sample Description wt % wt %
plant scale w/ ester compounds Surface __________________________________ oils 3.8 7.2 [00701 Example 4: Microencapsulation of a Functional Ingredient Containing Esterified Components with Increased Oil Loading in a Shellac / Zein Matrix Containing Whey Protein as an Emulsifier [0071] About 2400 g of D.I. H20 was added to a beaker and mixed using SteilFast Stirrer 51,1200 (Yamato Scientific; Tokyo, Japan) with a 4-pronged impeller blade at speed setting between 5 and 6. About 32.5 g of Jet Milled zein powder (F4000, Freeman Industries; Tuckahoe, NY) was added to the beaker and mixed until uniformly dispersed. About 10%
NaOH solution was added until the pH reached about 11.3 and mixed until the zein powder was completely dissolved and the solution was translucent. About 20 g of BiPro WPI (Da visco Foods International; Eden Prairie, MN) powder was next added and mixed until the powder was completely dissolved. Next, about 390 g of the pre-made shellac solution with about 25 percent solids (Temuss #594; Ajax, Ontario, Canada) containing ammonium hydroxide was added and mixed for about 5 to about 10 minutes until .the solution was homogeneous.

PM] About 151.4g of the essential oil blend (about 13% canola oil, about 10%
alpha-pinene, about 25% para-cymene, about 12% linalyl acetate, and 40% about thymyl acetate) was added and mixed for about 5 to about 10 minutes. Using the PowerGen 7000 (Thermo Fisher Scientific; Waltham, MA), the mixture was homogenized for about 4 minutes at about 15,000 rpm and then at an increased speed of about 20,000 rpm for about 1 additional minute to create a stable emulsion. About 3% citric acid solution was titrated into the emulsion using Master Flex pump until the pH reached about 3.8, thereby creating a slurry.
[00731 About 10 g of Si02 AB-D (PPG Industries; Pittsburg, PA) was added to the slurry and mixed for about 20 to about 30 minutes. The mixture was filtered using a #200 mesh screen to produce a filtrate cake. In a separate, dean 4000 ml plastic beaker, about 2000 g of D.I. H20 was added and mixed using a StedFast Stirrer. The pH was adjusted to 3.8 41-about 0.2 by adding about 3% citric acid solution. About 1 g sucrose stearate, S-1570 (Mitsubishi-Kagaku Food Corp.; Tokyo, Japan) was added and mixed until completely dissolved, followed by an addition of about 2.5 g of Si02 AB-D. The cake was resuspended in this solution and mixed for about 3 to about 5 minutes. The mixture was filtered using #200 mesh (75 micrometer) screen to produce a second filtrate cake. In a separate, clean 4000 ml plastic beaker, about 2000 g of D.I.
H20 was mixed and pH adjusted to 3.8 +/- about 0.2 by adding about 3.0 percent citric acid solution. About 1 g sucrose stearate was added and mixed until completely dissolved, followed by an addition of about 2.5 g of Si 02 AB-D. The cake was resuspended in this solution and mixed for about 3 to about 5 minutes. The mixture was filtered again using #200 mesh (75 micrometer) screen to produce a third filtrate cake.
[0074] The resulting filtrate was pressed using cheese cloth to reduce moisture content. The filtrate was spread evenly on a large tray on top of a cookie sheet to dry overnight, uncovered and at room temperature (about 20 to about 25 C).
[0075] The resultant particles were ground using a Magic Bullet MB1001 (Sino Link International Trading Co.; Zhejiang, China). The particles sized less than about 250 micrometers were separated from the rest using a #60 mesh screen. To reduce the moisture content to less than about 6 percent, the filtrate was dried in a Uni-Glatt fluid bed dryer (Glatt Air Techniques; Ramsey, NJ) at about 40C, checking approximately every 5 minutes. As a result, the final product had a moisture content of less than about 6 percent.
The composition, payload, and surface oil of the resultant product are illustrated in the table below.
alpha- para- Linaly1 Thyrnyl Canal a Essential Oil Pinerie Cyniene Una loot Acetate Thymol Acetate Oil Total Total wt % wt % wt % wt wt % wt % wt % wt % wt Payload 1,12 21 <0.10 21 <0.10 113 5.7 17.9 23.5 Surface oils 0.014 0.094 <0.001 0.11 <0.002 0.55 2.8 0.76 3.6 100761 Example 5: Microencapsulation of a Functional Ingredient Containing Some Esterified Components in a Matrix Containing About 48% Alginate, About 40%
Shellac and About 12% Whey Protein as an Emulsifier [00771 About 2,1 g of sodium alginate (LILV-1,3G, Kimica Corp; Tokyo, Japan) and about 11.2 g of sodium alginate (I-3G-150, Kimica Corp; Tokyo, Japan) were added to about 551 g of water. Under agitation, about 70 g of an about 10% BiPro (Davisco Foods International; Eden Prairie, MN) whey protein isolate solution and about 56 g of the pre-made shellac (Temuss #594; Ajax, Ontario, Canada) in ammonium hydroxide solution, (about 25%
solids) was added.
Next, the essential oil blend (about 17,4% canola oil, about 6.6% alplia-pinene, about 26.5%
para-cymeneõ about 7,9% linalyl acetate, and about 41,4% thymyl acetate) was added and mixed until a homogenous emulsion was formed with target droplet size of about 4 to about 7 micrometers, verified with the Horiba particle size analyzer (Floriba Industries; Irvine, CA), The solution was then atomized, creating moderately small drops between about 25 to about 300 micrometers, into an aqueous solution bath containing about 2.5% CaC12 and about 2.5%
citric acid. The spheres were placed on a 25 micrometer screen to remove the bath solution, after which they were dried at about 40 C in the MiniGlatt fluidized bed dryer (Glatt Air Techniques;
Ramsey, NJ) until the target moisture (about 5 to about 6%) was reached. The particles were sized to less than about 500 micrometers and greater than about 75 micrometers. The composition, payload, and surface oil of the resultant product are illustrated in the table below, alpha- para- Linalyl Thymyl Can.ola Essential Pinene Cylnene Linalool Acetate Th :mot , Acetate Oil Oil Total wt % wt %. wt % wt % wt wt % wt % wt wt %
Payload 1.96 7,5 N/A 2,6 NIA-7 14.6 7.0 267 33,7 Surface oils 0,002 0,007 0.002 0,004 <0.002 0.063 0,58 0.076 0,654 [00781 Example 6: Non-Esterified Functional Ingredient Mic.roencapsulated in an Alginate/Shellac Matrix [0079] About 48 g of sodium alginate (ULV-L3G, Kimica Corp; Tokyo, Japan) and about g of sodium alginate (I-3G-150, Kimica Corp; Tokyo, Japan) were added to about 840 g of water. Then, under agitated conditions, about 80 g of the pre-made shellac solution w/ about 25% solids (Marcoat 125, Emerson Resources; Norristown., PA) was added. Next, about 48 g of the essential oil blend (about 24% soybean oil, about 4% alpha-pinene, about 30% para-cyinene, about 7% linalool, and about 35% .thymol) was added and mixed and homogenized until a fine, stable emulsion was formed. Using a two-fluid nozzle, the solution was atomized, creating moderately small spheres of about 25to about 300 micrometers, into an aqueous hardening bath containing about 2.5% CaC12 and about 2.5% citric acid. After the particles were cross-linked, the particles were sieved on a 25 micrometer sieve and dried at about 40 C in the MiniGlatt fluid bed dryer (Glatt Air Techniques; Ramsey, NJ) until the target moisture (about 5 to about 6%) was reached. Particles were sized at less than about 2/2 micrometers.
[00801 As seen in the table below, the payload was low and the particles failed to mask the undesirable taste/flavor of the essential oil when tasted in a model beverage system. The composition and payload of the resultant product are illustrated in the table below.
alphatn para- Soybean Essential Oil Total ....... Pinene Cymene Limbo' Thyinol Oil .... Pa 'load Pa 'load wt wt % wt % wt % wt % wt wt Payload .01 I 2.8 .031 1.7 4.8 45 9.3 [0081] Example 7: Microencapsulation of an Essential Oil Blend Containing Some Esterified Components in an About 75% Alginate / About 25% Shellac Matrix [0082] About 5,5 g of sodium alginate (1.11N-L3Gõ Kimica Corp; Tokyo, Japan) and about 11 g of sodium alginate (1-3G-150, Kimica Corp; Tokyo, Japan) were added to about 495 g of water. Then, under agitation, about 22 g of the pre-made shellac (Temuss #594;
Ajax, Ontario, Canada) in ammonium hydroxide solution (about 25% solids) was added. Next, the essential oil blend (about 18,5% canola oil, about 5.4% alpha-pinene, about 32.3% para-cymene, about .11.2% butyric acid ester of linalool (Malyl butyrate) and about 32.3% acetic acid ester of thyrnol (thymyl acetate)) was added and mixed and homogenized until a fine, stable emulsion was formed with target droplet size of about 4 to about 7 micrometers, verified with the Horiba particle size analyzer (Horiba Industries; Irvine, CA), The solution was atomized, creating moderately small spheres between about 25 to about 300 micrometers, into an aqueous hardening bath containing about 2.5% CaCl2 and about 2.5% citric acid. The particles were then sieved on a 25 micrometer screen to remove the bath solution and then dried at about 40C in the MiniGlatt fluidized bed dryer (Glatt Air Techniques; Ramsey, NJ) until the target moisture (about 5 to about 6%) was reached. The particles were sized to less than about 212 micrometers.
100831 As shown in the table below and compared to Example 6, payload was increased significantly upon using a functional ingredient containing esterified components. In parti-cular, as can be seen in FIG. 2, an unexpected benefit of using an esterified component is that the payload of the non-esterified components also increased in the presence of esterified component. Further, the esterified components produced a less negative flavor!
taste impact than the product formed in Example 6. The composition, payload, and surface oil of the resultant product are illustrated in the table below.
E
alpha- i para-Unaly1 Thymyl Canola Essential Pinene 00-Ilene Unatool Butyrate Thymol Acetate Oil Oil Total wt 'f' Wt % wt % wt % wt % wt %
---,-- wt %
wt % wt %
Payload 1.80 9.2 N/A 3.9 N/A 10.8 8.0 25.70 33.70 _ ¨
Surface i I oils 0.002 0.019 N/A 0.006 N/A . 0.066 ---------------- 0.61 0.093 ; 0.701 [00841 Example 8: Comparison of Payload Retention with Non-Esterified and Esterified Functional Ingredients within an About 75% Alginate / About25% Shellac Matrix [00851 Comparison of the particles produced with the original essential oil blend (containing non-esterified components: alpha-pinene, para-cymene, linalool, thymolõ and canola oil) and particles produced with an essential oil blend containing some esterified components (alpha-pinene, para-cymene, linalyl butyrate, thymyl acetate, and canola oil) is illustrated in FIG. 2, The particles were produced. using .the same process conditions and compositions aside from the esterified versus non-esterified functional ingredients. In this Figure, the level of linalool (combined) is calculated by summing the measured linalool and the linalool equivalent' from the measured linaly1 acetate based on the molecular composition.

[00861 As shown in FIG. 2, it is evident that the use of esterified components in the essential oil blend led to about a 130% increase in payload retention, the payload retention increase seen in both the esterified and non-esterified components of the functional ingredient.
100871 Example 9: Effect of an Esterified Functional Ingredient on Gastric Release [0088] This example compares the release of the non-esterified functional ingredient to the esterified functional ingredient during a simulated gastrointestinal study using an in vitro digestion model.
[00891 FIG. 3 shows the known properties of the compounds. As shown in the table of FIG. 3, the solubility values for the ester compounds (linalyl acetate, linalyl butyrate and thymyl acetate) are significantly lower than the parent compounds (linalool and thymol). In addition, the partition coefficients for the ester compounds are greater than the parent compounds.
These factors indicate that the ester compounds have a greater affinity for the hydrophobic carrier and insoluble matrix material than the parent compounds. FIGS. 4 and 5 show that the release between -0.5 and 0.0 hours, representative of the residence time in the simulated gastric fluid, is greatly reduced for the particles containing some esterified functional ingredient. The reduced rate is most evident when comparing linalool and thymol release from FIG. 4 to linalyl acetate and thymyl acetate release from FIG. 5. This improvement in stability within the model stomach implies increased stability in other low pH systems, such as acidic beverages, and further illustrates the importance of the esters for successful microencapsulation and enteric release of the functional ingredients.
[00901 Example 10: Modulation of the Release from Microencapsulated Particles and the Hydrolysis of the Esterified Components [00911 This example shows how the selection of various acids for esterification can affect the resulting rate of delivery of the parent compounds. Example 9 showed the effect on release rate from the particles within a gastric model, as a result of inclusion of some esterified compounds. As evident in FIGS. 4 and 5, the gastric release rate was reduced, as well as the release rate from 0-24.5 h, representative of the residence time in the small intestine. FIGS. 6 and 7 show the release rates of two esters of linalool, linalyl acetate in FIG. 6 and linalyl butyrate in FIG. 7 within a digestion model simulating stomach and small intestine conditions and residence times. In addition, the levels of the parent compounds present in the digestion model over time were measured. The presence of the parent compound, linalool is a result of hydrolysis of the linalyl acetate. As seen in FIG. 6, the initial release of linalool was about 5%
and increases to about 20%, which correlates to about 33% hydrolysis of linalyl acetate to linalool. In FIG. 7, the initial release of linalool was about 2% and increases to about 4%, which correlated to about 5% hydrolysis of the linalyl butyrate to linalool. From those results, it can be seen that by formulating the functional ingredient with varying ratios of linalyl acetate to linalyl butyrate, the resulting level of linalool release through the gastric tract and small intestine can be modulated.
[00921 Example 11: Comparison of Model Beverage Systems with Esterified and Non-Estezified Functional Ingredient [0093] The taste profiles of two model beverages were compared. One beverage was prepared with particles comprising non-esterified functional ingredient with the other beverage was prepared with particles including esterified functional ingredients, namely linalyl and thymyl acetates. Particles were created in the same manner as Example 2. Two equal, one-serving amounts of powdered beverage mix were portioned out. To the first portion, a sufficient mass of the particles comprising the non-esterified functional ingredient was added so that about 70 mg of the functional ingredient was dosed. To the second portion, a sufficient mass of the particles including esterified functional ingredients were added so that about 70 mg of the functional ingredient was dosed. Each powder/particle mixture was then added to about 200 ml of cold water and mixed thoroughly.
100941 Upon tasting samples of each model beverage, the panel concluded that the model beverage containing particles comprised of some esterified functional ingredient had a significantly reduced undesirable taste and/or flavor profile, leading to an improved overall sensory experience.
[0095] Example 12: Synthesis of a Dithymol Ester [00961 In one case, a dithymol ester was produced by dissolving about 65 grams of thymol and about 50 milliliters of pyridine in about 400 milliliters of hexane. With the dissolved combination being stirred at room temperature(about 20 to about 25 C), about 50 grams of sebacoyl chloride was added one drop at a time over a period of about 30 to about 45 minutes.
After the sebacoyl chloride was added, the mixture was allowed to react overnight at room temperature (about 20 to about 25 C). The next day, the mixture was filtered to remove solid pyridine chloride. The clarified filtrate containing dithymol sebacate and hexane was then subjected to further purification by contact with solutions of about IN sodium hydroxide, about 1N hydrochloric acid, and then water to remove any unwanted byproducts, unreacted starting materials, and residual pyridine. The purified dithymol sebacate in hexane was then dried over anhydrous sodium sulfate overnight to remove traces of water. The sodium sulfate was removed by filtration and the hexane removed by distillation to yield about 80 grams (approximately 82% yield) of at least about 95 percent pure dithymol sebacate.
The identity and purity of the final product was determined by gas-liquid chromatography and mass spectrometry.
[0097] Example 13: Preparation of Sodium Thymolate (Sodium Thymoxide) [0098] In one case, sodium thymolate was produced by making a first solution by dissolving about 8 grams of sodium hydroxide in about 25 milliliters of water followed by the addition of about 225 milliliters of absolute ethanol. A second solution was prepared by dissolving about 31 grams of thymol in about 100 milliliters of absolute ethanol. With the second solution being stirred at room temperature (about 20 to about 25 C), the first solution was added one drop at a time to the second solution. The combined solution was stirred overnight. The next day, the combined solution was filtered to remove traces of any undissolved reactants or byproducts. The absolute ethanol, water, and residual thymol were then removed by placing the filtered combined solution under a vacuum overnight at a temperature of about 40 C. The dried sodium thymolate was then removed from the flask to yield about 32 grams (approximately 93% yield) of product. The dried sodium thymolate could be further purified to remove traces of residual thymol by admixing the sodium thymolate with hexane (about 2 milliliters of hexane per 1 gram of sodium thymolate), filtering to remove the hexane, and drying the further purified sodium thymolate under vacuum.
[0099] While the compositions and methods have been particularly described with specific reference to particular process and product embodiments, it will be appreciated that various alterations, modifications, and adaptations may be based on the present disclosure, and are intended to be within the spirit of this disclosure.

Claims (18)

1. A composition comprising:
a functional ingredient, at least a portion of the functional ingredient in the form of a modified functional ingredient selected from the group consisting of a salt form of the functional ingredient, a complex form of the functional ingredient, a glycoside form of the functional. ingredient and mixtures thereof;
a non-active-carrier; and an enteric matrix microencapsulating the functional ingredient and non-active carrier and comprising a food grade enteric polymer, wherein the modified functional ingredient is configured to hydrolyze into a parent, non-modified form of the functional ingredient.

2. The composition of claim 1 wherein the functional ingredient comprises at least one of linalool and thymol.

3. The composition of claims I or 2 wherein at least about 20% of the functional ingredient is in the form of the modified functional ingredient.

4. The composition of any of the preceding claims wherein at least about 50% of the functional ingredient is in the form of the modified functional ingredient.

5. The composition of any of the preceding claims wherein the non-active carrier comprises a lipid.

6. The composition of claim 5 wherein the lipid is a triglyceride.

7. The composition of claim 6 wherein the triglyceride is selected from the group including soybean oil and canola oil.

8. The composition of any of the preceding claims wherein the ratio of functional ingredient to enteric matrix material ranges from about 1:19 to about 1:1.

9. The composition of any of the preceding claims wherein the enteric matrix is selected from the group consisting of zein, shellac, calcium alginate, and mixtures thereof.

10. A method comprising:
agitating a combination of water and an enteric matrix material at an appropriate pH to solubilize the enteric matrix material;
adding a functional ingredient to the combination, at least a portion of the functional ingredient in the form of a modified functional ingredient selected from the group consisting of a salt form of the functional ingredient, a complex form of the functional ingredient, a glycoside form of the functional ingredient and mixtures thereof;
mixing the combination and the functional ingredient to create an emulsion;
and agitating while titrating the emulsion with a cross-linking or precipitating agent in an amount effective to form a particulate precipitate, wherein the modified functional ingredient is configured to hydrolyze into a parent, non-modified form of the functional ingredient.

11. The method of claim, 10 wherein the functional ingredient comprises at least one of linalool and thymol.

12. The method of claim 10 or 11 wherein at least about 20% of the functional ingredient is in the form of the modified functional ingredient.

13. The method of any of claims 10 to 12 wherein at least about 50% of the functional ingredient is in the form of the modified functional ingredient.

14. The method of any of claims 10 to 13 wherein the combination further includes an emulsifier.

15. The method of any of claims 10 to 14 further comprising the steps of filtering, washing and drying the particulate precipitate to produce a dry powder.

16. The method of any of claims 10 to 15 further comprising adding a surface oil remover in an amount effective to reduce the residual surface oil on the particulate precipitate,

17. The method of any of claims 10 to 16 further comprising the step of agitating the functional ingredient and combination to create a coarse emulsion,

18. The method of claim 17 further comprising homogenizing the coarse emulsion to create a fine, stable emulsion,