WO2008037577A1

WO2008037577A1 - Process for production of compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer

Info

Publication number: WO2008037577A1
Application number: PCT/EP2007/059326
Authority: WO
Inventors: Michael Francis Butler; Emmanuel Heinrich; Phillippa Rayment
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2006-09-29
Filing date: 2007-09-06
Publication date: 2008-04-03

Abstract

The present invention relates to process for production of compounds, which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers, characterized in that the process comprises a posthardening process step, as well as for the use of these compounds in food products.

Description

PROCESS FOR PRODUCTION OF COMPOUNDS , WHICH ARE STARCH CONTAINING PARTICLES COATED , EMBEDDED OR ENCAPSULATED BY AT LEAST ONE BIOPOLYMER

The present invention relates to process for production of compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer, characterized in that the process comprises a posthardening process step, as well as for the use of these particles in food products.

Starches as carbohydrates are the preferred energy source for the body. Starches occur naturally in vegetables and grains. During digestion, starches are broken down into glucose, which provides essential energy for brain, central nervous system and for muscles during activity. Starches are one prime source of energy. The other source are sugars. Carbohydrates are far easier to break down in the digestive tract (producing less metabolic waste products) than either fat or protein and as a result the body's reserves of carbohydrate energy (stored in the blood, liver and muscles) are utilised first and are rapidly depleted during exercise. If these starches are not converted to energy, they are mostly converted and stored as fat, with a small amount stored as glycogen in the liver and muscles. When the body calls for more fuel (such as during exercise), the fat or glycogen is converted back to glucose and used accordingly.

It is desirable that the digestibility of starch be slowed to provide a controlled and/or steady release of glucose to the body over a period of several hours. Contrarily to the transit time of a meal in the stomach that can vary mainly in function of the type and quantity of food ingested, the transit time in the small intestine where most of carbohydrate digestion occurs is in average of 2 hours roughly before large intestine is reached. Therefore it is desirable that starch hydrolysis happens in a controlled and gradual way in the small intestine so that sustained energy can be delivered to the body. Additionally, the starch digestion should be complete or close to complete after 2 hours transit in the small intestine in order to minimise the quantity of undigested starch entering into the colon.

The slow release should work in any kind of food product in which these compounds according to the present invention are incorporated in. The food products can be food for humans (human food product) as well as for animals. The food product, which contains the compounds according to the present invention, can have any physical form, which is common for food products. The food product can be solid or liquid, soft or hard, gel-like, frozen, cooked, boiled, pasteurised, unpasteurised, etc. The compounds according to the present invention must be incorporated into the food products without being destroyed.

When the compounds according to the present invention, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer are incorporated into food products, especially in food for humans, then it is desirable that these compounds can not be detected in mouth during the consumption. The mouthfeel of the food product is a very important criteria.

For a slow release of starch larger compounds are preferred, because the digestion takes place slower. But for a good mouthfeel smaller particles are usually preferred. Therefore a compromise regarding the dimension of the compounds has to be found.

It has to be said that the mouthfeel also depends on the softness of the compounds as well as on the format of food product wherein the compounds are to be incorporated in.

The present invention relates to a method providing a solution against the disintegration of calcium-alginate beads in an aqueous environment, especially when chelating agents or various anions such as phosphate, citrate or bicarbonate ions are present (the latter being also present in the small intestine, through pancreatic secretion). Calcium ions form indeed insoluble salt complexes with various anions (eg. phosphate, citrate, bicarbonate...), thus often depleting the calcium ions content of calcium-alginate microbeads. As a result of this the alginate gel network becomes looser and the microbeads erosion can be very rapid. The method described herein does not rely on the use of an extra ingredient / material such as in coating alginate beads with cationic polyelectrolytes.

Surprisingly, it has been found out that when the process of production compounds which are starch containing particles coated, embedded or encapsulated by at least one biopolymer, comprises a posthardening process step the release of the starch is improved significantly. Therefore, the present invention relates to a process of production of compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer, characterized in that the process comprises a posthardening process step.

In the context of the present invention the term compound means the coated, embedded or encapsulated product.

In the context of the present invention the term starch containing particle means the particle, which is not (yet) coated, embedded or encapsulated.

Obtained by the reaction according to the invention are compounds which are starch containing particles coated, embedded, encapsulated by at least one biopolymer. Starches are not part of the coating, embedding or encapsulating layer. That means that the biopolymer are no starches or do not comprise starches.

The posthardening process is carried out in a Ca²⁺ solution. The solvent can be any solvent wherein Ca²⁺ salts are soluble. Very preferred is water or a solvent which consists mostly of water.

In addition to (or as a replacement of) Ca²⁺ other alkaline-earth metals can be used as well, especially Mg²⁺. But because the coated, embedded- or encapsulated particle is used in a food product, the concentration of other ions than Ca²⁺ is usually low.

Preferably the posthardening process step is carried out in water. The concentration of that solution can go from 0.1 weight -% (wt-%) to 10wt-%, based on the total weight of the reaction solution. Preferably from 0.2 to 5 wt-%.

The Ca²⁺ can be added in form of any soluble salt. The counterion of the Ca²⁺ salt does not affect the posthardening step, therefore the choice of a Ca²⁺ salt is not dependent on the counterion. Suitable Ca²⁺ salts are for example CaCI₂, CaSO₄. It is also possible to use salt which are usually hardly soluble or even insoluble in water, but when using a low pH value they become soluble. An example for such a salt is CaCO₃.

The reaction temperature of the posthardening step can vary. It is usually done at room temperature as well as slightly cooler or higher temperature. That means the temperature range can go from 5^°C to 40^°C, wherein temperatures around 20^°C to 30^°C are preferred. - A -

The posthardening process step is carried out at the end of the compound synthesis.

After the posthardening process step the compounds which are starch containing particles coated, embedded or encapsulated by at least one biopolymer are usually washed and/or purified.

The compounds which are starch containing particles coated, embedded or encapsulated by at least one biopolymer and which are obtained by a process as described above are put into the solution and left in the solution for a defined duration. Afterwards the compounds are collected from the solution washed and/or purified.

The posthardening process step could be repeated once or more times.

The duration of the posthardening step can vary a lot. It can go from a few minutes up to several hours. In some cases the posthardening process can be continued when the end product (=compound) is stored (or sold) in a Ca²⁺ solution.

The compounds which are starch containing particles coated, embedded or encapsulated by at least one biopolymer can be produced in accordance to commonly known methods, such as extrusion methods, or emulsion processes.

The compounds as well as the starch containing particle can have any physical form. Usually the starch containing particles are solid or liquid. The starch could also be crystallised.

The preferred form of the starch containing particle is the solid and crystallised form.

The starch containing particles can have any shape, such as spheres, tubes, fibres, as well as ill-defined forms.

The same applies for the compounds. The compounds according to the present invention are usually solid, gel or in a liquid form. Preferably they are solid or gel-like.

The compounds can have any shape, such as spheres, tubes, fibres, as well as Nl- defined forms. The term "starch containing particles" means particles which are made out of starch material, but which can comprise further non-starch material. These materials are not carbohydrates.

This means that the term "starch containing particles" covers particles, which are pure starch or mixtures of different starches as well as starch (or mixture of starches) mixed with other non-carbohydrate compounds. The particles do not comprise any sugar compounds.

Furthermore it has to be stated that the coated, embedded or encapsulated particles are either compounds wherein the starches are concentrated in the core of the particle (coated, encapsulated) or they are starch particles dispersed in a matrix of biopolymeric material (embedded).

Under term "coated and encapsulated starch containing particles" we defined compounds wherein the starch(es) (or starch mixed with other ingredients) is located in the middle (core) of the compound and it is coated or encapsulated by at least one biopolymer. The starch is not part of the coating or the encapsulating material and vice versa the biopolymer is not part of the core.

Under the term "embedded starch containing particles, we defined compounds wherein the starch(es) (or starch mixed with other ingredients) are dispersed, so that the starches are always concentrated at certain spots in the matrix. In the sense of the present invention the starches are not part of the matrix and vice versa the biopolymer is not part of the starch.

The compounds according to the present invention are starch containing particles coated, embedded or encapsulated by at least one biopolymer, wherein the starch containing particles can optionally comprise at least one non carbohydrate compounds and wherein the biopolymer is no starch or do not contain starch.

The compounds according to the present invention can contain starch, which is from natural or synthetic origin. Of course in case that the starch comes from a natural source there are always other compounds present. But it is also possible to mix the starch with other useful compounds, which are not harmful to the animal or human body. Such compounds could be for example proteins, peptides, vitamins, probiotics, etc. The starch can be raw starches, modified starches, and pregelatinized starches. Preferred are raw and modified starches are preferred. The size of the starch containing particles can be a few microns as well as a few millimetres. For the purpose of the present invention the size of the starch containing particles is less than 1000 microns. Usually their size between 5 and 1000 microns, preferably between 10 and 800 microns, more preferably between 20 and 500 microns.

The size of the compounds according to the present invention can be a few microns as well as a few millimetres. For the purpose of the present invention the size of the compounds according to the present invention is less than 1000 microns. Usually it is between 5 and 1000 microns, preferably between 10 and 800 microns, more preferably between 20 and 500 microns.

Of course a compound is always larger than the corresponding starch containing particle. When the starch containing particles are embedded by at least one biopolymer the compounds is usually much larger than the starch containing particles, which are embedded therein.

The compounds as well as the starch containing particles can have any form. They can be a bead, a sphere, a fibre, or any other form. When these compounds are used in food products it is obvious that mixture of several forms can be used.

The compounds do not coat, embed or capsulate the particles in a permanent way. That means the resulting compounds release the starch during time as already stated above.

This release happens inside the human or animal body after the intake of the compounds according to the present invention.

If compounds according to the present invention are eaten the starch is released by the help of enzymes.

The compounds according to the present invention can be described as sponge-like compounds. Therefore the compounds according to the present invention have pores, which are about between 50nm and 100nm. The pores sizes can be measured by Transmission Electron Microscopy (TEM). The following procedure has been used to determine the pore sizes. To enhance fixation, the beads were cut in half and then placed in 0.1 % ruthenium tetroxide for 90 minutes. The beads were then rinsed using distilled water for 20 minutes and this was repeated. The beads were then stained in 1 % aq. uranyl acetate overnight. The beads were dehydrated in ethanol and infiltrated with epoxy resin, which was polymerised at 6O⁰C for 48 hours. Sections of approximately 100nm thickness were prepared and stained in lead citrate. The sections were then examined in Jeol 1200 TEM at 100KV.

The biopolymer can be any biopolymer which is able to coat, embed or encapsulate starch containing particles. Additionally, because the compounds according to the present invention are incorporated into food products, the biopolymer should be not harmful to humans and animals. The biopolymer is no starch or does not comprise starch.

Preferred biopolymers are physically (such as ionically) and/or covalently crosslinkable polysaccharides.

More preferred biopolymers are physically and/or covalently crosslinkable polysaccharides which are β-linked polysaccharides.

Such crosslinkable polysaccharide includes food hydrocolloids such as agarose, chitin, carrageenan, pectins, amidated pectines, xanthan, alginates, gum arabic, galactomannans like locust bean gum, guar and tara gum, and cellulosics like carboxymethylcellulose, methylcellulose, hydroxypropylcellulose and methylhydroxypropylcellulose as well as gellans, ispaghula, β-glucans, konjacglucomannan, gum tragacanth, detarium and tamarind.

Another preferred biopolymer is chitosan, which is a linear polysaccharide composed of randomly distributed β-(1-4)-linked D-glucosamine (deacetylated unit) and N-acetyl-D- glucosamine (acetylated unit). Chitosan is produced commercially by deacetylation of chitin (can be produced from chitin also), which is the structural element in the exoskeleton of crustaceans (crabs, shrimp, etc.). The degree of deacetylation (%DA) can be determined by NMR spectroscopy, and the %DA in commercial chitosans is in the range 60-100 % The most preferred physically and/or covalently crosslinkable and β-linked polysaccharide are alginates. Chemically, alginate is a linear copolymer with homopolymeric blocks of (1- 4)-linked β-D-mannuronate (M) and its C-5 epimer α-L-guluronate (G) residues, respectively, covalently linked together in different sequences or blocks. The ratio of the different blocks can differ widely. The relative amount of each block type varies both with the origin of the alginate. Preferred are alginates with a M:G ratio of 80:20 to 20:80. Alginates are commercially available.

In the present invention the biopolymer is usually present in the form of a gel, wherein the gel comprises 0.5 - 20 weight-% (wt-%) of at least one biopolymer and 80 - 99.5 wt-% of water. The weight percentages are based on the total weight of the biopolymer gel.

Preferably, the gel comprises 0.5 - 15 wt-%, more preferred 0.5 - 10 wt-%, especially preferred 1 - 10 wt-%, very especially preferred 1 - 5 wt-% of at least one biopolymer. The weight percentages are based on the total weight of the biopolymer gel.

As a consequence thereof, the water content is preferably 85 - 99.5 wt-%, more preferred 90 - 99.5 wt-%, especially preferred 90 - 99 wt-%, very especially preferred 95 - 99 wt-% of water. The weight percentages are based on the total weight of the biopolymer gel.

The content of starch in the compounds according to the present invention is 0.1 - 20 wt- %, based on the total weight of the compounds. Preferably the content of starch is 0.5 - 15 wt-%, more preferably, 0.5 - 10 wt-% equally preferred 1 - 15 wt-%, especially preferred 1 - 10 wt-%, based on the total weight of the compounds.

Therefore the present application relates to a process for production of compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer, wherein the compounds comprise 80 - 99.9 wt-% based on the total weight of the compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer, of at least one biopolymer gel which comprises

0.5 - 20wt-%, based on the total weight of the biopolymer gel, of at least one biopolymer and 80 - 99.5 wt-%, based on the total weight of the biopolymer gel, of water and

0.1 - 20 wt-% based on the total weight of the compounds, which are starch containing particles coated, embedded or encapsulated by at least one biopolymer, of at least one starch, is used characterized in that the process comprises a posthardening process step, as well as for the use of these compounds in food products.

The process for producing the compounds which are starch comprising particles coated, embedded or encapsulated by at least one biopolymer can be carried out by any commonly known process

The process for producing the compounds which are starch comprising particles coated, embedded or encapsulated by at least one biopolymer can be carried out by an extrusion process or by an emulsion process.

The compounds according to the present invention are incorporated into food products. Food products for animals as well as humans can be provided. Preferably food for humans is provided. The compounds obtained by the inventive process are very stable so they can be used in any food product which needs to have starch in it. The term food products covers any kind of drinks or other liquid food product, snacks, candies and confections, dessert mixes, granola bars, energy bars, various beverages, shelf stable powders, ready to eat foods such as puddings, frozen yogurts, ice creams, frozen novelties; cereals, snacks, meal replacements, baked goods, pasta products, confections, military rations, specially formulated foods for children, and specialized gastric enteral feeding formulations.

The food product can be treated with any usually used food technology process like cooking, baking, freezing, pasterizing, etc. without destroying the compounds obtained by the inventive process.

Because the active component is encapsulated by the method of the subject invention, the resulting coated compounds are relatively inert and bland in both aroma and taste. This allows the compounds of the subject invention to be incorporated in the disclosed foods without affecting the characteristic properties and flavours of the food.

In WO 2005/020717 (examples 1 , 2 and 3), WO 2005/020718 (examples 1 and 2) and WO 2005/020719 (examples 1 , 2 and 3) suitable food forms can be found, wherein the particles obtained by the process according to the present invention can be put in. Description of the figures:

Fig. 1 : Starch hydrolysis kinetic curves for rice starch granules entrapped in hardened

Ca-alginate beads versus non-hardened beads (both prepared with Tween 20 and

Span 80; and having an average size of 700 micron) and non-encapsulated rice starch (in-vitro test data); initial water phase in the emulsion method contained 2% alginate and 5% starch; pretreatment in temperature before hydrolysis assay: 15 min at 90⁰C.

Fig. 2.: Glucose release for "solid" alginate beads with encapsulated (white squares) and unencapsulated (white triangles) starch and "liquid-centre" alginate beads with encapsulated (black squares) and unencapsulated (black triangles) starch. The control system without starch for "solid" (white circles) and "liquid-centre" (black circles) is also displayed.

The following examples serve to illustrate the invention without limiting the invention to them.

If not otherwise stated the percentages are weight percentages and the temperatures are given in Celsius.

Example 1 :

A 1-2% alginate solution (Sigma-Aldrich no. A-7128: alginic acid sodium salt, high mannuronic acid content) containing 1 to 10% rice starch granules (Remy DR, ex. Remy, Orafti Group, Belgium) and 0.2% Tween 20 (Polysorbate 20, no. 233360010, ex. Acros Organics) was first emulsified at ambient temperature in sun flower oil. The water phase volume fraction was 30% and the oil phase contained Span 80 (Sorbitan monooleate, no. 85548, ex. Fluka Chemica), at a concentration of 0.2 weight % with respect to the water phase (or monoglycerides, Hymono 8903 (ex. Quest International, The Netherlands), predispersed at 60⁰C and at the same concentration of use). The water phase emulsification in oil was performed during 25 min with a rotating palette in combination with four wall baffles at a constant speed of rotation between 300 and 1000 rpm. While the emulsion was still under shear, a 1 M solution of calcium chloride was then added quickly along the side of the beaker to reach a final calcium ions concentration of 0.1 M (1.11wt-%) in the aqueous phase. The break-up of the water-in-oil emulsion was obtained as the alginate fine droplets start to gel. After full phase separation the oil was removed by repetitive washing of the gel beads on a filter with a 0.1 M CaC^ (1.11 wt-%) solution or pure water. Some of the microbeads were kept as such and some were finally hardened via a post-incubation in a 0.2M CaC^ (2.22wt-%) solution during 24 hours before use.

The hydrolysis rate of encapsulated starch was evaluated by means of an in-vitro test using alpha-amylase enzyme. First a suspension of gel beads containing 1 % starch (or a 1 % starch granules suspension as a control) was prepared in Pipes buffer (piperazine- 1 ,4-bis(2-ethanesulfonic acid), ex. Acros Organics) at pH 6.9. The starch-containing samples were then preheated at 75°C or 95°C during 15 min before cooling down to 37°C. 5 ml of the starch sample was added to 5 ml of a freshly made alpha-amylase solution prepared by adding 0.1026 g of porcine pancrease alpha-amylase (Sigma- Aldrich no. A-6255; 700-1400 units/mg protein) to 40 ml of a 0.9% NaCI solution. The starch/amylase mixture was then incubated straightaway at 37°C under gentle stirring. 500 μl_ samples were collected at different times in order to follow the kinetic of hydrolysis and build full hydrolysis profiles. 500 μl_ of DNSA solution (Aldrich no. 128848: 3,5- dinitrosalicylic acid) was added to each 500μl_ collected sample and the resulting mixture was heated up to 99°C during 10 min so that the DNSA reagent could react with the reducing end groups. After a ten or twenty-fold dilution step, the absorbance at 540 nm of the reacted samples was measured and compared to calibration curve of maltose conversion.

The hardened beads display an excellent stability in presence of anions complexing with calcium ions. Table 1 shows indeed that hardened beads incubated in sodium bicarbonate are fully stable and do not release any starch granules at all over 24 hours incubation. This is a drastic improvement since the non-hardened beads were found to be not stable in sodium bicarbonate, salt which led to the more pronounced effect of gel bead disintegration. The post-hardening step is believed to generate changes in the alginate gel network at the molecular level so that the intermolecular chain junctions become stronger, trapping better calcium ions as well.

The starch hydrolysis in-vitro data of the Fig. 1 show that applying a post-hardening step at the end of the microbead making process allows in addition to delay much further the starch hydrolysis by amylase. The post-hardening of the beads leads to a much more gradual digestion of the encapsulated starch.

Tablei : Encapsulate stability performance in presence of bicarbonate ions and under gentle stirring; performance of hardened alginate microbeads versus calcium-alginate beads.

Example 2

A 1.5% (w/w) sodium alginate (Manugel DMB, ex ISP Alginates, G content = 72%) solution was prepared by gradually sprinkling the biopolymer powder into deionised water whilst stirring at 22⁰C. The solution was stirred for approximately 2 hours to ensure complete hydration. For beads containing rice starch, 1 % (w/w) rice starch (ex. Remy Industries, Belgium) was added to the deionised water before the alginate powder and the same method was used as described for the alginate only beads. For preparation of "solid" (hardenened) beads, 100ml of 1.5% alginate solution was then dripped into 400ml 0.025M calcium chloride dihydrate (0.37%) solution using a 250ml funnel and 200μl Gilson tip cut to 39mm for increased drip rate. The Gilson tip was held in place using laboratory film (Parafilm, Pechiney Plastic Packaging). Once all the alginate solution dripped into the calcium chloride solution, the beads were sieved after 5 minutes and rinsed in fresh calcium chloride solution. The beads were placed into a storage container with fresh calcium chloride solution and posthardened at 5⁰C for 22 hours before characterisation.

For preparation of "liquid-centre" (soft) beads, 100ml of 1.5% alginate solution was dripped into 400ml 0.025M calcium chloride dihydrate (0.37%) solution for 2 minutes. The alginate beads were stood in the calcium chloride solution for a further 3 minutes with gentle stirring before being sieved and rinsed with 0.05mM (w/w) sodium chloride (NaCI) solution. Finally the beads were placed into a storage container with fresh sodium chloride solution (control solution) and stored at 5⁰C for 22 hours before characterisation.

A digestion assay was developed in order to determine the effect of bead preparation and composition on the digestibility of encapsulated native rice starch. Glucose was determined in the gastro-intestinal solutions containing alginate beads using a microdialysis sensor (SFP, Sycopel International Limited, U. K). The sensor was filled with glucose oxidase in phosphate-buffered saline (PBS) (0.5U glucose oxidase (G2133, Sigma-Aldrich, U. K) per ml). Before each experiment, the sensor was calibrated with glucose standards in PBS solution.

Approximately 10g of each of the alginate bead types were placed into beakers. A third beaker was set up containing approximately 10g of alginate only beads to which rice starch (1 % of bead weight) was added to 200ml gastric and intestinal solutions. Concentrated hydrochloric acid (BDH 28507BF) was added to gastric solutions at 15 minutes to simulate the stomach acidity being reduced to pH 2. After 120 minutes, the beads were then filtered and mixed with 200ml intestinal solution at 37⁰C. 2ml of diluted amylase (Sigma-Aldrich A6255; 1370U/mg protein; diluted ¹Λoo,ooo) and 1 ml maltase (Sigma Aldrich S9144-1VL; Reconstituted with 20ml de-ionised water) was added. The beads were stirred every 15 minutes and the glucose concentration determined using the glucose sensor. Fig. 2 shows the glucose release over time for each system.

Claims

1. A process for production of compounds, which are starch containing particles coated, embedded or encapsulated by a biopolymer or a mixture of biopolymers, characterized in that the process comprises a posthardening process step.

2. A process according to claim 1 , wherein the posthardening process step is carried out in a Ca²⁺ solution.

3. A process according to claim 2, wherein the concentration of the Ca²⁺ solution is 0.1wt-% to 10wt-%, based on the total weight of the reaction solution.

4. A process according to claim 2, wherein the concentration of the Ca²⁺ solution is 0.2 wt-% to 5 wt-%, based on the total weight of the reaction solution.

5. A process according to any of the preceding claims, wherein the compound can have any shape.

6. A process according to any of the preceeding claims, wherein the starch can be chosen from the group consisting of raw starches, modified starches, and pregelatinized starches.

7. A process according to any of the preceeding claims, wherein the biopolymer is present in the form of a gel.

8. A process according to claim 7, wherein the gel comprises

0.5 - 20 wt-%, based on the total weight of the biopolymer gel of at least one biopolymer and

80 - 99.5 wt-%, based on the total weight of the biopolymer gel, of water.

9. A process according to any of the preceeding claims, wherein the content of starch is 0.1 - 20 wt-%, based on the total weight of the compound.

10. A process according to any of the preceeding claims, wherein the size of the compounds is less than 1000 microns.

11. A process according to any of the preceeding claims, wherein the biopolymers are physically and/or covalently crosslinkable polysaccharides.

12. A process according to any of the preceeding claims, wherein the process is an extrusion process or an emulsion process.

13. Food products comprising compounds obtained by the process according to any of claims 1 - 12.

14. Food products according to claim 13, which are chosen from the group consisting of any kind of drinks or other liquid food product, snacks, candies and confections, dessert mixes, granola bars, energy bars, various beverages, shelf stable powders, ready to eat foods such as puddings, frozen yogurts, ice creams, frozen novelties; cereals, snacks, meal replacements, baked goods, pasta products, confections, military rations, specially formulated foods for children, and specialized gastric enteral feeding formulations.