WO2004082592A2

WO2004082592A2 - Metal amino acid chelates having nutritionally relevant anion radical (s)

Info

Publication number: WO2004082592A2
Application number: PCT/IN2004/000063
Authority: WO
Inventors: Ramu Krishnan
Original assignee: Ramu Krishnan
Priority date: 2003-03-19
Filing date: 2004-03-17
Publication date: 2004-09-30
Also published as: WO2004082592A3

Abstract

The present invention relates to compositions and methods for preparing Metal Amino Acid Chelates having a nutritionally relevant Anion Radical(s) having higher solubility and better bio absorption. The composition is prepared by reacting a metal Amino Acid Hydroxide Chelate with a nutritionally relevant acid radical in a suitable mole ratio such that the new chelate formed has the metal Amino Acid Structure unchanged but is bonded forming quarternary ammonium ion(s) to a nutritionally Relevant Anion Radical(s) obtained by ionic dissociation of a nutritionally Relevant acid(s).

Description

METAL AMINO ACID CHELATES HAVING NUTRITIONALLY RELEVANT ANION RADICAL(S)

FIELD OF THE INVENTION :

This invention lays emphasis on formation of metal alpha amino acid chelate, wherein the primary valency, if any and secondary valency of the metal is satisfied by amino acid(s) and normally highly soluble quarternary ammonium salt formed by the coordinate covalent bonding of the 'N' of amino acid group with nutritionally relevant anion radical(s).

This invention also includes chelates formed with the charge on the metal 1)0 ion being neutralized by amino acid(s) along with negatively charged elements / groups, the resultant products forming quarternary ammonium complex with nutritionally relevant anion radical(s) as mentioned above.

The present invention relates to the field of Biochemistry more particularly to compositions and methods for preparing Metal Amino Acid Chelates

15 having a nutritionally relevant Anion Radical. The composition is prepared by reacting a metal Amino Acid Hydroxide Chelate or Metal Amino Acid Salt Chelate with a nutritionally relevant acid radical in a suitable mole ratio such that the new chelate formed has the metal Amino Acid structure is unchanged but is bonded to a nutritionally relevant Anion

2 Q Radical obtained by ionic dissociation of a nutritionally Relevant acid or its salts and esters.

Amino Acid Chelates having a nutritionally relevant anion radical are those chelates which have the metal linked to the Amino Acid having a positive charge and the Nutritionally relevant Radical having the negative charge when ionized. The metal amino acid chelates of the present invention have a amino acid to metal to Nutritionally relevant Acid Radical in a molar ratio from 1 :1 :1 to 4:1 :2.

BACKGROUND OF THE INVENTION

Amino acid chelates are generally produced by the reaction between .alpha.-amino acids and metal ions having a valency of two or more to form a ring structure. In such a reaction, the positive electrical charge of the metal ion is neutralized by the electrons available through the carboxylate or free amino groups of the .alpha.-amino acid.

10 Traditionally, the term "chelate" has been loosely defined as a combination of a metallic ion bonded to one or more amino acids forming heterocyclic ring structures. Under this definition, chelate formation through neutralization of the positive charges of the metal ions may be through the formation of ionic, covalent, or coordinate covalent bonding.

I S A chelate is a definite structure resulting from precise requirement of synthesis. Proper conditions must be present for chelation to take place, including proper mole ratios of amino acids to metal ions, pH, temperature, solubility of reactants and proper catalysts. For chelation to occur, all components are generally dissolved in solution and are either

2 o ionized or of appropriate electronic configuration in order for coordinate covalent bonding and/or ionic bonding between the amino acid and the metal ion to occur.

Chelation can be confirmed and differentiated from mixtures of components by infrared spectra through comparison of the stretching of bonds or shifting of absorption caused by bond formation. The product, referred to as an "amino acid chelate," when properly formed, is a stable product having one or more five-membered rings formed by a reaction between the carboxyl oxygen, and the .alpha.-amino group of an .alpha.-amino acid with the metal or metal ion having a positive charge and an nutritionally relevant radical with a negative charge. Such a five-membered ring is defined by the metal atom / ion, the carboxyl oxygen, the carbonyl carbon, the alpha carbon and the .alpha.- amino nitrogen. During the formation of ring structure, the alpha amino nitrogen denotes a lone pair to the metal ion. It was also surprisingly found that there existing a weak bond between the metal and quarternary alpha amino nitrogen. The actual structure of the cation will depend upon the amino acid to metal mole ratio and whether the carboxyl oxygen forms a coordinate covalent bond or an ionic bond with the metal ion. Generally, the amino acid to metal molar ratio is at least 1:1 and is preferably 2:1 or 3:1. However, in certain instances, the ratio may be 4:1. Most typically, an amino acid chelate may be represented at a amino acid to metal molar ratio of 2:1. In all the cases the nutritionally relevant anion radicals are formed from an acid with a stoichmetry of atleast one mole, typically two moles and in rare cases upto four moles. The structure of the Metal o amino acid chelate having nutritionally relevant anion radical is presented below.

(i) Amino acid to metal to nutritionally relevant anion radical molar ratio of 1:1:1

STRUCTURE 1 Amino acid to metal to nutritionally relevant anion radical molar ratio of 2:1:1

) Amino acid to metal to nutritionally relevant anion radical molar ratio of 2:1:2

In the above structure, the solid lines represent coordinate covalent bonds and covalent bonds. The dashed lines between the alpha.-amino group and the metal (M) represent the weak bond. Further, when R is H, the amino acid is glycine which is the simplest of the .alpha.-amino acids. However, R could be a radical forming any other of the other twenty or so naturally occurring amino acids derived from proteins. All of the amino acids have the same configuration for the positioning of the carboxyl oxygen and the .alpha.-amino nitrogen with respect to the metal ion. In other words, the chelate ring is defined by the same atoms with respect to all alpha amino acids in each instance, even though the R group may vary.

The average molecular weight of the hydrolyzed Protein and / or amino acids must be approximately 150 and the resulting molecular weight of the chelate must not exceed 800.

The reason a metal atom / ion can accept bonds over and above the oxidation state of the metal is due to the nature of chelation. For example, at the .alpha.-amino group of an amino acid, the nitrogen contributes both of the electrons used in the bonding. These electrons fill available spaces in the d-orbitals forming a coordinate covalent bond. Thus, a metal ion with a normal valency of +2 can be bonded by four bonds when fully chelated.

In this state, the chelate is completely satisfied by the bonding electrons and the charge on the metal atom (as well as on the overall molecule) is neutral. According to the present invention, the metal ion is typically bonded to the .alpha.-amino group by coordinate covalent bond and weak bond as mentioned above.

In the place of using single Aminoacid, the amino acid chelates can also be prepared using small peptide amino acids wherein the peptide may be in the form of dipeptides, tripeptides, and sometimes tetrapeptides. One advantage of amino acid chelates in the field of mineral nutrition is attributed to the fact that these chelates are readily absorbed in the absorptive mucosal cells or plant cells by means of active transport or other know mechanisms. In other words, the minerals are absorbed along with the amino acids as a single unit utilizing the amino acids as carrier molecules.

Therefore, the problems associated with the competition of ions for active sites and the suppression of specific nutritive mineral elements by others are avoided.

Q > This is especially true for compounds such as Ferrous / Ferric sulphates that must be delivered in relatively large quantities in order for the Fauna & Flora to absorb an appropriate amount. This is significant because large quantities often cause nausea and other gastrointestinal discomforts in animals as well as create an undesirable taste. Additionally, in plants, 5 large amounts of these compounds can act to burn leaves and cause other undesirable results.

Use of enhancers to promote the bioavailability of a desired Mineral like Iron in a system has been well documented.

Ascorbic Acid, a unique acid which does not contain the carboxylic acid o group in its ring structure, is a strong enhancer of iron absorption. It may exert its "enhancing" effect by promoting acidic conditions within the stomach so that the dietary iron is efficiently solubilized; by reducing ferric iron to its better absorbed ferrous form; by forming chelates with iron in the stomach; and by maintaining the solubility of iron when the food 5 enters the alkaline environment of the small intestine - which counteracts the inhibitory effect of dietary amino acids such as phytates and tannins.

Iron absorption from a semisynthetic meal increased three-fold after adding 75 mg ascorbic acid and four fold after adding 100 mg ascorbic acid (Cook and Monsen 1977; Monsen 1988; Reddy and Cook 1991). Adding 15 mg ascorbic acid caused a three fold increase in iron absorption from a rice porridge meal (Gillooly et al 1983). Studies with maize meals have shown a six fold increase in iron absorption with 150 g papaya containing 65 mg ascorbic acid (Layrisse et al. 1974), to a ten fold increase with 50 or 100 mg ascorbic acid (Derman et al, 1977).

Ascorbic acid can improve iron absorption even in the presence of inhibitors such as phytates in cereals and soya, tannins in tea and calcium. In India, 54 anemic preschool children were supplemented with 100 mg synthetic ascorbic acid versus a placebo, at each of the two main meals, for two months (seshadri et al. 1985).

Usual iron and ascorbic acid intakes were low. Ascorbic acid treatment improved hemoglobin concentrations significantly, from 9.38 to 11.30 g/L on average. There was no change in controls (9.08 versus 9.18 g/L) . Weekly iron status assessment showed the 50 mg ascorbic acid supplement to be most effective, and an improvement in iron status could be detected in six weeks.

Organic acids such as citric acid, malic acid, tartaric acid and lactic acid also enhances iron absorption (Derman et al. 1980; Gillooly et al. 1983; Ballot et al. 1987). The geometric mean iron absorption form a rice meal increased significantly with the addition of 1 g citric acid (by 3 fold) 1 g L- malic acid (by 2 fold) and 1 g tartaric acid (by 2.3 fold) (Gillooly et al. 1983).

By simple corollary it can be inferred that linking the nutritionally relevant part of the acid radical with the metal amino acid, we find that the enhancer is linked and becomes a part of the amino acid chelate.This orientation is considered ideal as the enhancer is positioned nearest to the mineral to do it's job best.

To elaborate, consider Iron absorption in a Human system. Clinical Trials clearly elaborate the importance of Ascorbic acid (vitamin c) in enhancing the bio absorption of Iron. For this to happen, it is simply and naturally assumed that Ascorbic acid be present in the digestive system

a) at a dosage b) in an ionic effective state c) at a position d) in a manner and most importantly e) at a time when iron is ingested

This in normal practice NEVER HAPPENS.

Mixing of iron with ascorbic acid is also not a solution as the stability of _Q Ascorbic acid deteriorates in the presence of a Mineral, in this case Iron.

This problem can be overcome by use of Mineral amino acid chelate having a nutritionally relevant anion radical in this case Ferrous Glycine Ascorbate or Ferrous bis glycine di Ascorbate.

US Patent Nos.4067994, 4599152, 4830716, 5516925, 6166071, 5 6426424, 6458981 , 6518240 6541051 relates to method of manufacture of an amino acid chelates.

However, they restrict themselves to the relevance, use and method of manufacture of mineral amino acid chelates in general and not on the anions attached. Mention of a few of the anion radicals, if any, in the prior o art is only by outlining it's role as a non interfering anion. There is no mention of the anion being linked & forming a part of the chelate molecule in a stoichiometric proportion in any patents.

Our invention relates to the charge on the metal totally neutralised by the carboxylic acid group of the alpha amino acid forming a chelate and 5 the resulting chelate is optionally converted to a quarternary ammonium complex either partly or fully using the 'N' of the alpha amino acid group with nutritionally relevant anion radical. Here it is to be understood that either all the alpha amino nitrogens are converted into quarternary ammonium ion(s) or preferably some of the alpha amino nitrogens are converted into quarternary ammonium ion(s) depending on the need. These complexes have a better solubility, bioavailability, stability and palatability in comparison with the compounds / complexes / chelates wherein the quarternary ammonium ion is absent.

The peaks of Infra red spectrum observed at 2100cm^"1 of the alpha amino acid and the finger print area of the nutritionally relevant anion radical are absent in the products as claimed in claim 1 and claim 2 emphasing the 10 complete reaction & formation of quarternary ammonium complex.

Proof for presence of a weak bond between quarternary ammonium ion and metal ion can be identified by observing in detail the finger prints areas / peaks formed in the metal alpha amino acid chelate having nutritionally relevant anion radicals) as compared to the chelate wherein i 5 the quarternary ammonium ion is absent.

The position of a peak due to formation of quarternary ammonium ion(s) vary depending upon the metal ion linked to the alpha amino acid.

For example, but not as a limitation, the IR spectrum as accompanied goes to prove the structures as claimed in claim 1 and claim 2.

2o Comparison of the IR graphs of a) Glycine b) Iron bis Glycinate c) Iron bis Glycine ascorbate d) Iron bis Glycine Diascorbate scanned from 400 to 4000cm^"1 clearly reveals that Iron bis Glycine ascorbate and Iron bis Glycine Diascorbate are unique complexes formed

25 as per our Invention claims and not a simple mixture of Iron bis Glycinate, Ascorbic acid, Glycine, Iron salt, etc.

Similarly x-ray diffraction of Iron bis Ascorbate and Iron bis diascorbate revealed the formation of a unique new complex and not the presence of mixtures of raw material ingredients namely Iron bis Glycinate, Ascorbic Acid, Glycine, Iron Salt, etc. This invention, as noted just in the above paragraphs, lays high emphasis on the importance of the method of manufacture and use of nutritionally relevant anion radical linked stoichiometrically to the mineral amino acid chelate.

OBJECTS AND SUMMARY OF THE INVENTION :

It is an object of the invention to provide a chelated mineral composition containing the nutritionally relevant anion radical(s) that forms a quarternary ammonium complex with 'N' of the alpha amino acid(s) thereby resulting in an increased bio availability of the metal, amino o acid(s) and nutritionally relevant anion radicals).

It is also the object of the invention to provide the mineral in a manner that it does not exhibit its characteristic metallic flavour or after taste such that it is favourably used in food supplements, beverages, tablets and as a supplement in any food /feed ingredients.

5 it is also another object of the invention to provide a chelated mineral composition containing the nutritionally relevant anion radicals) such that metal, amino acid and nutritionally relavant anion radicals) are in the most stable forms and do not accelerate oxidation / rancidity to the supplement / food products to which they are added, thereby increasing o the shelf life of food / feed supplement.

DETAILED DESCRIPTION OF THE INVENTION Before the present invention is disclosed and described, it is to be understood that this invention is not limited to the particular process steps and materials disclosed herein because such process steps and materials 5 may vary somewhat. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only. The terms are not intended to be limiting because the scope of the present invention is intended to be limited only by the appended claims and equivalents thereof. It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates therewise.

Essentially, the present invention includes compositions and methods of manufacturing metal amino acid chelates having nutritionally relevant anion radical(s) as structured below.

1. A metal alpha amino acid chelate having a nutritionally relevant anion radicals), the resonance hybrid structure of which is shown as

Wherein 'R' is hydrogen, alkyl, aryl, alkoxy, arylalkoxy, a side chain having branches or ring structure optionally with an heteroatoms such as Sulphur, Nitrogen, Halo, etc or a peptide group;

'X' is a nutritionally relevant anion radical linked to the 'N' of the quarternary ammonium group of the alpha amino acid(s);

'a' is a numerical number that satisfies the valency of the metal 'M'and the amino acid(s) bonded to the Metal which totally satisfies the valency on the metal thus forming a chelate; 'b' defines an integer to obtain the electrical charge created by the formation of quarternary ammonium complex ion which can be 1 to a;

'e' is the number of nutritionally relevant anion radical and an electrical equivalent to nullify the charge 'b';

'M' is either metal atom or a metal ion having the positive charge "a" ranging from +1 to +6 preferably +2 to +4;

Amino acid(s) used for chelation may be the same, different or in a combination thereof;

The dotted line between 'N' of amino acid and the metal represents a weak bond, formed due to delocalization of a lone pair of electrons present on the carboxylic oxygen of the amino acid thus forming a five membered ring with the metal ion.

2. A metal alpha amino acid chelate having a nutritionally relevant anion radicals), the resonance hybrid structure of which is shown as

Where R, M, X, a,b and e are the same as in structure 1. Y is an element or a group having ionic charge "d" which can be 1 to 4 for example Cl^"1, SO₄ ^"2, H₂PO₄ ^"1, HPO₄ ^"2, NO₃ ^"1, HSeO₃ ^"1 etc. "Metal amino acid chelate" or "amino acid chelate" shall include metal ions bonded to amino acids forming heterocyclic rings. The bonds may be coordinate covalent, covalent, and/or ionic at the carboxyl oxygen group. However, at the .alpha.-amino group, the bond is typically a coordinate ' covalent bond. Preferred amino acids include all of the naturally occurring amino acids. Additionally, for purposes of the present invention, "amino acid chelate" shall further include any charged amino acid chelate that is electrically balanced by a acid counter ion/ions.

The "Metal amino acid Hydroxide chelate" and "Metal amino acid salt '0 chelate" includes any chelate where the metal is bonded to the amino acid and carries a positive charge with the negative charge ion being any conventionally known anions excluding Radicals formed from ionic dissociation of nutritionally relevant acids .Hydroxide, Chloride, Sulphate, Nitrate, Carbonate and bicarbonate radicals are a few examples of the 5 Anion forming the above chelates.

"Metals" include nutritionally relevant metals that are known to be needed by living organisms, particularly plants and mammals, including humans. Metals such as copper (Cu), zinc (Zn), iron (Fe),Calcium (Ca), cobalt (Co), magnesium (Mg), manganese (Mn), and/or chromium (Cr), among 0 others, are exemplary of nutritionally relevant metals.

The "amino acid" in the present invention is preferably one or more of the naturally occurring amino acid selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, cystine, glutamine, glutamic acid, glycine, histidine, hydroxyproline, isoleucine, leucine, 5 lysine, methionine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and combinations thereof. However, djpeptides, tripeptides, and tetrapeptides formed by any combination of the naturally occurring amino acids may also be used. "Nutritionally relevant acid radical" is meant to cover all radicals obtained by dissociation (including ionic) of the nutritionally relevant acid or it's salts & esters.

"Nutritionally Relevant Acids" includes acids and that are known to be 5 needed by living organisms particularly Humans, Animals (including

Aquatic organisms /animals and Farming animals and mammals) and plants. They could be directly necessary for an organism's anabolism/growth or they could be required to catalyze / synthesize other nutritive substances produced in the body of an organism (ex enzymes, I o Harmones etc) in turn necessary for the organism's anabolism / growth.

Examples of some nutritionally relevant anion radical that forms part of the Metal amino acid chelates having a nutritionally relevant anion radical is presented below.

The nutritionally relevant acid used in the manufacture of Metal Amino 15 Acid Chelates having a nutritionally relevant anion radical is presented within brackets.

Ascorbate (from Ascorbic acid)

Nicotinate (from Nicotinic acid)

Folate (from folic acid)

0 Biotinate (from biotin)

Retinate (from vitamin A acid)

Citrate (from citric acid)

Malate (from malic acid)

Tartrate (from tartaric acid)

5 Formate (from formic acid)

Fumerate (from fumeric acid) Acetate (from acetic acid)

Propionate (from propionic acid)

Phosphate (from phosphoric acid)

Selenate (from selenious acid)

Lactate (from lactic acid)

Gluconate (from gluconic acid)

The salt and ester forms of the above acids also come under the perview of this application.

These chelates are prepared by reacting a metal amino acid salt chelate ° and a nutritionally relevant acid at a ratio sufficient to allow substantially all of the ions present in solution to react forming a positively charged metal amino acid chelate having the desired acid radical as the counter ion. Further, the metal amino acid chelates of the present invention will have a amino acid to metal to acid radical molar ratio from about 1 :1:1 to 4:1:2.

While not wanting to be bound by any theory, a possible mechanism of the process may be as below.

The present invention also reveals the process of manufacturing the alpha amino acid chelates having nutritionally relevant anion radical(s) as described above.

In order to manufacture a metal amino acid chelate having nutritionally relevant acid radical, it generally requires that the desired metal aminoacid Hydroxide chelate and desired acid both be dissolved in water/solvent. The acid releases an Hydrogen ion which reacts with the existing anion radical namely Hydroxide group of the metal amino acid chelate forming water. The acid group devoid of the Hydrogen ion links with the metal amino acid and forms a neutral chelate which when ionized has the metal Amino acid with the positive charge and the acid radical with the negative charge.

The composition can also be manufactured by reacting a metal Amino Acid salt chelate and a salt or ester of the desired acid. Here again the chemistry of reaction is the same with the addition that a salt will also be formed as a byproduct.

Reaction of Metal Amino Acid Hydroxide chelate with a salt or ester of desired acid will also give the desired composition with salt / alcohol as a byproduct.

Direct blending and Drying of the Metal Amino Acid Hydroxide chelate / Metal Amino Acid Salt chelate with desired acid or it's salts/esters would also yield the desired product though not in pure scales.

FLOW CHART

l inole 1 or 2 moles

Metal

Amino Acid Nutritionally relevant Aquous Chelate + molecule which when solution Hydroxide Dissociated forms Nutritionally Relevant Anion radical and H Ions

1 mole or 2 m( )les

Relevant Anion Ri idical + H₂0 EXAMPLES

The following examples illustrate methods of preparing metal amino acid chelates .

The examples provided in the specification are given illustrative purpose only and it is not intended that the said invention be restricted to those illustrations alone. These above mentioned novelties including all other substitutions, alterations and modifications of the present invention, without departing from the spirit of the invention are also stressed as a part of this description.

Example - 1

Preparation of Iron bi glycinate di Ascorbate chelate.

Into about 3 litres of water was dispersed 240 gms (1 mole) of Iron bi glycine Hydroxide chelate.

Next (2 moles) 352 gms of Ascorbic acid was added. The solution was continually stirred till the colour of the solution changed to dark brown and a clear solution is obtained. No heat was applied for this particular reaction though heat could optionally be used.

The resultant reaction formed a Iron bi glycinate di Ascorbate chelate liberating 36 gms of water. When spray dried the weight of the Ascorbic Acid chelate at 558 gms (1 mole) tallied to formation of Iron bi glycinate di Ascorbic chelate. The product was analysed and found to contain Iron, glycine and ascorbic acid in propotions matching the composition of Iron bi glycinate di Ascorbate. Example - 2

Preparation of Ferrous Methionine Folate Chelate.

Into about 5 litres of water was dissolved 222 gms (1 mole) Ferrous Methionine Chelate. To this solution was added 464 gms (1 mole) of Sodium Folate i.e., Folic acid Sodium salt. The solution was stirred.

The reaction resulted in the formation of 663 gms (1 mole) of Ferrous Methionine Folate Chelate. This product being water insoluble separated out of the solution and was dried by conventional process known in the trade.

Claims

1. A metal alpha amino acid chelate having a nutritionally relevant anion radical(s), the resonance hybrid structure of which is shown as

Wherein 'R' is hydrogen, alkyl, aryl, alkoxy, arylalkoxy, a side chain having branches or ring structured optionally with an hetero atom such as Sulphur, Nitrogen, Halo etc or a peptide group;

'a' is a numerical number that satisfies the valency of the metal 'M'and the amino acid(s) bonded to the Metal which satisfies the valency on the metal thus forming a chelate; 'b' defines an integer to obtain the electrical charge created by the formation of quarternary ammonium complex ion which can be 1 to a; 'e' is the number of nutritionally relevant anion radical and an electrical equivalent to nullify the charge 'b';

+b

Where R, M, X, a,b and e are the same as in structure 1. Y is an element or a group having ionic charge "d" which can be 1 to 4 preferably 1 to 2 for example Cl^"1, SO₄ ^"2, H₂PO₄ ^"1, HPO ^"2, NO₃ ^"1, HSeO₃ ^"1 etc.

3. A metal alpha amino acid chelate having a nutritionally relevant anion radicals), as claimed in claim 1 and claim 2 where the nutritionally relevant anion radical contributes to improved solubility, stability, bioavilability and palatability due to the formation of quarternary ammonium complex and selected Q from Ascorbate, Citrate, Isocitrate, Malate, Tartrate, Nicotinate and naturally occurring organic acids.

4. A metal alpha amino acid chelate having a nutritionally relevant anion radical(s), as claimed in claim 1 and claim 2 when the nutritionally relevant anion radical contributes to improved bioavilability due to the -5 formation of quarternary ammonium complex and selected from Folate, Biotinate, Retinate, Malonate, Succinate, Nicotinate, Formate, Fumerate, Acetate, Propionate, Lactate, Gluconate, Selanate.

5. A metal alpha amino acid chelate as claimed in the preceding claims wherein 'M' is a metal atom / ion selected from Copper, Cobalt, Calcium, 0 Iron, Manganese, Magnesium, Zinc, Chromium.

6. A metal alpha amino acid chelate having nutritionally relevant anion radicals) as claimed in claim 1 and claim 2 wherein the amino acid is selected from a list Alanine, arginine, asparagines, aspartic acid, cysteine, cystine, glutamine, glutamic acid, glycine, histidine, hydroxyproline, 5 isoleucine, leucine, lysine, methionine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and combinations thereof.

7. A metal alpha amino acid chelate as claimed in the preceding claims wherein 'R' is a radical of a naturally occurring amino acid, dipeptide or polypeptide.

8. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 1 and claim 2 wherein the aminoacid chelate may be represented by a ligand to metal molar ratio of 1 :1 , 2:1 , 3:1 or 4:1.

9. Metal Alpha Amino acid chelates having a nutritionally relevant anion radicals) as claimed in claim 1 and claim 2 wherein nutritionally relevant anion radicals are formed from preforms with a stoichmetry of atieast one 0 mole, typically two moles and in rare cases upto four moles, depending on the valency.

10. Metal Alpha Amino acid chelates as claimed in the preceding claims wherein 'M' is a metal, capable of exhibiting the variable valency preferably from 2 to 4.

5 11. Metal Alpha Amino acid chelates having a nutritionally relevant anion radicals) as claimed in claim 1 , in a form as Metal mono amino acid mono nutritionally relevant anion radical.

12. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 1 , in a form as metal bis amino acid mono o nutritionally relevant anion radical.

13. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 1 , in a form as metal bis amino acid bis nutritionally relevant anion radicals.

14. Metal Alpha Amino acid chelates having a nutritionally relevant anion radicals) as claimed in claim 1 , in a form as metal tri amino acid mono nutritionally relevant anion radical.

15. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 1, in a form as metal tri amino acid bis nutritionally relevant anion radicals.

16. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 1, in a form as metal tri amino acid tri nutritionally relevant anion radicals

17. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 2, in a form as metal mono amino acid mono element / group mono nutritionally relevant anion radical

8. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 2, in a form as metal bis amino acid mono element / group mono nutritionally relevant anion radical

19. Metal Alpha Amino acid chelates having a nutritionally relevant anion radieal(s) as claimed in claim 2, in a form as metal bis amino acid mono element / group bis nutritionally relevant anion radicals

20. Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 2, in a form as metal bis amino acid bis element / group mono nutritionally relevant anion radical

21. Metal Alpha Amino acid chelates having a nutritionally relevant anion radicals) as claimed in claim 2, in a form as metal bis amino acid bis element / group bis nutritionally relevant anion radicals

22. A Metal Alpha Amino acid chelates having a nutritionally relevant anion radical(s) as claimed in claim 1 and claim 2 preferably is Iron Glycine

Ascorbate, Iron bis Glycine Ascorbate, Iron bis Glycine Diascorbate, Iron Methionine Ascorbate, Iron bis Methionine Ascorbate and Iron bis Methionine Diascorbate.

23. A method of manufacturing Metal Alpha Amino acid chelates having a nutritionally relevant acid radical comprising by reacting directly or in an aqueous solution / solvent

a) a Metal Alpha Amino acid chelate with

b) a nutritionally relevant acid radical at a ratio sufficient to allow the reactants present in aqueous solution / solvent to react forming a product as claimed in claim 1 and claim 2.

24. A method of manufacturing Metal Alpha Amino Acid Chelates having a nutritionally relevant Acid Radical, as claimed in 23, wherein the Amino Acid Chelate includes any charged Amino Acid Chelates that is electrically balanced by a acid counter ion/s and wherein the amino acid chelate may be in a solution, in which case, the acid anion and the charged chelate may be in a solution.

25. A method of manufacturing Metal Alpha Amino Acid Chelates having a nutritionally relevant Acid Radical, as claimed in 23, wherein, the raw material used for its manufacture consisits of using Metal Alpha Amino Acid Hydroxide / salt Chelate including any chelate wherein the metal is bonded to Amino Acid and carries a positive charge with the negative charge ion being any conventional anions excluding radicals formed from ionic dissociation of nutritionally relevant acids and are inclusive of Hydroxide, Chloride, Nitrate, Sulphate, Carbonate and Bi Carbonate radicals.

26. A method of manufacturing Metal Alpha Amino Acid Chelates having a nutritionally relevant Acid Radical, as claimed in claim 23, wherein, the metal is divalent / trivalent / tetravalent and positive in charge and selected from the group consisting Calcium, Iron, Chromium, Copper, Zinc, Cobalt, Magnesium, Manganese, etc and combinations thereof.

27. A method of manufacturing Metal Alpha Amino Acid Chelates having a nutritionally relevant Acid Radical, as claimed in claim 23, wherein, the Amino Acid is selected from the group of naturally occurring Amino Acids, namely Alanine, arginine, asparagines, aspartic acid, cysteine, cystine, glutamine, glutamic acid, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and combinations thereof.

28. A method of manufacturing Metal Alpha Amino Acid Chelates having a nutritionally relevant Acid Radical, as claimed in claim 23, wherein the single Amino Acids may be substituted by a small peptide ligand, which may be in the form of dipeptide, tripeptides and in some cases even tetrapeptides.

29. A method as in claim 23, wherein in invention further comprising a subsequent step of drying the Metal Alpha Amino acid chelate having nutritionally relevant anion radical(s).

30. A method of manufacturing Metal Alpha amino Acid Chelates having nutritionally relevant anion radical wherein the compounds of claim 1 are highly soluble in comparison with the compounds wherein the quarternary ammonium ion is absent.

31. A method of manufacturing Metal Alpha Amino Acid Chelates as claimed in claim 1 and claim 2, wherein nutritional relevant radicals are derived from natural sources preferably from Citrus fruits.

32. The use of the compounds of claim 1 and claim 2 for better bio absorption of metals.

33. The use of the compounds of claim 1 and claim 2 for better bio absorption of amino acids.

34. The use of the compounds of claim 1 and claim 2 for better bio absorption of nutritionally relevant anion radicals).

35. The use of the compounds as claimed in the claim 1 and claim 2 wherein the stability of the metal, amino acid(s), nutritionally relevant anion radical(s) are improved resulting in the increased shelf life of the food / feed supplement in which they are incorporated.

36. The use of the compounds as claimed in the claim 1 -and claim 2 resulting in a product which does not exhibit characteristic metallic taste of the metal.