WO2013067603A1

WO2013067603A1 - Encapsulation of food ingredients supplements and pharmaceuticals

Info

Publication number: WO2013067603A1
Application number: PCT/AU2012/001393
Authority: WO
Inventors: Craig Stewart PATCH; Ian Lewis Brown; Brenda Louise MOSSEL; Sarah Catherine CRENNAN; Glenn Stewart ELLIOTT
Original assignee: Clover Corporation Limited
Priority date: 2011-11-10
Filing date: 2012-11-12
Publication date: 2013-05-16
Also published as: AU2012280935A1; CN103987279A

Abstract

This invention relates to a composition comprising the reaction products of a mixture comprising: (a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg, albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterols selected from the group consisting of vegetable oil, fish oil and animal fats and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting of, monosaccharide, disaccharide, trisaccharide, oligosaccharide, maltodextrin, resistant maltodextrins, starch, starch derived materials, glucose syrup, glucose syrup solids and honey; wherein the said at least one protein and/or at least one lipid, are reactive to the said at least one carbohydrate, such that when the mixture is heated for a period to allow sufficient Glycation lo occur without coagulation and dried, the composition is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives.

Description

"Encapsulation of Food Ingredients Supplements and Pharmaceuticals"

Cross-Reference to Related Applications

The present application claims priority from Australian Provisional Patent Application No 201 1904676 filed on 10 November 201 1 , the content of which is incorporated herein by reference.

Technical Field

This invention relates to the encapsulation of oxygen sensitive oils alone or in combination with other bioactive materials for the use in food ingredients, functional foods, supplements, pharmaceuticals, medical foods, animal feeds and pet foods. In particular this invention relates to compositions for use as encapsulation aides, and methods for their use in encapsulation together with alternati ve processing aides.

Background of the Invention

A significant class of food ingredients are those containing oxygen sensitive oils, or. oxygen sensitive oil soluble bioactives. Oils and other fat soluble bioactives of commercial significance falling into this class are generally those containing monounsaturated and polyunsaturated fatty acids. Owing to their susceptibility to oxidation, these food ingredients need to be in a form that is both protective and enhances their ease of use. These food ingredients need to be prepared in a form suitable as ingredients for general foods, novel foods, functional foods and nutraceuticals. The form of the ingredients needs to be such that they are storage stable under the usual transport conditions. Usually the ingredients are processed into stable water-in-oil-in-water, water-in-oil, or oil-in-water emulsions, or encapsulated stable powders depending on their end use.

WO 01/741 75 discloses the microencapsulation of oxygen sensitive oils containing oil soluble oxygen sensitive substances, in proteins which have been reacted with carbohydrates that contain reducing sugar groups. The disclosed method involves heating an aqueous mixture of a protein and a carbohydrate at a temperature range wherein Glycation (also known as non-enzymatic glycosylation (NEG)) products are formed. Up to 50% by weight of an oil phase is then emulsified with the aqueous phase containing the Glycation products to form microencapsulated oil particles. The resulting emulsions can then be used as food ingredients or dried to form microencapsulated powders of oxygen sensitive oils. Glycation products can exhibit anti-oxidative activity in the presence of polyunsaturated fatty acids. It was found in WO 01 /74175 that the Maillard Reaction Products (MRP), which are formed by glycation of a protein and carbohydrate provided superior encapsulation for oxygen sensitive oils or oil soluble ingredients. The Maillard reaction is a form of nonenzymatic browning reaction. It results from a chemical reaction between an amino acid and a reducing sugar, usually requiring heat. The encapsulants had a stable robust film around the oil droplets and exhibited significantly improved resistance to oxygen deterioration.

WO 01/74175 does not disclose the isolation of the intermediate Glycation. Rather, it is disclosed that the formation of the Glycation and microencapsulation of oxygen sensitive oils occur sequentially in the same process. Therefore the entire process must occur at the same manufacturing plant, thus limiting the flexibility of the manufacturing procedure.

Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.

Summar^y of the Invention

It is an aim, at least in its preferred form, of the present invention to capture a glycation composition in the form of a dry powdered composition which is stable under the usual transport conditions, so it can be moved to another site, to be homogenised with an oxygen sensitive oil and other oil dispersible bioactives alone or together with alternative processing aides, in order to form stable microencapsulated oil particles. Accordingly, in a first aspect of the invention, there is provided a composition comprising the reaction products of a mixture comprising:

(a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg. albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterols selected from the group consisting of vegetable oil, fish oil and animal fats and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting of, monosaccharide, disaccharide, tri saccharide, oligosaccharide, maltodextrin, resistant maltodextrins, starch, starch derived materials, glucose syrup, glucose syrup solids and honey;

wherein the said at least one protein and/or at least one lipid, are reactive to the said at least one carbohydrate, such that when the mixture is heated for a period to allow sufficient Glycation to occur without coagulation and dried, the composition is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives.

Accordingly, in a second aspect of the invention, there is provided a composition comprising at least one additive and the reaction products of a mixture comprising:

(a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg, albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterols selected from the group consisting of vegetable oil. fish oil and animal fats, and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting of, monosaccharide, disaccharide, trisacchartde. oligosaccharide, maltodextrin, resistant maltodextrins, starch, starch derived materials, glucose syrup, glucose syrup solids and honey; wherein the said at least one protein and/or at least one lipid, are reactive to the said at least one carbohydrate, such that when the mixture is heated for a period to allow sufficient Glycation to occur without coagulation and dried either before or after mixing with at least one additive, the composition is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives.

In a third aspect of the invention, there is provided a method for forming a composition according to the first aspect, comprising the steps of:

(a) preparing an aqueous mixture of at least one protein or lipid comprising free amino groups and at least one carbohydrate which contains a reducing sugar group;

(b) heating the mixture for a period to allow sufficient Glycation to occur without coagulation: and

(c) drying the aqueous mixture to provide a composition which is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives. According to a fourth aspect of the invention, there is provided a method for forming an emulsion encapsulating an oxygen sensitive oil or an oxygen sensitive oil soluble bioactive comprising the steps of:

(a) rehydrating the composition according to the first or second aspects in an aqueous phase, which optionally contains at least one additive; and

(b) homogenising the said aqueous phase with an oil phase comprising an oxygen sensitive oil, or an oxygen sensitive oil soluble bioactive to obtain an emulsion. According to a fifth aspect of the invention, there is provided a method for forming a powder encapsulating an oxygen sensitive oil or an oxygen sensitive oil soluble bioactive comprising the steps of:

(b) homogenising the said aqueous phase with an oil phase comprising an oxygen sensitive oil, or an oxygen sensitive oil soluble bioactive to obtain an emulsion: and

(c) drying the emulsion to form an encapsulated powder.

In a sixth aspect of the invention, there is provided a use of a composition according to the first or second aspect for the preparation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives, wherein the encapsulants are used in food ingredients, functional foods, supplements, pharmaceuticals, medical foods and animal feeds. In results leading up to the present invention, the inventors found that the reconstituted Glycation dry powdered compositions were substantially equivalent to the standard Glycation emulsion prior to spray drying. For the first time the inventors surprisingly found, that the dry Glycation powdered composition could be rehydrated and retain its functionality.

In addition, the Glycation dry powdered compositions could be used in conjunction with other processing aides, such as maltodextrin, in order to form stable microencapsulated products, such as for ingredients used in infant formula products. Description of the preferred embodiments of the Invention Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

As used herein, the term "encapsulation" will be understood to include the terms "microencapsulation^" and "nanoencapsulation".

In a preferred embodiment of the invention, composition according to the aqueous mixture according to the first or second aspect is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying. Most preferably, the aqueous mixture is dried by spray drying.

In another preferred embodiment, the composition according to the first or second aspect comprises a carbohydrate which has a dextrose equivalent (DE) value of between 10 and 100%. Dextrose equivalent (DE) is a measure of the amount of reducing sugars present in a sugar product, relative to glucose, expressed as a percentage on a dry basis. The amount of non-enzymatic glycosylation in the protein and/or lipid-carbohydrate mixture according to the first or second aspect is critical as an amount sufficient to provide antioxidant activity for the period of a given product's shelf life is needed. The extent of the MRP formed can be monitored for a particular protein/'carbohvdrate combination by the degree of colour change that occurs during the reaction. Alternatively, the amount of unreacted reducing sugar can be monitored.

In a preferred embodiment of the invention, according to the first or second aspect, the ratio of protein to carbohydrate depends on the type of protein and carbohydrate used. This ratio of protein to carbohydrate may be from 1 : 1 0 to 10: 1 ,

Any protein useful in encapsulating oils can be used as the protein component of this invention, provided it has sufficient reactive free amino groups in order to undergo non-enzymatic glycosylation. The protein is preferably soluble and needs to be stable in the heating range of the Maillard reaction. Care also ^"needs to be taken in reacting the protein and the carbohydrate to ensure that the conditions do not result in gelling or coagulation of the protein, as this will render the protein incapable of forming a good film on rehydration and formation of an oil-in-water emulsion.

In a preferred embodiment of the invention, the protein according to the first or second aspect is casein, whey protein, whey protein concentrate or soy protein isolate. The most preferred protein in many applications is casein due to its low cost and its greater resistance to gelling and denaturation during the heat treatment step to form the Glycation. In a preferred embodiment according to the first or second aspect of the invention at least one lipid comprising a free amino acid group may be genetically modified. In another embodiment at least one lipid may be a natural oil. Γη yet another embodiment at least one lipid may be a concentrate. In a preferred embodiment of the invention according to the first or second aspect, at least one carbohydrate which contains a reducing sugar group is a monosaccharide selected from glucose or fructose. In another preferred embodiment the carbohydrate is a disaccharide selected from maltose or lactose. In a preferred embodiment according to the second, fourth or fifth aspects, at least one additive is selected from the group consisting of surfactants, wetting agents, emulsifiers, antifoaming agents and dispersanls.

Preferably, the additive is selected from the group consisting of dioctyl sodium sulfo succinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and polydimethylsiloxane.

The addition of a surfactant or antifoaming agent facilitates the ease of reconstitution through significant reduction in the amount of foam produced on incorporation of the reconstituted composition and results in further improvement in oxidative stability. Without being bound to any particular theory, this may be due to a more superior film formation in the oi l and water emulsion or may be related to a reduced concentration of dissolved oxygen in the aqueous phase, when foam formation is limited through the addition of a surfactant or antifoaming agent. In a preferred embodiment according to the third aspect, at least one additive is added after step (b) and before ste (c). In another preferred embodiment according to the third aspect, at least one additive is added after step (c) by dry blending or sprayed on using a lipid carrier.

^■5

In a preferred embodiment according to the fourth or fifth aspect, at least one additive is added. Preferably, the at least one additive is dispersed in the aqueous phase prior to rehydrating the composition. 0 In a preferred embodiment according to the first, second or third aspect of the invention, the protein content in the aqueous phase is from 5 to 30% by weight, together with between 1 to 60% by weight of the carbohydrate.

The pH of the aqueous phase, according to the first, second or third aspect, may be5 from 4 to 10, preferably from 6 to 8. Ultimately, the pH of the aqueous phase will depend on the isoelectric pH of the protein used, which in turn influences the solubility of the protein at various pH's. The heating period will depend on the temperature to which the aqueous mixture is heated. For sensitive proteins, heating at lower temperatures for longer periods may be appropriate. In a preferred embodiment of the0 invention, the aqueous mixture of MRP is heated to 60 - 160 °C.

The aqueous phase containing MRP can be dried by any conventional drying method in order to form a dry powder with moisture content of no greater than 8%. Preferably the aqueous phase is spray dried to form a dry powdered composition according to the first5 or second aspects.

In a preferred embodiment according to the fourth aspect, the emulsion is a stabilized liquid emulsion. In another preferred embodiment the emulsion is ultra high temperature (UHT) treated and aseptically packaged.

0

It will be appreciated that in the first and second aspects of the invention, any of a variety of food approved additives may be included in the composition. These additives include casein, whey proteins, starches, maltodextrins and oligosaccharides. Such additives may be included in amounts ranging from 1 -99% w/w. preferably 5- 5 95% w/w, more preferably 20-90% w/w. In another preferred embodiment, the composition according to the first or second aspect further comprises an oxygen sensitive oil and at least one other processing aide selected from, maltodextrin, gelatine, gum arabic, modified starches, water soluble antioxidants, emulsifiers.

As used herein, the term "an oxygen sensitive oil" means an oil, fat, or an oil soluble product that is oxygen sensitive and which is dissolved or dispersed in an oil phase.

The oils or oil soluble products useful in the present invention are those used in the food and pharmaceuticals, which are susceptible to deterioration by oxidation. These oils include polyunsaturated long chain fatty acids; one or more omega-3 fatty acids which may be derived from a marine source, a plant source an algal source or a fungal source. The marine source may be selected from the group consisting of: crustaceans such as krill, molluscs such as oysters, and fish such as tuna, salmon, trout, mackerel, sardines, pilchards, herring, kipper, eel, whitebait, menhaden and sea bass. The plant source (both genetically modified and non -genetically modified) may be selected from the group consisting of: flaxseed, walnuts, sunflower seeds, canola oil, safflower oil, soy, wheat germ, leafy green plants and corn oil. The one or more omega-3 fatty acids may be present in the composition as a component of fish oil. The fish oil may be encapsulated, for example microencapsulated. The fish oil may be selected from the group consisting of: salmon oil, trout oil, tuna oil, mackerel oil, sea bass oil, menhaden oil, herring oil and sardine oil. Dairy fats or other fats that are oxygen sensitive can also be encapsulated in accordance with this invention. This includes modified oils such as concentrates. Oil soluble bioactives that need protection from oxidation include, but are not limited to, vitamin A [retinol], vitamin D [calciferol], vitamin E. tocopherols, tocotrienols, vitamin K [quinone] and beta-carotene [pro-vitamin- A].

In a preferred embodiment of the invention the oil or oil soluble products may be genetically modified. In another embodiment the oil is a natural oil. In yet another embodiment the oil or oil soluble product is a concentrate.

The emulsions and powders prepared in accordance with the fourth and fifth aspects of the present invention are suitable as ingredients in fortifying infant formulae, infant foods, yoghurts, beverages. UHT drinks, pasta products, bread and bakery products, processed cheese, medical foods, pharmaceuticals, enteral feeds and the like. They may also be used as an alternative source of oils and fats in ice cream, dairy desserts. creamers, soup bases and filled dairy products. The powders may also be suitable for use in nutraceutical applications.

In one embodiment of the present invention, in the method according to the third, fourth of fifth aspects, the aqueous phase in step (a) is heated to at least room temperature (i.e. about 20°C)

In another embodiment according to the fourth or fifth aspects, a carrier is added after rehydrating the composition and before homogenising the aqueous phase with the oil phase. In a preferred embodiment the carrier is casein, whey proteins, starches, maltodextrins and/or oligosaccharides.

In one embodiment of the invention, the method according to the fourth or fifth aspects, the dry composition is present in an amount of between 5 - 95 weight percent. In a preferred embodiment of the method, the dry composition is present in an amount of from 10-80 weight percent. In another preferred embodiment the dry composition is present in an amount from 10-50%. In yet another preferred embodiment the dry composition is present in an amount from 40-50%. Preferably, the spray dried composition is present in an amount of 20 weight percent. Most preferably, the spray dried composition is present in an amount of 50 weight percent.

It will be appreciated that in the fourth or fifth aspects of the invention, any of a variety of food approved additives may be included in the composition. These additives include casein, whey proteins, starches, maltodextrins. water soluble antioxidants and oligosaccharides. Such additives may be included in amounts ranging from 1 -99% w/w, preferably 5-95% w/'w, more preferably 20-90% w/w.

In another embodiment of the present invention, in the method according to the fourth of fifth aspect, at least one other processing aide is selected from, maltodextrin, gelatine, gum arabic, modified starches, water soluble antioxidants, emulsifiers.

In another embodiment of the present invention, in the method according to the fourth or fifth aspect, the oil phase loading is from 10-80% w/w, preferably 10-70% w/w. In one embodiment, the oil phase loading is 25% w/w. In yet another embodiment, the oil phase loading is 50% w/w. In another embodiment of the present invention, the homogenisation step, according to the fourth and fifth aspects, is carried out preferably at 350/100 bar.

In yet another embodiment of the present invention, the dispersed particle size in the emulsion, according to the fourth and fifth aspects, is from 1 to 10 micron. In another embodiment, the dispersed particle size in the emulsion is from 1 -5 micron. Preferably, the dispersed particle size in the emulsion is less than 1 micron. Most preferably, the dispersed particle size in the emulsion is about 0.3 micron. In yet another embodiment of the methods disclosed herein, the spray drying step is earned out using a spray drier; the feed containing 30-42% total dissolved solids maintained at least 40 °C throughout spay drying, preferably 60-65 °C; and the inlet and outlet air temperatures 1 80 °C and 80 °C respectively. Example Embodiments

A. A composition comprising the reaction products of a mixture comprising:

(a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg, albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterols selected from the group consisting of vegetable oil, fish oil and animal fats and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting of, monosaccharide, disaccharide, trisaccharide, oligosaccharide, maltodextrin, resistant maltodextrins, starch, starch derived materials, glucose syrup, glucose syrup solids and honey;

B. The composition according to example embodiment A, wherein the composition is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying. C. The composition according to example embodiment B, wherein the composition is dried by spray drying. D. The composition according to any one of example embodiments A to C, wherein the at least one carbohydrate has a combined dextrose equivalent (DE) value of from 10 - 100%.

E. The composition according to any one of example embodiments A to D. wherein the ratio of protein to carbohydrate is 1 : 10 to 10: 1.

F. The composition according to any one of example embodiments A to E. wherein the at least one protein is casein, whey or soy protein isolate.

G. The composition according to any one of example embodiments A to F. wherein the at least one carbohydrate is a monosaccharide selected from glucose or fructose. H. The composition according to any one of example embodiments A to F, wherein the at least one carbohydrate is a disaccharide selected from maltose or lactose.

1. A composition comprising at least one additive and the reaction products of a mixture comprising:

(a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg, albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterols selected from the group consisting of vegetable oil, fish oil and animal fats, and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting of, monosaccharide, disaccharide, trisaccharide, oligosaccharide, maltodextrin, resistant maltodextrins, starch, starch derived materials, glucose syrup, glucose syrup solids and honey; wherein the said at least one protein and/or at least one lipid, are reactive to the said at least one carbohydrate, such that when the mixture is heated for a period to allow sufficient Glycation to occur without coagulation and dried either before or after mixing with at least one additive, the composition is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives. J. The composition according to example embodiment 1, wherein the at least one additive is selected from the group consisting of surfactants, wetting agents, emulsifiers, anti foaming agents and dispersants. K. The composition according to example embodiment J, wherein the at least one additive is selected from the group consisting of dioctyl sodium sulfosuccinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and polydimethylsiloxane. L. A method for forming a composition, according to any one of example embodiments A to K, comprising the steps of:

(b) heating the mixture for a period to allow sufficient Glycation to occur without coagulation; and

(c) drying the aqueous mixture to provide a composition which is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives. M. The method according to example embodiment L, wherein at least one additive is added after step (b) and before step (c).

N. The method according to example embodiment L, wherein at least one additive is added after step (c) by dry blending or sprayed on using a lipid carrier.

O. The method according to example embodiment M or N, wherein the at least one additive is selected from the group consisting of surfactants, wetting agents, emulsifiers, anti foaming agents and dispersants. P. The method according to example embodiment O, wherein the at least one additive is selected from the group consisting of dioctyl sodium sulfosuccinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and polydimethylsiloxane. Q. The method according to any of example embodiments L to P, wherein the aqueous mixture is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying. R. The method according to example embodiment Q, wherein the aqueous mixture is dried by spray drying.

S. The method according to any one of example embodiments L to R, wherein the protein component in the aqueous mixture is present in a range of I to 30% by weight, and the carbohydrate component is present in a range of 1 to 60%.

T. The method according to any one of example embodiments L to S, wherein the mixture in step (b) is heated in the range 60 - 160 °C. U. A method for forming an emulsion encapsulating an oxygen sensitive oil or an oxygen sensitive oil soluble bioactive comprising the steps of:

(a) rehydrating the composition according to any one of example embodiments A to K. in an aqueous phase, which optionally contains at least one additive; and

(b) homogenising the said aqueous phase with an oil phase comprising an oxygen sensitive oil, or an oxygen sensitive oil soluble bioactive to obtain an emulsion.

V. The method according to example embodiment U in which the at least one additive is dispersed in the aqueous phase prior to rehydrating the composition. W. A method for forming a powder encapsulating an oxygen sensitive oil or an oxygen sensitive oil soluble bioactive comprising the steps of:

(a) rehydrating the composition according to any one of example embodiments A to in an aqueous phase, which optionally contains at least one additive; and

(c) drying the emulsion to form an encapsulated powder.

X. The method according to example embodiment W in which the at least one additive is dispersed in the aqueous phase prior to rehydrating the composition. Y. The method according to any one of example embodiments T to X wherein at least one carrier is added after rehydrating the composition and before homogenising the aqueous phase with the oil phase. Z. The method according to example embodiment Y wherein the carrier is selected from the group consisting of casein, whey proteins, starches, maltodextrins and oligosaccharides.

AA. The method according to any one of example embodiments U to Z. wherein the at least one additive is selected from the group consisting of surfactants, wetting agents, emul.sifie.rs, antifioaming agents and dispersants.

AB. The method according to example embodiment AA, wherein the additive is selected from the group ednsisting of dioctyl sodium sulfosuccinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and polydimethylsiloxane.

AC. The method according to example embodiment W or X. wherein the emulsion is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying.

AD. The method according to example embodiment AC, wherein the emulsion is dried by spray drying.

AE. The method according to any one of example embodiments U to AD, wherein the oil phase is selected from long chain polyunsaturated fatty acids, marine sourced oils, dairy fats, algal oils, fungal oils; plant derived oils, and oil soluble ingredients including vitamin A [retinol], vitamin D [calciferol], vitamin E, tocopherols, tocotrienols, vitamin K [quinone] and beta-carotene [pro-vitamin- A]. AF. The method according to any one of example embodiments L to T wherein the composition is present in an amount of from 1 - 99 weight percent.

AG. The method according to any one of example embodiments L to T wherein the composition is present in an amount of from 20 - 80 weight percent. AH, The method according to any one of example embodiments U to AE wherein the oil phase loading is from 10 - 70%.

AI. The method according to any one of example embodiments U to AE wherein the oil phase loading is from 25 - 60%.

AJ. The method according to any one of example embodiments U to AE wherein the composition is present in a range 10-80% on a dry basis. AK. The method according to any one of example embodiments U to AE wherein the composition is present in a range from 1 0-50% on a dry basis.

AL. The method according to any one of example embodiments U to AE wherein the composition is present in a range from 40-50% on a dry basis.

AM. The method according to any one of example embodiments U to AL wherein the homogenisation step is carried out at 350/100 bar.

AN. The method according to any one of example embodiments U to AM wherein the dispersed particle size in the emulsion is from 1 to 10 micron.

AO. The method according to any one of example embodiments U to AM wherein the dispersed particle size in the emulsion is from 1 to 5 micron. AP. The method according to any one of example embodiments U to AM wherein the dispersed particle size in the emulsion is less than 1 micron.

AQ. The method according to any one of example embodiments U to AM wherein the dispersed particle size in the emulsion is about 0.3 micron.

AR. Use of a composition according to any one of example embodiments A to for the preparation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives. wherein the encapsulants are used in food, food ingredients, functional foods, supplements, pharmaceuticals, medical foods, infant foods including formula and animal feeds Modes for Carrying Out the Invention

In order to better understand the nature of the invention a number of examples will now be described as follows:

Glycation Product Spray Dried Composition - General Procedure

The protein was dispersed in water at 50-60 °C and allowed to hydrate in the water bath for at least 30 min. The carbohydrate(s) were then added and the pH was adjusted to the desired pH. The protein-carbohydrate mixture was then heated at 90- 1 00 °C for 30- 90 min before cooling to 50 °C. The glycation mixture was then dried using a Production Minor pilot spray dryer with a rotary atomiser. The feed was heated to 60 °C prior to atomisation and the inlet and outlet air temperatures were 180 °C and 80 °C respectively.

A: Control

Step 1 : Glycation product Aqueous Solution:

Add Water: Heat to 55°C

Add Sodium Caseinate heat to 60-65°C

Hydrate for 30 mins

Add Dextrose Monohydrate and Maltodextrin and agitate for 10 minutes Adjust pH with Sodium Hydroxide solution (6 °baume) to pH7-7.5 .

Conduct glycation by retorting mixture at 100°C for 50mins Glvcation product Final Emulsion:

7. Weight out Glvcation Solution and heat to 60-65°C

8. Add Sodium Ascorbate dissolved in retained water

9. Add hot Oil Phase (60-70°C) high sheer mixing for 5 mins

10. Homogenise at 350/100 bar using two stage homogeniser - 1 pass

1 1 . Spray Dry (production minor - rotary atomiser) at Inlet temperature 180°C:Out let 80°C (feed 39% solids to the dryer)

12. Collect and Pack off under modified atmosphere packaging (MAP).

B: Glvcation product DRIED, RECONSITUTED & DRIED

Step 1 : Glycation product aqueous Solution:

1 . Add Water; Heat to 55°C

2. Add Sodium Caseinate heat, to 60-65°C

3. Hydrate for 30 minutes

4. Add Dextrose Monohydrate and Maltodextrin and agitate for 10 minutes 5. Adjust pH with Sodium Hydroxide solution (6 °Baume) to pH7-7.5

6. Conduct glycation in Retort at 100°C for SOinins

7. Hold for step 2 & 3

Step 2: Glycation product aqueous for spray drying (DRY premix powd

1. Weight out initial glycation aqueous and heat to 60-65°C

2. Add Sodium Ascorbate to retained water, allow to dissolve and add to bulk liquid.

3. Spray Dry (production minor - rotary atomiser) at Inlet temperature

180°C:Outlet 80°C (feed 30-32% (w/w) solids to the dryer)

4. Collect and pack off DRY Glycation product powder

Step 3: Glycation premix preparation for final emulsion spray drying (reconstituted)

1 . Weigh out DRY glycation product

2. Add water and re-hydrate at 60-60°C

3. Add hot oil phase (60-70°C) with high sheer mixing for 5 minutes

4. Homogenise at 350/100 bar using two stage homogeniser - 1 pass 5. Spray dry (production minor - rotary atomiser) at nlet temperature

1 80°C:Outlet 80°C (feed 39% w/w solids to the dryer)

6. Collect and pack off under MAP The following trial products were produced according to the following operating procedures for the microencapsulation process.

Microencapsulation -- General Procedure

Water was heated to between 40 and 65 °C, the dry Glycation product was dispersed and allowed to hydrate in the water bath under mild agitation. Glucose syrup solids, emulsifier and/or dextrose were added at this point if required. Sodium ascorbate solution was added followed by the oil phase using a Silverson high shear mixer at high speed for five minutes, sufficient to form a coarse emulsion. The resulting reaction mixture was then homogenised at 350/100 bar pressure using a Rannie pilot high- pressure homogeniser.

The resulting emulsion was either used directly in a subsequent application, or ultra high temperature (UHT) treated and aseptically packaged, or spray dried using a pilot Production Minor pilot spray dryer with a rotary atomiser. The feed containing 39% total dissolved solids was maintained at 65 °C throughout spay drying and the inlet and outlet air temperatures were 180 °C and 80 °C respectively.

Properties of Spray Dried Slurry Composition

A. Glycation product control (48% Oil Loaded Powder - No isolation step involved)

B. Glycation product reconstituted (48% Oil Loaded Powder)

Table 1 Results for comparison of Control (A), Glycation product control powder and (B), Glycation reconstituted and dried powder:

Bulk density ( 100 taps) using the methodology specified in AS2300.4.3 ( 1994)

In summary. Table 1 reveals that the reconstituted and spray dried glycation sample was equivalent to the control sample. Organoleptic and oxidative stability results are comparable. Further 24 month 'equivalent' shelf life on the raw material was conducted with oxidative and sensory results compared, i.e. after the encapsulation procedure, no discernible difference between using the reconstituted Glycation product sample and the Glycation product control sample were shown.

The results of shelf life evaluation are shown in the accompanying figures 1 -7.

Sensory Results:

· Scale: Marine and Rancid odour and flavor (15 = no detection 0 = detected)

• Overall quality (15 = Acceptable 0=Unacceptable)

Oxidative results:

GOED voluntary monograph

• TOTOX Maximum 26 (results of calculation, (2 x PV) + AV)

Anisidine Value Maximum 20; AOCS official Method Cd 18-19

Peroxide Value Maximum 5meq/kg; AOCS Official Method Cd 8-53

• Acid Value Maximum 3 mg KOH/g; AOCS Official Method Cd 3d-93 Figure 1 shows sensory results for glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 40°C approximates 24 months real time storage. Figure 2 shows the TOTOX value for glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 40°C approximates 24 months real time storage.

Figure 3 shows the anisidine value for glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 40°C approximates 24 months real time storage.

Figure 4 shows the peroxide value for glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 40°C approximates 24 months real time storage.

Figure 5 shows the acid value for glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 40°C approximates 24 months real time storage.

Figure 6 shows the Omega-3 and DHA content for glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 40°C approximates 24 months real time storage. Figure 7 shows the total fat (%) of glycation control powder vs glycation reconstituted powder over 24 months equivalent storage. 24 weeks @ 4fJ°C approximates 24 months real time storage.

Stability trials

A number of variants (B - Glycation product reconstituted. V4, V6, V8, V9) were prepared and evaluated against A - Glycation product control). Details of the trial variant formulations are shown in Table 2 below. The aim of this study was to evaluate the stability and performance of prototype powders and their use in a target application with and without a surface active agent and progressive reductions in the absolute ratio of dry glycation powder to bulking agent (Table 2). Table 2 Trial Variant Formulations

Microencapsulation - General Procedure for he preparation of V4, V6, V8, V9 Water was heated to 55 °C, Maltodextrin was added at this point if required followed by sodium ascorbate solution. The oil phase (Monomuls® 90-35 added as required) was heated to 60-70 °C and added to the aqueous phase under constant agitation to from a coarse emulsion. The resulting reaction mixture was then homogenised at 350/100 bar pressure using a Rannie pilot high-pressure homogeniser. The emulsion was then spray dried using a pilot NIRO FSD two stage spray dryer. The feed containing 39% total dissolved solids was maintained at 65 °C throughout spay drying and the inlet and outlet air temperatures were 180 °C and 80 °C respectively. The resulting powder was collected and packed under 100% food grade nitrogen (Residual Oxygen <3%). Test Protocols

The variants and controls were evaluated using testing protocols as detailed in Table 3. Specifically;

· Oxidative stability of oils in a heterogeneous product monitored by induction period - "ML-Oxipres"

• Exposure of raw material and target application to elevated temperatures under modified atmosphere in barrier packaging. - "Accelerated shelf life determination

Table 3: Oxidative Stabilit testin matrix

ML-Oxipres

The variants in table 2 were evaluated for the oxidative stability of oils in a heterogeneous product monitored by induction period. Oils were analysed using an ML Oxipres (Mikrolab Aarhus A/S Denmark). A sample containing a minimum of 4 g of fat (Oil) is weighed into the reactor pressure vessels and placed into ML Oxipres pressure vessels and sealed. The vessels are filled with oxygen to a defined initial pressure of 5 bar (70psi). The vessels are placed into the thermostat block pre-heated and maintained at 70°C. Changes in pressure are recorded and the curve is plotted on a graph. The induction period is calculated as the time after which the pressure begins to decrease rapidly as measured from the cross sectional point of tangents from the first and second parts of the curve recoding pressure changes.

Accelerated Shelf Life Testing

• Microencapsulated powders packed under vacuum into l OOg foil sachets (5 layer laminate) and sealed under an artificial atmosphere of standard food grade 100% nitrogen.

• Sachets stored at -18°C (control) and 40°C for 24 weeks.

• 24 month accelerated shelf life simulated storage study

• 1 week at 40°C approximates 1 month at ambient (20-25°C) storage

• Sampling at baseline (0), 6 12, 18 and 24 week intervals.

Accelerated shelf life testing protocol in application

• Trial prototype dosed Stage 1 Infant Formula

• Microencapsulated powders blended into base to achieve desired active using K blade of kitchen mixer set on medium speed for 1 0 minutes

• Samples packed under vacuum into l OOg foil sachets (5 layer laminate) and sealed under an artificial atmosphere of standard food grade 100% nitrogen

• Sachets stored at -18°C (control) and 40°C for trial duration

• 24 weeks accelerated shelf life simulated storage study

• 24 month accelerated shelf life simulated storage study

Primary shelf life determined using a combination of stability and sensory data (Table 4 and Table 5).

Table 4. : Stability Testing

Test Parameter for Microcapsules Test Method

Fatty acid determination and quantification AOCS Ce 1 B-89

Total fat AS 2300. 1 .3

Acid value AOCS Ca 5a-40

Free fatty acids AOCS Cd 3d-63

Peroxide value AOCS Cd 8-53c

Anisidine value AOCS Cd 18-90c Table 5.: Sensor Testin

Results:

Prototype comparison A comparison of the principle physicochernical properties of the trial variants is detailed in Tabic 6. All variants met the target prototype profile with regard to moisture content and bulk density. All trial variants with the exception of the trial variant formulated to contain only 10% dry glycation powder (V8) were below specified maximum for surface free fat (Table 6). Surface free fat did not differ between the Sample A and Sample B indicating that encapsulation efficiency is not compromised in the drying reconstitution and re spray-drying of the encapsulation premix (Table 6). Interestingly, back filling with maltodextrin DE 30 resulted in a product with lower surface free fat as compared to the trial variant back filled with maltodextrin DE 10 at equivalent premix concentrations. Reducing the percentage of dry glycation powder in the capsule wall to 10% dry basis resulted in a product with poor microencapsulation efficiency with high (7.5%) free surface fat.

Table 6 : Physico-chemical properties

ML Oxipres;

Figure 8 shows the induction period of trial powders at 70^DC and 5 bar pressure. Two trial variants exceeded the target prototype profile with regard to induction period (IP). That is, had IP in excess of 60 hours at 70°C; trial variants B (glycation product reconstituted) and V4 (Figure 8). Trial variant V4 recorded an IP 13% greater than A (glycation product reconstituted), as the two variants had substantially equivalent formulations, the only difference being addition of 0.5% emulsifier to trial version 4, the reason for the increased oxidative stability as determined by IP is unclear.

However, it is possible that addition of the emulsifier to the oil phase may result in greater encapsulation efficiency; although physico-chemical results for these trial variants (Table 6), specifically surface free fat do not support this hypothesis. The remaining trial variants (Variants 6, 8 and 9) show substantially equivalent oxidative stability as measured by induction period with only slight differences recorded (Figure 8).

Summary of results

Results from the stability trials are shown in figures 9- 16. Figure 9 shows the total fat ( ) in trial powders when exposed to accelerated temperature conditions over 24 weeks

Figure 10 shows the concentration of actives (mg/g) in trial powders when exposed to accelerated temperature conditions over 24 weeks

Figure 11 shows the percentage Free fatty acid and acid value in trial powders when exposed to accelerated temperature conditions over 24 weeks. Figure 12 shows the primary (peroxide value (PV)) and secondary oxidation (p-Anisidine (PAV)) of trial powders when exposed to accelerated temperature conditions over 24 weeks.

Figure 13 shows the overall sensory quality of trial raw materials A, B and V4 when exposed to accelerated temperature conditions over 24 weeks

Figure 14 shows the overall sensory quality of trial raw materials V6, V8 and V 9 when exposed to accelerated temperature conditions over 24 weeks

Figure 15 shows the overall sensory quality of trial raw materials A, B and V4 when dosed into infant formula application and exposed to accelerated temperature conditions over 24 weeks.

Figure 16 shows the overall sensory quality of trial raw materials V6, V8 and V9 when dosed into infant formula application and exposed to accelerated temperature conditions over 24 weeks.

The superior film forming and antioxidant scavenging potential of the glycation product is not compromised by further processing of the glycation product through spray-drying and subsequent rehydration. In addition, further processing does not reduce its ability to form stable spray dried oil in water emulsions. Addition of an emulsifier as an additive may offer greater oxidative stability as evidence by a longer induction period. Reducing the percentage of dry glycation powder in the capsule wall to 22% dry basis resulted in powders with substantially equivalent sensory acceptance and oxidative stability to control powders. Reducing the percentage of dry glycation powder in the capsule wall to 10% dry basis however, resulted in a powder with unacceptably high surface free fat indicating that a threshold for reduction is to 10% dry basis in the formulation (Table 6). Accelerated shelf life stability indicates that all trial powders remains stable to oxidation over the 24 week test period (Figure 9- 12). In addition all trial powders remain organoleptically acceptable over the 24 week accelerated test period (Figures 1 3- 14). Furthermore, trial variants are considered to be fit for target infant formula application (Figure 15-16). It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.

Claims

CLAIMS:

1 . A composition comprising the reaction products of a mixture comprising:

(a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg, albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterol^'s selected from the group consisting of vegetable oil, fish oil and animal fats and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting o , monosaccharide, disaccharide, trisaccharide, oligosaccharide, maltodextrin, resistant maitodextrins, starch, starch derived materials, glucose syrup, glucose syrup solids and honey;

2. The composition according to claim 1 , wherein the composition is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying.

3. The composition according to claim 2, wherein the composition is dried by spray drying.

4. The composition according to any one of claims 1 to 3, wherein the at least one carbohydrate has a combined dextrose equivalent (DE) value of from 10 - 100%.

5. The composition according to any one of claims 1 to 4, wherein the ratio of protein to carbohydrate is 1 : 10 to 10: 1.

6. The composition according to any one of claims I to 5, wherein the at least one protein is casein, whey or soy protein isolate.

7. The composition according to any one of claims 1 to 6, wherein the at least one carbohydrate is a monosaccharide selected from glucose or fructose.

8. The composition according to any one of claims 1 to 6, wherein the at least one carbohydrate is a disaccharide selected from maltose or lactose.

9. A composition comprising at least one additive and the reaction products of a mixture comprising:

(a) an aqueous solution of at least one protein comprising free amino groups selected from the group consisting of casein, soy, whey, gelatine, egg, albumin, proteins from algal, yeast or fungal sources, and hydrolysed versions thereof, and/or at least one lipid comprising free amino groups, including fats, waxes and sterols selected from the group consisting of vegetable oil. fish oil and animal fats, and mixtures thereof; and (b) at least one carbohydrate which contains a reducing sugar group, selected from the group consisting of, monosaccharide, disaccharide. trisaccharide, oligosaccharide, maltodextrin, resistant maltodextrins. starch, starch derived materials, glucose syrup, glucose syrup solids and honey; wherein the said at least one protein and/or at least one lipid, are reactive to the said at least one carbohydrate, such that when the mixture is heated for a period to allow sufficient Glycation to occur without coagulation and dried either before or after mixing with at least one additive, the composition is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives.

10. The composition according to claim 9, wherein the at least one additive is selected from the group consisting of surfactants, wetting agents, emulsifiers, antifoaming agents and dispersants.

1 1 . The composition according to claim 10, wherein the at least one additive is selected from the group consisting of dioctyl sodium sulfosuccinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and polydimethylsiloxane.

12. A method for forming a composition, according to any one of claims 1 to 1 1 , comprising the steps of:

(b) heating the mixture for a period to allow sufficient Glycation to occur without coagulation; and (c) drying the aqueous mixture to provide a composition which is adapted for rehydration and formation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives.

13. The method according to claim 12, wherein at least one additive is added after step (b) and before step (c).

14. The method according to claim 12, wherein at least one additive is added after step (c) by dry blending or sprayed on using a lipid carrier.

15. The method according to claim 13 or 14, wherein the at least one additive is selected from the group consisting of surfactants, wetting agents, emulsifiers, antifoaming agents and dispersants.

16. The method according to claim 15. wherein the at least one additive is selected from the group consisting of dioctyl sodium sulfosuccinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and

po lydimethytsi loxane.

17. The method according to any of claims 12 to 1 6, wherein the aqueous mixture is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying.

18. The method according to claim 17, wherein the aqueous mixture is dried by spray drying.

19. The method according to any one of claims 12 to 18, wherein the protein component in the aqueous mixture is present in a range of I to 30% by weight, and the carbohydrate component is present in a range of 1 to 60%.

20. The method according to any one of claims 12 to 1 , wherein the mixture in step (b) is heated in the range 60 - 160 °C.

21. A method for forming an emulsion encapsulating an oxygen sensitive oil or an oxygen sensitive oil soluble bioactive comprising the- teps of:

(a) rehydrating the composition according to any one of claims 1 to 1 1 in an aqueous phase, which optionally contains at least one additive; and (b) homogenising the said aqueous phase with an oil phase comprising an oxygen sensitive oil, or an oxygen sensitive oil soluble bioactive to obtain an emulsion.

22. The method according to claim 21 in which the at least one additive is dispersed in the aqueous phase prior to rehydrating the composition.

23. A method for forming a powder encapsulating an oxygen sensitive oil or an oxygen sensitive oil soluble bioactive comprising the steps of:

(a) rehydrating the composition according to any one of claims 1 to 1 1 in an aqueous phase, which optionally contains at least one additive; and

(b) homogenising the said aqueous phase with an oil phase comprising an oxygen sensitive oil, or an oxygen sensitive oil soluble bioactive to obtain an emulsion; and

(c) drying the emulsion to form an encapsulated powder.

24. The method according to claim 23 in which the at least one additive is dispersed in the aqueous phase prior to rehydrating the composition.

25. The method according to any one of claims 21 to 24 wherein at least one carrier is added after rehydrating the composition and before homogenising the aqueous phase with the oil phase.

26. The method according to claim 25 wherein the carrier is selected from the group consisting of casein, whey proteins, starches, maltodextrins and oligosaccharides.

27. The method according to any one of claims 21 to 26, wherein the at least one additive is selected from the group consisting of surfactants, wetting agents, emulsifiers, antifoaming agents and dispersants.

28. The method according to claim 27, wherein the additive is selected from the group consisting of dioctyl sodium sulfosuccinate, mono and diglycerides of fatty acids, lecithin, modified starches, xanthan gum, octanoic acid and

polydimethylsiloxane.

29. The method according to claim 23 or 24, wherein the emulsion is dried by spray drying, drum drying, freeze drying, or membrane osmosis drying.

30. The method according to claim 29, wherein the emulsion is dried by spray drying.

31. The method according to any one of claims 21 to 30. wherein the oil phase is selected from long chain polyunsaturated fatty acids, marine sourced oils, dairy fats, algal oils, fungal oils: plant derived oils, and oil soluble ingredients including vitamin A [retinol], vitamin D [calciferol], vitamin E, tocopherols, tocotrienols, vitamin [quinone] and beta-carotene [pro-vitamin-A].

32. The method according to any one of claims 12 to 20 wherein the composition is present in an amount of from 1 - 99 weight percent.

33. The method according to any one of claims 12 to 20 wherein the composition is present in an amount of from 20 - 80 weight percent.

34. The method according to any one of claims 21 to 31 wherein the oil phase loading is from 10 - 70%.

35. The method according to any one of claims 21 to 31 wherein the oil phase loading is from 25 - 60%.

36. The method according to any one of claims 21 to 31 wherein the composition is present in a range 1 0-80% on a dry basis.

37. The method according to any one of claims 21 to 31 wherein the composition is present in a range from 10-50%) on a dry basis.

38. The method according to any one of claims 21 to 31 wherein the composition is present in a range from 40-50% on a dry basis.

39. The method according to any one of claims 21 to 38 wherein the homogenisation step is carried out at 350/ 100 bar.

40. The method according to any one of claims 21 to 39 wherein the dispersed particle size in the emulsion is from 1 to 1 0 micron.

41 . The method according to any one of claims 21 to 39 wherein the dispersed particle size in the emulsion is from 1 to 5 micron.

42. The method according to any one of claims 21 to 39 wherein the^* dispersed particle size in the emulsion is less than 1 micron.

43. The method according to any one of claims 21 to 39 wherein the dispersed particle size in the emulsion is about 0.3 micron.

44. Use of a composition according to any one of claims 1 to 1 1 for the preparation of an encapsulant of oxygen sensitive oils and oxygen sensitive oil soluble bioactives, wherein the encapsulants are used in food, food ingredients, functional foods, supplements, pharmaceuticals, medical foods, infant foods including formula and animal feeds.