Fatty acid composition and method for fortifying nutritional products with fatty acids

Abstract

A fatty acid composition is provided which can be used to make fatty acid fortified nutritional products. In one embodiment, the fatty acid composition comprises a fatty acid component, inorganic salts (which can include a phosphate salt), vitamins, and optionally a protein source and optionally a carbohydrate source. The composition can further include additional nutrients and combinations thereof. In another embodiment, the fatty acid composition is only the fatty acid (i.e., consists of a sodium or potassium fatty acid) which is spray dried. In both embodiments, the fatty acid composition is not microencapsulated in a waxy or carbohydrate substrate, yet the powdered composition is flowable and is easily dispersible in a liquid to form a stable dispersion in the liquid by stirring or shaking the powder in the liquid for only a short period of time.

Claims

1. A fatty acid composition for making fatty acid fortified nutritional products; the fatty acid composition being in powder form; the fatty acid composition comprising: a fatty acid component including a desired fatty acid chosen from the group consisting of arachidonic acid (ARA), eicosapentaenoic acid (EPA), docosapentaenoic acid (DPA), eicosatetraenoic acid, heneicosapentaenoic acid, docosahexaenoic acid (DHA), and combinations thereof, optionally at least one vitamin, a salt that is not a fatty acid salt, an optional protein source, and an optional carbohydrate source; wherein the fatty acid component consists of a monovalent simple fatty acid salt, wherein the desired fatty acid comprises at least 24 wt % of the fatty acid composition, wherein the fatty acid composition is not microencapsulated; and wherein the fatty acid composition is substantially instantizable in liquid upon stirring, shaking, or otherwise agitating in any effective manner the fatty acid composition powder in the liquid for less than one minute.

2. The fatty acid composition of claim 1 wherein if the fatty acid composition is 100% fatty acid salt, the fatty acid salt is a dried fatty acid salt.

3. The fatty acid composition of claim 1, wherein the fatty acid component is an ARA salt or a DHA salt.

4. The fatty acid composition of claim 1, wherein the fatty acid component is a sodium or potassium salt of the fatty acid.

5. The fatty acid composition of claim 1 wherein the fatty acid component is a long-chain polyunsaturated fatty acid (LCPUFA) of 18 carbons or longer.

6. The fatty acid composition of claim 5 wherein the LCPUFA contains at least four double bonds.

7. The fatty acid composition of claim 1 wherein the fatty acid component disassociates in a human stomach to be readily available for absorption within the human digestive tract.

8. The fatty acid composition of claim 1, wherein the fatty acid component comprises one or more monovalent cations chosen from the group consisting of sodium, potassium, ammonium and free base forms of choline, lecithin, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, ornithine, proline, selenocysteine, serine, tyrosine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, and valine, and combinations thereof.

9. The fatty acid composition of claim 1, wherein the fatty acid composition is substantially free of triglycerides.

10. The fatty acid composition of claim 1, wherein the fatty acid composition comprises up to about 3% by weight vitamin, the at least one vitamin being chosen from the group consisting of vitamin C (ascorbic acid), vitamin E, vitamin A, vitamin D, vitamin K, vitamin B12, choline, folic acid, thiamine, riboflavin, carotenoids, niacin, pantothenic acid, biotin, mixed isomers of tocopherol, salts and their derivatives and combinations thereof.

11. The fatty acid composition of claim 10 wherein the at least one vitamin comprises vitamin C, vitamin E, their salts and derivatives, and combinations thereof.

12. The fatty acid composition of claim 10 wherein the vitamin source is an ascorbate salt.

13. The fatty acid composition of claim 1, wherein the salts are chosen from salts of citric acid, citric acid derivatives, phosphates, and combinations thereof.

14. The fatty acid composition of claim 13 wherein the phosphates are chosen from dibasic sodium phosphate, tetrasodium diphosphate, tricalcium phosphate, dibasic potassium phosphate, tetrapotassium diphosphate, ammonium phosphate salt, and combinations thereof.

15. The fatty acid composition of claim 1, wherein the composition includes up to about 30% by weight of a protein source, the protein source being chosen from the group consisting of skim milk powder, whole milk powder, nonfat milk powder, caseinates, whey, soy protein isolate, pea protein isolate, their derivatives, and combinations thereof.

16. The fatty acid composition of claim 13, wherein the caseinate is chosen from the group consisting of casein and salts thereof and combinations thereof.

17. The fatty acid composition of claim 16 wherein the caseinate salt is selected from the group consisting of sodium caseinate, calcium caseinate, potassium caseinate, and combinations thereof.

18. The fatty acid composition of claim 1 wherein composition includes up to about 5% by weight of a carbohydrate source, the carbohydrate source being selected from the group consisting of maltodextrin, sugar, modified sugar, starch, modified starch, glucose, derivatives thereof, and combinations thereof.

19. The fatty acid composition of claim 1, wherein the fatty acid composition comprises by weight about 10% to about 98% fatty acid component; about 1% to about 4% vitamins, about 1% to about 50% salts, 0% to about 40% protein, and about 0% to about 70% carbohydrates.

20. The fatty acid composition of claim 19, wherein the fatty acid composition comprises about 20% to about 50% by weight of a desired fatty acid.

21. The fatty acid composition of claim 19, wherein the salt is a phosphate, and the ratio of desired fatty acid to a phosphate is about 0.3:1 to about 99:1.

22. The fatty acid composition of claim 21, wherein the ratio of desired fatty acid to phosphate source is about 0.9:1 to about 10.4:1.

23. The fatty acid composition of claim 19, wherein the composition is about 30% by weight desired fatty acid component.

24. The fatty acid composition of claim 19, wherein the composition is about 10% by weight salts.

25. The fatty acid composition of claim 19, wherein the composition is about 5% carbohydrates.

26. The fatty acid composition of claim 19, wherein the composition is about 20% by weight protein.

27. The fatty acid composition of claim 19, wherein the composition is about 3% to about 4% by weight vitamins.

28. The fatty acid composition of claim 1, wherein the fatty acid composition comprises milk powder or milk substitute powder; said milk powder or milk substitute powder being the protein source, wherein said fatty acid composition is added to water to form a fatty acid fortified milk-based or milk substitute-based beverage.

29. The fatty acid composition of claim 28, wherein the fatty acid composition is about 25% by weight milk powder or milk substitute powder.

30. A fatty acid composition for making fatty acid fortified nutritional products; the fatty acid composition being in powder form; the fatty acid composition comprising by weight: about 10% to about 89% simple fatty acid component, about 1% to about 4% vitamins, about 2.4% to about 50% salts which are not fatty acid salts, 0% to about 70% carbohydrate, and 0% to about 40% protein; the fatty acid component consisting of a monovalent simple fatty acid salt; wherein the fatty acid composition is not microencapsulated and wherein the fatty acid composition is substantially instantizable in liquid upon stirring, shaking, or otherwise agitating in any effective manner the fatty acid composition powder in the liquid for less than one minute.

31. A fatty acid fortified milk product comprising milk or a milk substitute and the fatty acid composition of claim 30.

32. The fatty acid fortified milk product of claim 31, wherein the fortified milk product contains triglycerides, and the triglycerides are dispersed in the milk product.

33. The fatty acid component fortified milk product of claim 31, wherein the milk substitute is infant formula.

34. The fatty acid fortified milk product of claim 31, wherein the fortified milk product is about 10% to about 20% by weight milk powder or milk substitute powder.

35. The fatty acid fortified milk product of claim 33, wherein both the infant formula and the fatty acid composition are in powder form.

36. The fatty acid fortified milk product of claim 33 wherein the fortified milk product has a fat content of between about 2% and about 5%.

37. The fatty acid fortified milk product of claim 36, wherein the fatty acid composition comprises between about 20% and about 50% by weight desired fatty acid component.

38. The fatty acid fortified milk product of claim 33 wherein the fatty acid component is an ARA or DHA salt; said ARA or DHA salt being present in the fatty acid fortified milk product in an amount approximately equal to the amount of ARA or DHA in human breast milk.

39. A method of preparing a fatty acid fortified infant formula, the method comprising: adding the fatty acid composition of claim 30 to an infant formula in an amount sufficient to provide a desired fatty acid in an amount such that the fatty acid content of the fatty acid fortified infant formula corresponds to the amount of the desired fatty acid present in human breast milk; and stirring, shaking, or otherwise agitating the infant formula with the powdered fatty acid composition in any effective manner for less than one minute to accomplish mixing the infant formula with the fatty acid composition, whereby a stable dispersion of the fatty acid composition in the infant formula is formed.

40. A method of fortifying a milk or milk substitute with a desired fatty acid component comprising combining the fatty acid composition of claim 28 with a milk or milk substitute and dispersing the fatty acid composition in a liquid by stirring, shaking, or agitating in any effective manner to accomplish mixing.

41. The method of claim 40, wherein the milk or milk substitute is a liquid milk or milk substitute such that the liquid is the milk or milk substitute.

42. The method of claim 40, wherein the milk or milk substitute is a milk powder or milk substitute powder and wherein said liquid is water; said method comprising adding the milk powder or milk substitute powder and the fatty acid powder to the water.

43. The method of claim 40, wherein the milk powder or milk substitute powder and the fatty acid composition are added to the liquid at the same time.

44. A fatty acid fortified infant formula composition comprising infant formula having milk solids and the fatty acid composition of claim 30; the fatty acid fortified infant formula comprising a sufficient amount of the fatty acid component being such that the fatty acid fortified infant formula has a fat content of between about 2% and about 5%; the fatty acid composition being between about 20% and about 50% by weight of the desired fatty acid component; and wherein the fortified infant formula has a fatty acid component to milk solids ratio corresponding to the fatty acid to milk solids ratio of human breast milk.

45. A method of producing a nutritional supplement coprising the fatty acid composition of claim 30; the method comprising: preparing an aqueous mixture containing the fatty acid composition; and spray drying the mixture to form a powder of the fatty acid composition; whereby, the fatty acid composition powder is readily dispersed in liquid to form a stable suspension in the liquid.

46. The method of claim 45 wherein the fatty acid composition further includes a vitamin source, a salt, and optionally additional nutrients, and combinations thereof; the method including either: (1) dry mixing selected ingredients with the fatty acid component after the fatty acid component has been spray dried; or (2) including selected ingredients in the aqueous mixture and spray drying the fatty acid component and ingredients together.

47. The method of claim 45 including preparing the fatty acid component by saponification of a triglyceride or of a fatty acid ester with an alkaline metal hydroxide.

48. The method of claim 47 wherein the alkaline metal hydroxide is chosen from the group consisting of sodium hydroxide and potassium hydroxide, and combinations thereof.

49. The fatty acid composition of claim 1 wherein the fatty acid composition may comprise by weight about 63% to about 90% fatty acid component; about 0.5% to about 3% vitamins; about 0.5% to about 32% inorganic salts wherein about 0% to about 32% of the inorganic salts comprise phosphate salts; 0% to about 25% of a protein, and 0% to about 30% carbohydrates.

50. A fatty acid composition for making fatty acid fortified nutritional products; the fatty acid composition being in powder form; the fatty acid composition comprising: a) about 56% to about 89% by weight of a fatty acid component, the fatty acid component being in the form of a fatty acid salt, the fatty acid component being derived from a fatty acid source comprised of multiple fatty acids and including a desired fatty acid; wherein the desired fatty acid comprises about 26% to about 40% by weight of the fatty acid component; the desired fatty acid being chosen from the group consisting of arachidonic acid (ARA), eicosapentaenoic acid (EPA), docosapentaenoic acid (DPA), eicosatetraenoic acid, heneicosapentaenoic acid, docosahexaenoic acid (DHA), and combinations thereof; b) about 2.4 to about 31% of a salt that is not a fatty acid salt; c) about 1% to about 4% by weight vitamin; d) 0% to about 38% by weight protein, and e) 0% to about 5% carbohydrate; wherein the fatty acid composition is not microencapsulated; and wherein the fatty acid composition is substantially instantizable in liquid upon stirring, shaking, or otherwise agitating in any effective manner the fatty acid composition powder in the liquid for less than one minute.

51. The fatty acid composition of claim 50 wherein the salt is a phosphate salt, the fatty acid composition comprising a desired fatty acid to phosphate ratio of about 0.9:1 to about 10.4:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The following detailed description illustrates the claimed invention by way of example and not by way of limitation. This description will clearly enable one skilled in the art to make and use the claimed invention, and describes several embodiments, adaptations, variations, alternatives and uses of the claimed invention, including what we presently believe is the best mode of carrying out the claimed invention. Additionally, it is to be understood that the claimed invention is not limited in its application to the details of construction and the arrangements of components set forth in the following description. The claimed invention is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.

(2) We have developed a fatty acid composition which readily disperses in liquids, such as water, formula, milk, milk products and milk-like products (such as milk substitutes)) to form a stable dispersion without the need for traditional microencapsulation of the fatty acids. The composition is a mixture of free-flowing salts of fatty acids (e.g., omega-3 or omega-6 fatty acids) that rapidly disperses in an aqueous medium and is able to be reconstituted in milk or a milk-based food composition. The dried powder forms a stable dispersion in the liquids.

(3) The terms nutritional product or nutritional composition or nutritional formulation are used interchangeably and refer to liquid and solid, including semi-liquid and semi-solid. Examples of semi-liquids are gels, oil-in-water emulsions, and shakes. Examples of semi-solids are creams, gelatins, and doughs. The solids may be powders that may be reconstituted to form a nutritional liquid which is suitable for human consumption.

(4) The term nutritional powder as used herein, unless otherwise stated, refers to nutritional products in free-flowing or scoopable form that can be reconstituted with water, milk, milk-like liquids, or other liquids prior to consumption. This includes both spray-dried, dry mixed, and dry blended powders.

(5) The term nutritional liquid as used herein, unless otherwise stated, refers to nutritional products in ready-to-feed liquid form, concentrated form, and nutritional liquids made by reconstituting the powder disclosed herein prior to use.

(6) The term fatty acid component as used herein, unless otherwise stated, refers to free fatty acids or fatty acid salts.

(7) Product Form

(8) The fatty acid-containing nutritional product and associated methods disclosed herein may be formulated and administered in any known or suitable oral form.

(9) The fatty acid composition can be formulated as a powder, and can be provided to consumers as a powder which can then be added to a liquid. Alternatively, the powder can be provided to manufacturers who then add the powder to formula, milk, milk products and milk-like products (including milk substitutes) to provide a fatty acid fortified liquid product. The fatty acid composition can, alternatively, be combined, for example, with milk powder, to produce a fatty acid fortified milk powder. This fatty acid fortified milk powder would then be mixed with water to form a fatty acid fortified milk beverage. The nutritional product (i.e., the powdered fatty acid composition or a commercial food or beverage which includes the fatty acid composition) is commercially stable after being packaged and then stored at 20-25 C. for at least 3 months, including 6 to 24 months, and including 12 to 18 months. Accelerated stability (i.e., shelf life) studies show that the fatty acid composition will be stable for 36 months and even as long as 48 months.

(10) In one embodiment, the fatty acid composition comprises a desired fatty acid component combined with vitamins, inorganic salts, protein and carbohydrates. In another embodiment, the fatty acid composition includes the fatty acid component combined with vitamins and inorganic salts. This embodiment does not include protein or carbohydrates. Hence, the protein and carbohydrates can be considered optional components to the fatty acid composition, and either or both of these components can be omitted from the fatty acid composition. In a further embodiment, the fatty acid composition comprises only a spray dried fatty acid salt (i.e., excludes vitamin, inorganic salt, protein and carbohydrate).

(11) Preferred fatty acids are ARA, DHA and any omega-3 or omega-6 fatty acid either individually or in combinations. The omega-3 rich fatty acid can be chosen from the group consisting of predominantly alpha-linolenic acid (C18:3, n-3), eicosatetraenoic acid (C20:4, n-3), moroctic acid (C18:4, n-3), eicosapentaenoic acid (EPA) (C20:5, n-3), heneicosapentaenoic acid (C21:5, n-3), docosapentaenoic acid (C22:5, n-3), and docosahexaenoic acid (DHA) (C22:6, n-3), and combinations thereof. The omega-6 fatty acid can be chosen from the group consisting of linoleic acid 18:2 (n-6), eicosatrienoic acid 20:3 (n-6), arachidonic acid 20:4 (n-6), and combinations thereof. In one embodiment, the fatty acid component selected is a long-chain polyunsaturated fatty acid (LCPUFA's) of 18-carbon chains or longer containing at least two, and preferably at least four, double bonds.

(12) The fatty acid(s) come from a source (e.g., fungal oil, algal oil, or fish oil) which comprises a complex mixture of fatty acids rich in ARA, EPA, DHA, omega-3 fatty acids, and/or omega-6 fatty acids. The fatty acid source is not exclusively composed of one acid; that is, the fatty acid source is not, for example, pure DHA, but is rather a complex mix of different fatty acids. Another source of fatty acid can be a fungal oil, such as is produced by a species of Mortierella, and in particular such as is produced by M. alpina. M. alpina advantageously produce ARA in a concentration amount practical for incorporation into infant formula with an ARA concentration similar to that in human breast milk. Thus, a fatty acid component wherein the fatty acid source is M. alpina can be used to produce ARA-salt fortified infant formula. Additional suitable sources of fatty acids include corn oil, coconut oil, high oleic sunflower oil, soybean oil, medium chain triglycerides (MCT) oil, safflower oil, high oleic safflower oil, palm oil, palm kernel oil, olive oil, oleic acids, canola oil, and mixtures and combinations thereof

Composition Examples

(13) In accordance with one aspect of the invention, the dried fatty acid composition comprises a mixture of free fatty acid salts (derived as described above) that may be formulated in combination with inorganic salts, vitamins, and optionally a protein and carbohydrates. The inorganic salt can be a sodium or a potassium citrate or a sodium or a potassium phosphate.

(14) Vitamins:

(15) The vitamins in the fatty acid composition can include suitable sources, for example, of vitamin C, vitamin A, vitamin E, vitamin D, vitamin K, vitamin B12, choline, folic acid, thiamine, riboflavin, carotenoids, niacin, pantothenic acid, biotin, mixed isomers of tocopherol, salts and derivatives of the noted vitamins, and combinations thereof. Other vitamins can be included as well if desired. To provide a shelf-stable fatty acid composition, low levels of both vitamin C and vitamin E derivatives may be required. The reasonable expectation is that a maximum of about 3% ascorbate salt will be needed, and that tocopherols will be required in levels of less than 1%.

(16) Protein:

(17) The fatty acid composition or fatty acid fortified nutritional product may optionally comprise protein. Examples of suitable protein sources include skim milk powder, whole milk powder, nonfat milk powder, casein, caseinates (such as sodium, potassium or calcium caseinate), soy, pea, and whey protein. Proteins such as casein and whey have emulsifying properties and are also able to inhibit lipid oxidation by scavenging free radical intermediates and chelating pro-oxidant metals thus increasing oxidative stability. Both proteins are generally regarded as safe (GRAS).

(18) Carbohydrates:

(19) The fatty acid composition may optionally comprise a carbohydrate source. Any carbohydrate source that is suitable for use in nutritional products and is compatible with the elements of such products is suitable for use in combination with the fatty acid component. Non-limiting examples of suitable carbohydrate sources, if used, include maltodextrin, sugar, modified sugar, modified starch or cornstarch, glucose, corn syrup or solids, rice-derived carbohydrates, bran-derived carbohydrates, various vegetable-derived carbohydrates, sugar alcohols, artificial sweeteners, and combinations thereof.

(20) Inorganic Salts:

(21) The inorganic salts of the composition can include citric acid and its salts and derivatives and phosphate sources such as dibasic sodium phosphate, tetrasodium diphosphate, tricalcium phosphate, dibasic potassium phosphate, tetrapotassium diphosphate, ammonium phosphate salt, and combinations thereof. Other inorganic salts could be used as well.

(22) Other Optional Ingredients

(23) The fatty acid composition may optionally comprise other ingredients in addition to the fatty acid component. Such optional ingredients may modify the physical, chemical, aesthetic, or processing properties of the composition. Such ingredients are known or suitable for use in nutritional products and may be used in the fatty acid composition described herein. Such ingredients are safe for oral consumption and are compatible with the ingredients of the nutritional product. Non-limiting examples of such optional ingredients, if used, include preservatives, anti-oxidants, emulsifying agents, flow agents, buffers, flavoring, thickening agents, additional nutrients and combinations thereof. The preservatives can, for example, include butylated hydroxytoluene (BHT). The anti-oxidants can, for example, include ascorbyl palmitate. The emulsifying agents can, for example, include soy lecithin. The flow agents can, for example, include tricalcium phosphate or silicates. The buffers can, for example, include calcium carbonate.

(24) A preferred composition of the fatty acid powder comprises a sodium (Na) salt of the fatty acid, an inorganic salt, vitamins, a protein source, and a carbohydrate source. As an alternative, a potassium (K) salt of the fatty acid can used instead of (or in combination with) a sodium (Na) fatty acid component. The inorganic salt can be a phosphate. If a mixture of sodium and potassium salts of the fatty acid is used, then the phosphate may be a combination of sodium, calcium and potassium phosphates. The free fatty acid component could include other monovalent cations, such as sodium, potassium, ammonium and the free base forms of choline, lecithin, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, ornithine, proline, selenocysteine, serine, tyrosine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, valine, and combinations thereof. However, regardless of the monovalent cation of the fatty acid component, the phosphate salts will be potassium, sodium, calcium, and/or ammonium phosphates or combinations thereof.

(25) The concentration of the fatty acid component present in the final powder product varies based on the concentration of a particular fatty acid in the starting triglyceride oil. Commercially available triglyceride oils vary from about 30% EPA+DHA content to higher than 90% pure EPA or DHA, which can also be in triglyceride form.

(26) Table I below shows the percentage by weight of the various compounds in the powder composition.

(27) TABLE-US-00002 TABLE I % by weight of dried Compound Function/Purpose powder Fatty acid component Source of fatty acid for about 10% to about supplementation 100% by weight, preferably about 50% to about 90%, and preferably about 65% to about 75% by weight or preferably about 90% to about 100% by weight Phosphate source inorganic salt, Buffer, flow 0% to about 50% by modifier, improves color weight, preferably about 2% to about 30%, and prefer- ably about 10% Sodium citrate inorganic salt, Sequestering about 0% to about agent, buffer 3%, and preferably about 1% Sodium ascorbate Vitamin, Anti-oxidant about 0% to about 4%, preferably about 2% to about 4%, and prefer- ably about 1% Maltodextrin, sugar or Source of carbohydrates, 0% to about 70%, starch derivatives, rice improves color, texture and preferably, about or bran derivative flow properties 0% to about 5%, and preferably about 5% Skim milk powder, Source protein, also acts 0% to about whole milk powder, as emulsifier, wetting, 40%, and preferably sodium or calcium dispersing, and instantizing about 20% caseinate/whey agent protein
Methods of Manufacture

(28) The fatty acid component or composition may be prepared by any known or otherwise effective manufacturing technique. The fatty acid component or composition can be prepared by one skilled in the art based on the disclosed information herein. The fatty acid component can also be purchased (or otherwise prepared elsewhere).

(29) The method of preparing the fatty acid component initially comprises saponification of a triglyceride or of an ester to form the free fatty acid. The free fatty acid can then be converted to a fatty acid salt.

(30) Saponification Followed by Conversion

(31) Saponification of a triglyceride or of an ester to the free fatty acid is carried out in a manner well known in the field. The manner of performing the saponification thus need not be described.

(32) Conversion of the Free Fatty Acid into the Corresponding Fatty Acid Salt

(33) In one method, the fatty acid component may be prepared by converting the free fatty acid to the corresponding salt with an alkaline metal hydroxide under an inert atmosphere. The resulting emulsion is then spray dried to yield the fatty acid component as a powder. Examples of suitable alkaline metal hydroxides include sodium hydroxide or potassium hydroxide.

(34) In another method, the free fatty acid can be converted to a fatty acid salt using an alkaline metal hydroxide. The fatty acid salt may be mixed with the ingredients described herein to form the fatty acid composition. The fatty acid composition can be dried or placed into an aqueous suspension for spray drying.

(35) The disclosed methods can be performed under an inert atmosphere, e.g., under nitrogen or argon.

(36) The source of fatty acids and alkaline metal hydroxide can be mixed by any method known in the art, and can be accomplished mechanically or manually, and using any desired mixing equipment or technology.

(37) Mixing can be performed at various temperatures. The temperature is dependent upon the particular source of fatty acid, the identity of the alkaline metal hydroxide, and other factors, e.g. the amounts of the raw materials being used. Non-limiting examples of suitable temperatures include from about 10 C. to about 100 C., from about 15 C. to about 100 C., and from about 20 C. to about 80 C. Pre-heating of the reaction mixture may be performed at any of the temperature ranges disclosed herein. Heating and/or pre-heating can occur over a period of time from about 10 minutes to about 90 minutes.

(38) The powdered fatty acid composition can be formed via a spray drying process or by a dry mixing process. Such processes and the equipment for carrying out such processes are well known, and need not be described herein.

(39) In accordance with one aspect of the spray-drying method, an aqueous slurry or liquid comprising the fatty acid component, and protein, carbohydrates, inorganic salts (which can optionally include a phosphate salt), and vitamins is prepared. This slurry/liquid is then spray dried to produce a spray dried powder. As noted above, the powder can be formed without the protein or carbohydrates. It has been observed that in compositions including caseinates, that the caseinate salt preferentially reside at the surface of the fatty acid salts, such that the caseinate surrounds the fatty acid salt component. This migration of the caseinate relative to the fatty acid salt has been termed in-situ microencapsulation or substance segregation. Having the caseinate salt at the surface of the composition particles is believed to help with the flowability and stability of the fatty acid composition powder. It is expected that other compounds such as soy protein isolate, pea protein isolate, and hydrolyzed protein may also enhance flowability and stability. Although this results in an in-situ microencapsulation of the fatty acid component, this in-situ microencapsulation is to be distinguished from the intentional or traditional microencapsulation of the triglycerides, as discussed in the Background Section. Because of this, our powder is deemed to not be microencapsulated.

(40) When traditionally microencapsulated PUFAs (as discussed above in the Background) are compared to our fatty acid composition, several desirable advantages favor our fatty acid composition. The fatty acid composition is instantizable (i.e., it quickly and easily disperses in liquid) and generates a stable dispersion with little or no load issue. The fatty acid component has a similar fatty acid profile to the microencapsulated PUFAs. Because of these attributes, the fatty acid composition may provide superior performance for oxidative degradation, odor, taste and stability in many formulations.

Composition Examples

(41) Tables IIA-IIE below summarize the weight percentages of the components for 17 different fatty acid compositions.

(42) TABLE-US-00003 TABLE IIA Ingredients, % Weight Example 1 Example 2 Example 3 Example 4 Total Sodium Fatty 56.20 70.00 65.97 65.97 Acid Mixture Sodium ARA (26) (32.00) Sodium DHA (26.00) (26.00) Sodium phosphate 2.40 20.00 5.00 5.00 Sodium caseinate 38.40 25.00 Nonfat Instant dry milk 25.00 Sodium ascorbate 2.90 3.00 1.00 1.00 Maltodextrin 5.00 2.00 2.00 Sodium citrate 2.00 1.00 1.00 Antioxidant 0.03 0.03 ARA:Phosphate Ratio 1.6:1 DHA:Phosphate Ratio 5.2:1 5.2:1 Wt % ARA/DHA of 24 29 24 24 dried powder composition

(43) TABLE-US-00004 TABLE IIB Example Example Ingredients, % Weight 5 6 Total Sodium Fatty 65.00 63.47 Acid Mixture Potassium ARA (29.00) (29.00) Sodium phosphate 8.00 Potassium phosphate 8.50 Calcium phosphate 0.97 1.00 Sodium caseinate 19.00 20.00 Sodium ascorbate 1.00 1.00 Maltodextrin 5.00 5.00 Sodium citrate 1.00 1.00 Antioxidant 0.03 0.03 DHA:Phosphate Ratio 3.8:1 3.3:1 Wt % DHA of dried 26 25 powder composition

(44) TABLE-US-00005 TABLE IIC Example Example Example Example Ingredients, % Weight 7 8 9 10 Total Sodium Fatty Acid 63.97 76.00 75.00 70.00 Mixture Sodium ARA (29.00) (35.00) (34.00) Sodium DHA (28.00) Sodium phosphate 8.00 20.00 20.00 25.00 Calcium phosphate 1.00 Sodium caseinate 20.00 Sodium ascorbate 1.00 4.00 3.00 3.00 Maltodextrin 5.00 Sodium citrate 1.00 2.00 2.00 Antioxidant 0.03 ARA:Phosphate Ratio 3.6:1 1.7:1 1.7:1 DHA:Phosphate Ratio 1.1:1 Wt % ARA/DHA of dried 27 33 32 26 powder composition

(45) The fatty acid compositions of Examples 1-7 were all relatively free flowing when dry. When mixed with milk, they dispersed quickly (i.e., in a matter of seconds) by stirring or shaking. Any other desired method of agitating the powder in the liquid such that the powder disperse in the liquid could have been used as well. The milk/powder mixture remained dispersed for at least several hours (at which point monitoring ceased). Thus, the fortified liquid drink formed with the powder compositions were all considered to be highly stable; that is, the composition remained dispersed in the liquid. Composition Examples 8-10 differ from Examples 1 and 3-7 in that they exclude protein and carbohydrates. They too dispersed quickly in liquid and remained dispersed in the liquid for extended periods of time. Hence, the compositions of Examples 8-10 are also deemed to be stable.

(46) TABLE-US-00006 TABLE IID Example Example Example Ingredients, % Weight 11 12 13 Total Sodium Fatty Acid 89.00 85.00 75.70 Mixture Sodium ARA (40.00) (38.00) (34.00) Sodium phosphate 6.00 10.00 20.00 Rice bran extract 1.00 1.00 0.80 Sodium ascorbate 4.00 4.00 3.50 ARA:Phosphate Ratio 6.9:1 3.7:1 1.7:1 Wt % ARA of dried 37 35 31 powder composition

(47) TABLE-US-00007 TABLE IIE Example Example Example Example Ingredients, % Weight 14 15 16 17 Total Sodium Fatty Acid 70.00 65.97 74.50 85.00 Mixture Sodium ARA (31.00) (38.00) Sodium DHA (28.00) (32.00) Sodium phosphate 20.00 30.00 20.00 6.00 Rice bran extract 5.00 Sodium ascorbate 3.40 1.00 3.50 4.00 Maltodextrin 5.00 2.00 Sodium citrate 1.60 1.00 2.00 Antioxidant 0.03 ARA:Phosphate Ratio 1.5:1 0.29 DHA:Phosphate Ratio 0.9:1 1.6:1 Wt % ARA/DHA of dried 29 27 30 36 powder composition

(48) Examples 11, 12, 13 and 17 demonstrate that the use of rice bran can improve dissolution rates. Examples 11-14 and 16-17 use higher sodium ascorbate levels and can be expected to have greater stability than the other compositions.

(49) Fatty Acid Component Only Composition Examples

(50) Two examples were also prepared that, as shown in Table IIF below, comprised only spray dried fatty acid component. That is, the compositions were 100% fatty acid salt, and had no proteins, vitamins, carbohydrates, or inorganic salts mixed with the fatty acid component. The powder form of the fatty acid composition was formed by spray drying the fatty acid composition.

(51) TABLE-US-00008 TABLE IIF Composition Example Composition Example 18 (ARA) 19 (DHA) Quantity Percent of Quantity Percent of Ingredients (grams) Formulation (grams) Formulation Total Sodium fatty acid 10.7 100 10.8 100 mixture Sodium ARA content in 4.83 45 the sodium gatty acid mixture Sodium DHA content in 4.24 39 the sodium fatty acid mixture Wt % ARA/DHA of dried 42 37 powder composition

(52) From Examples 18 and 19, we determined that spray dried fatty acid compositions comprised only of Na-ARA, Na-DHA, K-ARA, or K-DHA dispersed quickly and easily in liquids.

(53) In examples 1-19 above, the fatty acid composition for each example was not microencapsulated. That is, although some of the compositions may have exhibited in-situ microencapsulation, none of the compositions were exposed to a microencapsulation step which would encapsulate the composition in a waxy or carbohydrate substrate, as occurs with traditional (intentional) microencapsulation.

(54) Table III below tabulates the percentages of the various ingredients of the powder compositions when broadly categorized. As noted above, currently available microencapsulated fatty acid supplements contain only 10-15 wgt % PUFA. As seen from Table III below, our fatty acid composition contains a range of about 24 wgt % to about 42 wgt % of the desired fatty acid. This represents a substantial increase in available fatty acid relative to currently available products. This increase in the weight percent of fatty acid in the powder means that less of our powder is needed to deliver the same amount of fatty acid than if the currently available 10-15 (wgt) % PUFA product is used.

(55) For example, assuming that an infant formula manufacturer preparing a batch of infant formula by dry mixing, specifies the addition of 100 kg of the currently available Cargill 15% ARA Powder, the same manufacturer, choosing to use the our 37% ARA-Sodium Composition (Example No. 11, above) would need to add only about 40 kg, representing approximately a 60% reduction in the amount of fatty acid composition needed to achieve the same loading. An additional benefit is that, because of the higher concentration of ARA or DHA in our formulation, there are much lower levels of other excipients in the formulation. This simplifies the formulator's task of formulating a sole nutritional source product, like an infant formula, and clearly increases the flexibility of defining the formulation.

(56) TABLE-US-00009 TABLE III % % Inorganic desired desired fatty Salt Desired fatty Com- Desired Total Na/K acid % of (including acid/ % position Fatty % Na/K fatty dried any phosphate % % Carbo- Example Acid fatty acid acid powder phosphate) ratio Protein Vitamins* hydrates 1 ARA 56 26 25 2.4 10.4:1 38 2.9 0 2 ARA 70 32 29 22 1.6:1 0 3 5 3 DHA 66 26 24 6 5.2:1 25 1 2 4 DHA 66 26 24 6 5.2:1 25 1 2 5 ARA 65 29 26 9 3.8:1 19 1 5 6 ARA 63 29 25 10.5 3.3:1 20 1 5 7 ARA 64 29 27 10 3.6:1 20 1 5 8 ARA 76 35 33 20.7 1.7:1 0 4 0 9 ARA 75 34 32 22 1.7:1 0 3 0 10 DHA 70 28 26 27 1.1:1 0 3 0 11 ARA 89 40 37 5.8 6.9:1 0 4 1 12 ARA 85 38 35 10 3.7:1 0 4 1 13 ARA 76 34 31 20 1.7:1 0 3.5 0.8 14 ARA 70 31 29 22.1 1.5:1 0 3.4 5 15 DHA 66 28 27 31 0.9:1 0 1 2 16 DHA 75 32 30 22 1.6:1 0 3.5 0 17 ARA 85 38 36 5.5 7:1 0 4 5 18 ARA 100 45 42 0 0 0 0 19 DHA 100 39 37 0 0 0 0 Range 56-89 26-40 24-42 2.4-31 0.9:1-10.4:1 0-38 1-4 0-5 (wt %) *The vitamins in the examples included sodium ascorbate is vitamin. The percentages reflect the correction for the Na-content of the sodium ascorbate (by multiplying by 0.89).

(57) TABLE-US-00010 TABLE IVA Powder Powder Powder Powder Powder Example 1 Example 2 Example 3 Example 4 Example 5 Ingredient Function (ARA) (ARA) (DHA) (DHA) (DHA) % Na/K fatty acid Fatty acid mixture 56.2 70 66 66 65 % desired Fatty acid 26 32 26 26 29 Na/K fatty acid % Na/K/Ca Phosphate Inorganic salt, 2.4 20 5 5 9 source Buffer, flow modifier, improves color % Skim, whole, nonfat Protein, Emulsifier, 38 25 25 19 milk powders, wetting, caseinates (such as dispersing, and sodium or calcium), instantizing agent whey protein % Maltodextrin, Carbohydrate, 5 2 2 5 sugar/sugar improves color, derivatives texture, and flow % Na-ascorbate Vitamin, 3 3 1 1 1 antioxidant % Na-citrate Inorganic salt, 2 1 1 1 sequestering agent, buffer

(58) TABLE-US-00011 TABLE IVB Powder Powder Powder Powder Powder Example 6 Example 7 Example Example Example 10 Ingredient Function (ARA) (ARA) 8 (ARA) 9 (ARA) (DHA) % Na/K fatty Fatty acid 63.5 64 76 75 70 acid mixture % desired Fatty acid 29 29 35 34 28 Na/K fatty acid % Na/K/Ca Inorganic, 9.5 9 20 20 25 phosphate Salt, source Buffer, flow modifier, improves color % Skim, Protein, 20 20 whole, nonfat Emulsifier, milk powders, wetting, caseinates dispersing, (such as and sodium or instantizing calcium), whey agent protein % Carbohydrate, 5 5 Maltodextrin, improves sugar, and color, texture, sugar and flow derivatives % Na- Vitamin, 1 1 4 3 3 ascorbate antioxidant % Na-citrate Inorganic 1 1 2 2 Salt, sequestering agent, buffer

(59) TABLE-US-00012 TABLE IVC Powder Powder Powder Powder Powder Example 11 Example 12 Example 13 Example 14 Example 15 Ingredient Function (ARA) (ARA) (ARA) (ARA) (DHA) % Na/K fatty acid Fatty acid mixture 89 85 75.7 70 66 % desired Fatty acid 40 38 34 31 28 Na/K fatty acid % Na/K/Ca Inorganic Salt, 6 10 20 20 30 phosphate Buffer, flow modifier, source improves color % Skim, whole, Protein, Emulsifier, nonfat milk wetting, dispersing, and powders, instantizing agent caseinates (such as sodium or calcium), whey protein % Maltodextrin, Carbohydrate, improves 5 2 sugar, and sugar color, texture, and flow derivatives Lecithin, rice Carbohydrate, 1 1 0.8 bran extract Emulsifier, wetting, dispersing, and instantizing agent % Na-ascorbate Vitamin, 4 4 3.5 3.4 1 Antioxidant % Na-citrate Inorganic Salt, 1.6 1 sequestering agent, buffer

(60) TABLE-US-00013 TABLE IVD Powder Powder Powder Powder Range (wt %) Example 16 Example 17 Example 18 Example 19 (exclusive of Ingredient Function (DHA) (ARA) (ARA) (DHA) Examples 18 & 19) % Na/K fatty acid Fatty acid 74.5 85 100 100 63.5-89 mixture % desired Fatty acid 32 38 45 39 26-40 Na/K fatty acid % Na/K/Ca Inorganic Salt, 20 6 phosphate source Buffer, flow 2.4-30 modifier, improves color % Skim, whole, nonfat Protein, 0-38 milk powders, wetting, caseinates (such as dispersing, and sodium or calcium), instantizing whey protein agent % Maltodextrin, sugar, Carbohydrate, 0-5 and sugar derivatives improves color, texture, and flow Lecithin, rice bran Carbohydrate, 5 0-5 extract Emulsifier, wetting, dispersing, and instantizing agent % Na-ascorbate Vitamin, 3.5 4 1-4 antioxidant % Na-citrate Inorganic Salt, 2 0-2 sequestering agent, buffer

(61) Examples of Fortified Nutritional Drink Products with a Fatty Acid Composition:

(62) Test solutions of fatty acid compositions were prepared for taste and organoleptic evaluations. These test sample solutions comprise reconstituted milk solids in water as the medium, along with a fatty acid composition. Test solutions were evaluated against a blank which did not contain the fatty acid composition.

(63) The milk fat concentration may be in the range of 12 g/L (about 1% milk fat) to 26 g/L (about 2.5% milk fat), with a target of about 24 g/L (about 2.4% milk fat). The precise fat content of an infant formula drink, along with the precise fatty acid contents are strictly regulated by national food standards codes. The desired fat concentrations were achieved using a blend of whole milk powder (WMP) and skim milk powder (SMP).

(64) Examples of fatty acid fortified infant formula were prepared by adding the milk powder blend and the fatty acid composition to water using the compositions from Example Numbers 8, 13, 14, and 16 above. The slurry of solids was shaken vigorously by hand until dispersed. Dissolution time was typically in the range of 45 seconds. The formulated Na-ARA and Na-DHA powders employed in the following Drink Preparation Examples 1 and 2 below, were completely dispersed after the vigorous shaking step without exception.

(65) In the preparation of the DHA Fortified Breakfast Drink described below in Drink Example 3, cold skim milk was added to the dry breakfast drink powder and the sodium DHA composition as recommended by the manufacturer.

(66) Drink Preparation Example 1:

(67) Infant Formula Fortified With ARA and DHA, in ratios specified by Food Safety Guidelines:

Preparation of Fatty Acid Fortified Milk with a Na-DHA Composition with and without a Na-ARA Component in the Same Solution

(68) TABLE-US-00014 Test Solution Name: A: DHA Only B: DHA + ARA Blank Sample Name: Na-DHA Composition: Na-ARA Component: DHA or ARA, % weight, 30.1 28.6 0.0 calc'd Taste Test Solution Volume: 250-mL 250-mL 250-mL Target Weight Fat: 5.91 5.91 5.91 Target Weight DHA: 0.0296 0.0296 0.00 Target Weight ARA: 0.0000 0.0591 0.0 (weights to use in bold italics below) Na-DHA Composition: 30.1% DHA Component (Powder Example 16) Na-ARA Composition 28.6% ARA Component (Powder Example 14) Blank No ARA WMP SMP Water Milk Powder Compositions: % Fat: Whole Milk Powder (WMP) 30.0 Skimmed Milk Powder (SMP) 0.0

(69) Drink Preparation Example 2:

(70) An Example of a Potential Infant Formula Fortification With ARA Only:

Preparation of Fatty Acid Fortified Milk with a Sodium ARA Composition with and without an Emulsifier

(71) TABLE-US-00015 Test Solution Test Solution A Test Sol. B Blank Name: Sample Name: Na ARA Na ARA Composition Component w/o with Emulsifier: Emulsifier: ARA, % weight 31.1 31.4 0.0 calc'd Emulsifier (Rice 0.8 0.0 0.0 bran) Conc., wt. %: Taste Test Solution 250-mL 250-mL 250-mL Volume: Target Weight Fat: 6.56 6.56 6.56 Target Weight ARA: 0.0656 0.0656 0.0 (weights to use in bold italics below) Na ARA Compo- sition with Emulsifier: 31.1% ARA Powder (Powder Example 13) Na ARA Composition w/o Emulsifier.: 31.4% ARA Powder (Powder Example 8) Blank No ARA WMP SMP Water Milk Powder Compositions: % Fat: Whole Milk Powder (WMP) 30.0 Skimmed Milk Powder (SMP) 0.0

(72) Drink Example 3:

(73) Breakfast Drink Fortified With DHA, Aimed at Delivering 25% of the recommended daily allowance (RDA) for DHA as determined by the Global Organization for EPA and DHA omega-3s (GOED).

Preparation of a Skim Milk Based Vanilla Breakfast Drink Fortified with a Na-DHA Composition to Provide 25% of RDA for DHA

(74) TABLE-US-00016 Test Solution Name: DHA Fortified Breakfast Drink Sample Name: Na-DHA Fortified Breakfast Drink Powder: DHA, % weight calc'd 30.1 Taste Test Solution Weight, g: 285 Target Weight DHA: 0.0625 (to provide 25% RDA) (weights to use in bold italics below) Na-DHA Composition: 30.1% DHA Powder Weight Vanilla Drink Mix Powder, g: (1-metallized packet) Volume Cold Fat-free Milk, 1-cup: Weight 1-cup Fat-free Milk, g:

(75) Mixing Instructions for breakfast, from bag label:

(76) (1) Empty vanilla drink mix powder packet into a large glass.

(77) (2) Add the specified amount of Na-DHA Composition to the powder in the glass.

(78) (3) Add 1 cup cold fat-free milk.

(79) (4) Stir to dissolve until consistent.

(80) The Tables below put in table form fortified liquids made by mixing selected compositions in water.

Preparation of Fatty Acid Fortified Milk with Na-DHA Composition with and without a Na-ARA Component

(81) TABLE-US-00017 Example Example Example Example Blank Ingredient 8 13 Blank 1 14 16 2 Na-DHA 0.00 0.00 0.00 30.10 30.10 0.00 Composition, % Weight Na-ARA 31.40 31.10 0.00 28.60 0.00 0.00 Composition, % Weight DHA, Fatty 0.00 0.00 0.0000 0.0982 0.0982 0.0000 Acid Composition, (g) ARA Fatty Acid 0.209 0.211 0.0000 0.207 0.0000 0.0000 Composition, (g) Target Fat 6.56 6.56 6.56 5.91 5.91 5.91 Weight (g) Target DHA 0.00 0.00 0.0000 0.0296 0.0296 0.0000 Weight (g) Target ARA 0.0656 0.0656 0.0000 0.0591 0.0000 0.0000 Weight (g) Whole Milk 21.88 21.88 21.88 19.70 19.70 19.70 Powder (g) Skimmed Milk 11.38 11.38 11.38 13.55 13.55 13.55 Powder (g) Water (g) 216.50 216.50 216.80 216.50 216.70 216.80 Solution 250 250 250 250 250 250 Volume (mL)

Preparation of a Skim Milk Based Vanilla Breakfast Drink Fortified with Na-DHA Composition to Provide 25% of RDA for DHA

(82) TABLE-US-00018 Vanilla Solution Solution Drink % Volume, Weight, Mix Weight, Target Cold Fat- Cold Fat- Powder PUFA DHA DHA free milk free milk Weight (DHA) Weight (g) (mL) (g) (g) Na-DHA For- 30.10 0.0625 0.205 240 285 36 tified Break- fast Drink

(83) The table below shows calculated amounts protein, fat, and carbohydrate of a commercially available milk-based drink both prior to and after inclusion of a 40% by weight Na-ARA fatty acid composition (Example 11). The calculations were performed such that each infant formula or drink would be fortified with 1% by weight arachidonic acid (ARA) based on the fat content of the drink or infant formula powder. The initial weight of each drink is 100 g.

(84) TABLE-US-00019 Nestle Neosure Infant CarnationBreakfast Formula, Similac Advance, Drink, Weight % Weight % Weight % Composition Composition Composition with With With Nutrient As fortifica- As fortifica- As fortifica- Component is tion is tion is tion Protein 2.0 2.0 1.4 1.4 Fat 4.0 4.10 3.7 3.79 2.4 2.46 Carbohydrate 7.3 7.3 7.1 7.1 Total Weight 13.3 13.4 12.2 12.3 13.3 13.4 Per Cent Milk Solids in the Drink Weight of 0.10 g 0.09 g 0.05 g Fatty Acid Salt Composition Used to Fortify

(85) Results Demonstrating Instant Dispersion

(86) There is a significant benefit in using the sodium and potassium salt compositions described above, compared to the traditionally microencapsulated triglycerides used in the existing prior art (examples of which are noted in the Background Section). The beneficial properties of our fatty acid salt compositions arise mainly from the higher water solubility and emulsifiability of the contained sodium and potassium fatty acid salts. The microencapsulated triglycerides of the prior art lack these attractive properties.

(87) The disclosed sodium and potassium fatty acid salt compositions have the very desirable property of being substantially instantly soluble or dispersible in water by stirring or shaking for a very short time (i.e., in less than 1 minute, and preferably less than about 30 seconds). This property is a prerequisite for dry powders that must be reconstituted into a drinkable form before using. Usually the act of reconstitution of the fatty acid composition powder occurs in simple water, or in a milk-based drink. Typical drinks that require this reconstitution prior to use notably include powdered infant formula, breakfast drink powders, and meal replacement drink powders.

(88) Further, it is evident from the emulsifying power of these salts that their significant aqueous solubility confers on them the capacity for dispersing even more fatty acid salt or triglyceride species in aqueous medium, in the form of stable salt dispersions, or oil-in-water emulsions.

(89) Therefore, our fatty acid composition provides monovalent salts of long-chain polyunsaturated fatty acids (LCPUFA's) of 18-carbon chains or longer, which are used as delivery systems for fortifying

(90) water or milk-based nutritional drinks with nutritionally important omega-3's and omega-6's. The dispersabitliy of the fatty acids surprisingly exceeded the expected dispersion of the fatty acids in liquid. This is true of the PUFAs that have four or more double bonds.

(91) Analysis of the dissolution time of the dried powder was performed within 1-2 days of preparation. The dried powders were coarsely ground; however, particle sizes were not measured.

(92) For the dissolution time analysis, 13 mg of the dried powder was mixed with 10 g of deionized water in a sealed vial at 25 C. The vial was then shaken by hand. The dissolution time was the time required for the last visible particle to fully dissolve.

(93) Upon dissolution, the dried powders typically produced colorless solutions that were clear to slightly hazy. The solution remained stable for many hours i.e. no particulates settled out of the solution.

(94) For comparison, a sodium arachidonic acid (ARA) component and sodium docosahexaenoic acid (DHA) component (i.e., Examples 18 and 19) were prepared without any additives and the dissolution times were measured. The pure sodium arachidonic acid (ARA) component (Powder Example 18) and sodium docosahexaenoic acid (DHA) component (Powder Example 19) consistent with the other formulations were easily dispersed. The following tables compare results.

(95) When compared to the pure sodium arachidonic acid (ARA) component, the addition of a phosphate salt to the formulation generally decreased the dissolution time.

(96) TABLE-US-00020 Total percent of Percent sodium fatty acid phosphate Dissolution Time Powder Ex. 18 100 0 ~1 min Powder Ex. 11 89 6 47.9 seconds Powder Ex. 12 85 10 33.2 seconds Powder Ex. 13 76 20 22.7 seconds

(97) The following examples (sodium ARA) illustrate the dissolution rate with changes in the formulation.

(98) TABLE-US-00021 Percent Percent Percent Dissolution Phosphate Protein Carbohydrates Time Powder 6 0 5 3.3 seconds Ex. 17 (Rice bran extract) Powder 20 0 5 16.9 seconds Ex. 14 (Maltodextrin) Powder 20 0 0.8 21.8 seconds Ex. 13 (Rice bran extract) Powder 20 0 0 25.5 seconds Ex. 8

(99) The following examples of sodium DHA powders illustrate the dissolution rate with changes in the formulation.

(100) TABLE-US-00022 Percent Percent Percent Dissolution Phosphate Protein Carbohydrates Time Powder 0 0 0 42.0 seconds Ex. 19 Powder 5 25 2 32.4 seconds Ex. 3 (Na (Maltodextrin) Caseinate) Powder 5 25 2 25.4 seconds Ex. 4 (Nonfat (Maltodextrin) Milk Powder) Powder 25 0 0 24. seconds Ex 10 Powder 30 0 2 24.5 seconds Ex. 15
Use of Fatty Acid Salt to Enhance Dispersability of Co-Salts

(101) When the fatty acid composition is mixed in liquid that contains a low concentration of calcium ions, it is believed that the fatty acid component (Na-ARA, Na-DHA, etc.) reacts with calcium ions (which are present in liquid milk or in milk powder) to produce a calcium co-salt of the fatty acid and phosphate, such as described in U.S. Pat. Nos. 8,178,707 and 8,378,131 which are incorporated herein by reference.

(102) It is believed that the simple fatty acid salt of the composition enhances the instantizability of the fatty acid composition. As shown by the examples below, the co-salt disclosed in U.S. Pat. Nos. 8,178,707 and 8,378,131 does not emulsify in liquid. However, when the co-salt is combined with a simple fatty acid salt, the complete composition (co-salt and simple fatty acid salt) emulsify or disperse in the liquid.

(103) (A) Working Example Using K-Salts of PUFA's to Emulsify Calcium Phosphate-PUFA Co-Salt of the U.S. Pat. Nos. 8,178,707 and 8,378,131: 1. Charge to 1-L reaction flask, equipped with Teflon paddle stirrer, N.sub.2-inlet, and jacket for heating and cooling: 500-mL degassed, deionized water 2. Using the heating medium in the jacket, heat to 40 C. Next add 9.30 g mixed ARA-rich free fatty acids. With rapid stirring, add sufficient 45% KOH(aqueous) to dissolve the free fatty acids and resulting in a final pH of 10.0-10.8 This should require about 3.7 g of the 45% KOH. 3. In a separate container, make up a solution of 0.96 g K.sub.2HPO.sub.4 in 150-mL degassed, deionized water. 4. Mix the two solutions well. Then, with vigorous stirring add dropwise a total of 6.00 g of a 21.6% CaCl.sub.2 solution to the mixture. 5. After the addition of the CaCl.sub.2 solution has been completed, dilute with an additional 200-mL degassed, deionized water. Then stir under high-shear agitation sufficient time to completely emulsify. Additional triglyceride oils (20-25 g) may be added before the high-shear stir period to form a stable oil-in-water emulsion.

(104) Result:

(105) A similar experiment with only the Calcium Phosphate-PUFA Co-Salt present with none of the K-salts of the PUFA acids results in a slurry of filterable solids instead of the oil-in-water emulsion/dispersion obtained above. The filterable solids are Calcium Phosphate-PUFA Co-Salts.

(106) (B) Working Example Using K-Salts of PUFA's to Emulsify Calcium Phosphate-PUFA Co-Salt of the U.S. Pat. Nos. 8,178,707 and 8,378,131 Along with Simple Calcium PUFA Salt: 1. Charge to 1-L reaction flask, equipped with Teflon paddle stirrer, N.sub.2-inlet, and jacket for heating and cooling: 150-mL degassed, deionized water 2. Using the heating medium in the jacket, heat to 40 C. Next add 23.5 g mixed ARA-rich free fatty acids. With rapid stirring, add 0.92 g 45% KOH, (aqueous) to partially dissolve the free fatty acids. 3. Then add 3.10 g Ca(OH).sub.2. Stir well for 1-2 minutes. 4. In a separate container, make up a solution of 2.78 g K.sub.2HPO.sub.4 in 150-mL degassed, deionized water. 5. Mix the two solutions well, by adding the fatty acid containing mixture to the K.sub.2HPO.sub.4 solution. 6. Stir vigorously the two combined solutions for 2-3 hours at 40 C.-50 C. until the pH is stable. Then stir under high-shear agitation sufficient time to completely emulsify. Additional triglyceride oils (20-25 g) may be added before the high-shear stir period to form a stable oil-in-water emulsion.

(107) Result:

(108) A similar experiment with only the Calcium Phosphate-PUFA Co-Salt and the Simple Calcium PUFA Salt present with none of the K-salts of the PUFA acids results in a slurry of filterable solids instead of the oil-in-water emulsion/dispersion obtained above. The filterable solids are Calcium Phosphate-PUFA Co-Salts and Simple Calcium PUFA Salts.

(109) (C). Working Example Using Na-Salts of PUFA's to Emulsify Calcium Phosphate-PUFA Co-Salt of the U.S. Pat. Nos. 8,178,707 and 8,378,131: 1. Charge to 1-L reaction flask, equipped with Teflon paddle stirrer, N.sub.2-inlet, and jacket for heating and cooling: 500-mL degassed, deionized water 2. Using the heating medium in the jacket, heat to 40 C. Next add 9.30 g mixed ARA-rich free fatty acids. With rapid stirring, add sufficient 50% NaOH(aqueous) to dissolve the free fatty acids and resulting in a final pH of 10.0-10.8 This should require about 2.4 g of the 50% NaOH. 3. In a separate container, make up a solution of 0.96 g K.sub.2HPO.sub.4 in 150-mL degassed, deionized water. 4. Mix the two solutions well. Then, with vigorous stirring add dropwise a total of 6.00 g of a 21.6% CaCl.sub.2 solution to the mixture. 5. After the addition of the CaCl.sub.2 solution has been completed, dilute with an additional 200-mL degassed, deionized water. Then stir under high-shear agitation sufficient time to completely emulsify. Additional triglyceride oils (20-25 g) may be added before the high-shear stir period to form a stable oil-in-water emulsion.

(110) Result:

(111) A similar experiment with only the Calcium Phosphate-PUFA Co-Salt present with none of the Na-salts of the PUFA acids results in a slurry of filterable solids instead of the oil-in-water emulsion/dispersion obtained above. The filterable solids are Calcium Phosphate-PUFA Co-Salts.

(112) Conclusion: The enhanced dispersibility demonstrated by the long chain PUFA (LCPUFA) salts can be used to disperse and emulsify the co-salts disclosed in the Jost Chemical Co.'s U.S. Pat. Nos. 8,178,707 and 8,378,131. The fatty acid concentration levels thereby obtained can exceed the otherwise expected levels

(113) The dispersibility tests show that a spray dried fatty acid (such as a spray dried sodium and potassium salts of ARA and DHA) in powder form disperses without the need for additional components to the composition. Thus, in such instances, the fatty acid composition comprises only the fatty acid salt.

(114) Bioavailability

(115) The fatty acid compositions have a higher bioavailability of the fatty acids than do currently available microencapsulated triglycerides, such as noted above. Generally, when fat or lipid boluses are swallowed, they must be broken down and emulsified with the help of bile salts and other amphipathic molecules to form small emulsion droplets. This increases the surface area sufficiently so that water-soluble lipase can begin to hydrolyze the fatty acids from the triglycerides. In the case of both infant formula products (whether made with our above-noted compositions or a triglyceride source) this hydrolysis can begin relatively rapidly as the powder particles are already small. (Parada Ji, Aguilera J M. Food microstructure affects the bioavailability of several nutrients. J Food Sci. 2007 March; 72(2):R21-32.) As the mixture moves from the stomach to the duodenum, the enzyme concentration is markedly increased by pancreatic lipase and the rate of hydrolysis is increased.

(116) In the formula made with a triglyceride source, the enzymatic process cleaves the fatty acids from the triglycerides leaving intact only the monoglycerides which enter into micelles and become suspended in solution. Micellular formation occurs because ARA and the other long chain fatty acid molecules and the monoglycerides in the added fat are insoluble in water (Handbook of Chemistry and Physics, 84.sup.th Edition 2003-2004 CRC Press, page 7-6) and are only solubilized by their incorporation into micelles. Since the ARA-glycerides are minor components of both the fats and the gastric medium, the micelle composition itself consists mainly of endogenous bile salts, phospholipids, cholesterol, vitamins and the other fatty acids.

(117) In the case of the formula made with the above-noted compositions, the digestion process is similar with one exception. The fatty acids from the sodium salts, once released from the powder particles, are immediately reconstituted into the free acids by the strong stomach acid. For example: the protonation of the ARA anion is: ArA.sup.+H.sup.+.fwdarw.[ARA.sup.0] or ARA, and the high acid concentration drives the reaction to the right. The rates of acid: base reactions involve only proton transfers and are well known to be extremely fast (the order of 10.sup.12 sec). ((a) RP. Bell, (1959) 13: 168-182. The rates of simple acid-base reactions, Q. Rev. Chem. Soc., 1959, 13, 169-182, and (b) EF Caldin (2001) The Mechanisms of Fast Reactions in Solution, page 11, Table 1.2 Distributed by Jos Press 5795G Burke Center Parkway, Burke Va. 22015). The diffusion constants of molecules in water are on the order of 10.sup.6 s/cm.sup.2. The fastest possible time for a single molecule to aggregate into a micelle 10 nm in diameter, using the Einstein diffusion formula, is =.sup.2/6D. Thus, the noted rates are much faster than the subsequent aggregation of released fatty acids into micelles which can take several microseconds or longer. Because the formation of the unionized fatty acid from its salt is so rapid, this reaction cannot affect the overall digestion process as long as sufficient acid is present.

(118) A key enzyme required for the metabolism of triglycerides is lipase, most of which is secreted by the pancreas. At birth this enzyme is not fully expressed and does not reach full development until six months of age. In the interim, while there are compensating mechanisms, the amount of available lipase is a limiting factor in the hydrolysis of triglycerides. (Koldovsky O. (1998) Digestive-Absorption Functions in Fetuses, Infants and children, Chapter 128 p 1404 in Fetal and Neonatal Physiology 2nd Ed Vol 2. R A Polin and W W Fox, W.B Saunders Co. Philadelphia.) The sodium salts of the fatty acids do not require hydrolysis once they are converted into the free acid, so this limitation does not exist for our fatty acid composition. Thus, it is expected that the fatty acid composition will break down in the stomach, such that the fatty acid component becomes bioavailable in the stomach.

(119) Stability

(120) As a general matter, the high sensitivity of omega fatty acids to oxygen is related to their molecular structure and physical state. Polyunsaturated fatty acids (PUFAs) such as eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and arachidonic acid (ARA) contain more than two double bonds in the cis-configuration. As the number of double bonds within a PUFA increases, the fatty acid becomes more susceptible to oxidative degradation. The physical state (i.e., liquid or solid) determines the rate of diffusion of oxygen throughout the substance. Diffusion of oxygen through a liquid occurs more rapidly than through a solid matrix. Thus, oxygen saturation occurs faster in liquids than in solids, allowing oxidation to occur more rapidly. ((a) Hsu H, Trusovs S, Popova T., Preparation of Fatty Acids in Solid Form; (b) U.S. Pat. No. 8,203,013 (Jun. 19, 2012)). For this reason, solids generally are considered more stable toward oxidation than liquids.

(121) Fatty Acid Composition Example Nos. 2 and 9 (which both contained an Na-ARA salt) were placed on stability studies under real time conditions and accelerated conditions in metalized and low density polyethylene (LDPE) storage bags. The stability of the compositions was determined by measuring the level of oxidative degradation of the fatty acid composition. For the real time conditions, the powder compositions were stored at 25 C. and 60% R.H.; and for the accelerated conditions, the powder compositions were stored at 40 C. and 75% R.H. These conditions are designated by the Q1A guideline produced by the International Conference On Harmonisation Of Technical Requirements For Registration Of Pharmaceuticals For Human Use (hereinafter, ICH Q1A). Measurements of oxidative degradation were performed using GC analysis, Peroxide values and Anisidine values at selected time intervals. Real time storage conditions and accelerated storage conditions were both run for 13 months. Under the ICH Q1A, 13 months under the accelerated conditions simulates 4 years of storage. The data from the studies is tabulated in Tables VA.

(122) The data below represents data collected from ongoing stability studies on two Na-arachidonate salt formulations (Composition Example Nos. 2 and 9, as noted above). Two packaging forms were used: (1) metalized bags, which is the preferred packaging material, and (2) low density polyethylene (LDPE) bags which function as positive controls. Both long-term, room temperature and accelerated conditions were studied, with the results of the long term, room temperature study being tabulated in Tables VA and VB below and the results of the accelerated study being tabulated in Table VIA and VIB below.

(123) Long Term Real Time Study

(124) In the real time stability study, Powder Example 2 (comprised of 70% PUFA (43.1% ARA), 20% disodium hydrogen phosphate, 5% Maltrin OD M550 (a maltodextrin available from Grain Processing Corporation of Muscatine, Iowa), 3% sodium ascorbate, 2% trisodium citrate) and Powder Example 9 (comprised 75% PUFA (43.1% ARA), 20% Disodium hydrogen phosphate, 3% sodium ascorbate, 2% trisodium citrate) were stored at 25 C. (essentially room temperature) and 60% R.H. The results are tabulated in Tables VA and VB. The results show that the fatty acid compositions oxidized very little over a 12 month period, although the oxidation for the samples stored in the LDPE bags was greater than for the samples stored in the metalized bags. This was due to the greater air permeability of the LDPE bag relative to the metalized bag.

(125) TABLE-US-00023 TABLE VA Long-Term Real Time Conditions Composition 9 Metalized Bag LDPE Bag Months 0 12 0 12 ARA (% of Total Fatty Acid) 36.78 36.07 36.78 33.17 Peroxide Value 0 0 0 6.6 Anisidine Value 0 3.61 0 N/A

(126) TABLE-US-00024 TABLE VB Long-Term Real Time Conditions Composition 2 Metalized Bag LDPE Bag Months 0 12 0 12 ARA (% of Total Fatty Acid) 33.92 33.51 33.92 31.45 Peroxide Value 0 6.6 0 12.3 Anisidine Value 0 N/A 0 n/a

(127) In the accelerated storage study Powder Example 2 (comprised of 70% PUFA (43.1% ARA), 20% disodium hydrogen phosphate, 5% Maltrin OD M550, 3% sodium ascorbate, 2% trisodium citrate) and Powder Example 9 (comprised 75% PUFA (43.1% ARA), 20% Disodium hydrogen phosphate, 3% sodium ascorbate, 2% trisodium citrate) were stored at 40 C. and 75% R.H. The results are tabulated in Tables VIA and VIB below. As with the real-time/room temperature study, the fatty acid compositions oxidized very little over a 13 month period, although the oxidation for the samples stored in the LDPE bags was greater than for the samples stored in the metalized bags. Thirteen months of an accelerated study is generally considered to correspond to about 4 years (48 months) of real time storage at room temperature. Thus, it is expected that the fatty acid compositions would be shelf storage stable for at least 36 months, and for as long as 48 months (and possibly longer).

(128) TABLE-US-00025 TABLE VIA Accelerated Study Composition 9 Metalized Bag LDPE Bag Months 0 1 2 13 0 1 2 ARA (% Total Fatty 36.78 36.77 36.94 36.74 36.78 37.09 33.81 Acid) Peroxide Value 0 0 0 0 0.00 15.00 12.70 Anisidine Value 0 1.14 3.12 1.6 0.00 13.06 28.23

(129) TABLE-US-00026 TABLE VIB Accelerated Study Composition 2 Metalized Bag LDPE Bag Months 0 1 2 13 0 1 2 ARA (% Total Fatty 33.92 34.35 34.39 33.50 33.92 33.24 33.11 Acid) Peroxide Value 0 0 0 0 0 8.50 6.70 Anisidine Value 0 1.39 1.17 2.11 0 5.43 12.23

(130) In further studies, the stability of the solid powdered fatty acid compositions were compared to a liquid state triglyceride-containing PUFA. It would be expected that a PUFA-containing triglyceride (Tg) liquid would exhibit more rapid oxidative degradation than a similar solid PUFA-Na salt.

(131) To test this hypothesis, experimental data was collected on stability experiments run on these liquid and solid samples. In the comparison test, the oxidation of a liquid triglyceride fish oil was compared to that of solid sodium arachidonate salt formulations of Composition Example Nos. 2 and 9.

(132) The experiment compared liquid fish oil, having a PUFA concentration (EPA+DHA content) of about 30% to that of solid sodium arachidonate salt formulations of Composition Nos. 2 and 9 with a very similar 30% PUFA concentration. The PUFA concentration in the PUFA sodium salt formulation is found by normalizing the PUFA concentration to the level of PUFA salt in the formulation, i.e., (0.75)(40)=30%. The remainder of the formulated sodium salt product is comprised of dibasic sodium phosphate, sodium citrate, and sodium ascorbate.

(133) The test period ran for one month at accelerated conditions of 40 C. and 75% relative humidity. At the end of the one-month period, the degree of oxidation was measured employing commonly used analytical method from the U.S. Pharmacopoeia, namely the peroxide value and the anisidine value. The composite of these two determinations was used to express the TOTOX Value, also a commonly used oxidation metric from the U.S. Pharmacopoeia. The lower the TOTOX value, the lower the degree of oxidation that occurred.

(134) The results are tabulated in Tables VII and VIII below. Table VII includes the results for the samples packaged in metalized bags. These bags have essentially no O.sub.2-transfer rate or moisture transfer rate. Table VIII shows the results for the samples contained in low-density polyethylene (LDPE) bags. This bag is meant to be a positive control, allowing some O.sub.2 and water vapor transmission into the sample.

(135) TABLE-US-00027 TABLE VII Samples run for 1 month in metalized bags at accelerated conditions (40 C., 75% R.H.) Time 0 1 Month Per- Ani- Per- Ani- Sample oxide sidine oxide sidine Sample Origin Value Value TOTOX Value Value TOTOX Liquid ONC oil 0 4 4 3 6 11 Tg A: Solid M. alpina 0 0 0 0 1 1 ARA-Na oil B: Solid M. alpine 0 0 0 0 1 1 ARA-Na oil

(136) TABLE-US-00028 TABLE VIII Samples run for 1 month in LDPE bags at accelerated conditions (40 C., 75% R.H.) Time 0 1 Month Per- Ani- Per- Ani- Sample oxide sidine oxide sidine Sample Origin Value Value TOTOX Value Value TOTOX Liquid ONC oil 0 4 4 377 555 1309 Tg A: Solid M. alpina 0 0 0 15 13 43 ARA-Na oil B: Solid M. alpine 0 0 0 9 5 22 ARA-Na oil

(137) The large difference in TOTOX values measured from samples in the LDPE bag demonstrates that the solid/powder fatty acid composition degrades at a substantially lower rate than the liquid triglyceride. The difference between the results of the metalized and LDPE bags demonstrates the effect the type of bag can have on the oxidation of the sample. As seen, the results from the samples packaged in the metallized bags show clearly that no oxidative degradation occurs if the solid Na-arachidonate salts are stored and packaged in these bags.

(138) The results in Table VIII strongly and clearly demonstrate the superior oxidative stability of the solid state Na-arachidonate salt formulations compared to the liquid triglyceride.

(139) The following conclusions can be drawn from the studies outlined above: in the preferred metalized bag packaging, acceptable results are observed under both long-term and room temperature conditions up to twelve months' time period, and accelerated conditions up to 13-months' time period; Packaging form is clearly important. It appears that proper packaging can guarantee stability of the PUFA salt under the conditions and time studied While packaging is important, it is even more significant to note that the salt form of the PUFA has clear oxidative stability advantages over the triglyceride form.

(140) As can be seen from the results above, the noted compositions exhibited excellent long term stability (i.e., shelf life). Although the long term stability study only monitored the two compositions for 12 months, it is expected that the composition would be stable for up to 18 months and even up to 36 months. Testing further predicts stability for up to 48 months.

(141) In view of the above, it will be seen that we have developed a fatty acid composition that is simple to produce and does not require micro-encapsulation, as is required by currently available powder composition. The fatty acid composition is quickly and easily dissolved in a liquid by simple shaking or stirring to form a dispersion that is stable for at least several hours.

(142) As various changes could be made in the above constructions without departing from the scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.