WO2004082592A2 - Chelates d'acides amines metalliques comprenant un radical/des radicaux anionique(s) important(s) d'un point de vue nutritionnel - Google Patents

Chelates d'acides amines metalliques comprenant un radical/des radicaux anionique(s) important(s) d'un point de vue nutritionnel Download PDF

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Publication number
WO2004082592A2
WO2004082592A2 PCT/IN2004/000063 IN2004000063W WO2004082592A2 WO 2004082592 A2 WO2004082592 A2 WO 2004082592A2 IN 2004000063 W IN2004000063 W IN 2004000063W WO 2004082592 A2 WO2004082592 A2 WO 2004082592A2
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amino acid
metal
nutritionally relevant
radical
alpha amino
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PCT/IN2004/000063
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English (en)
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WO2004082592A3 (fr
Inventor
Ramu Krishnan
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Ramu Krishnan
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Publication of WO2004082592A3 publication Critical patent/WO2004082592A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/76—Metal complexes of amino carboxylic acids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/17—Amino acids, peptides or proteins

Definitions

  • 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 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
  • 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.
  • 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.
  • 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.
  • 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
  • the product 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.
  • 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.
  • 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.
  • 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.
  • an amino acid chelate may be represented at a amino acid to metal molar ratio of 2:1.
  • 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.
  • 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.
  • R is H
  • the amino acid is glycine which is the simplest of the .alpha.-amino acids.
  • 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.
  • 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.
  • a metal atom / ion can accept bonds over and above the oxidation state of the metal is due to the nature of chelation.
  • 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.
  • a metal ion with a normal valency of +2 can be bonded by four bonds when fully chelated.
  • the metal ion is typically bonded to the .alpha.-amino group by coordinate covalent bond and weak bond as mentioned above.
  • 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.
  • 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.
  • inhibitors such as phytates in cereals and soya, tannins in tea and calcium.
  • 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).
  • 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).
  • US Patent Nos.4067994, 4599152, 4830716, 5516925, 6166071, 5 6426424, 6458981 , 6518240 6541051 relates to method of manufacture of an amino acid chelates.
  • 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.
  • a quarternary ammonium complex either partly or fully using the 'N' of the alpha amino acid group with nutritionally relevant anion radical.
  • 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.
  • the present invention includes compositions and methods of manufacturing metal amino acid chelates having nutritionally relevant anion radical(s) as structured below.
  • a metal alpha amino acid chelate having a nutritionally relevant anion radicals having a nutritionally relevant anion radicals
  • '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.
  • 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 , SO 4 "2 , H 2 PO 4 "1 , HPO 4 "2 , NO 3 "1 , HSeO 3 "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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • Nicotinate from Nicotinic acid
  • Citrate (from citric acid)
  • Tartrate from tartaric acid
  • Lactate (from lactic acid)
  • 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.
  • 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.
  • the present invention also reveals the process of manufacturing the alpha amino acid chelates having nutritionally relevant anion radical(s) as described above.
  • a metal amino acid chelate having nutritionally relevant acid radical 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.
  • composition can also be manufactured by reacting a metal Amino Acid salt chelate and a salt or ester of the desired acid.
  • a metal Amino Acid salt chelate and a salt or ester of the desired acid.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)

Abstract

La présente invention concerne des compositions et des procédés pour préparer des chélates d'acides aminés métalliques comprenant un radical/des radicaux anionique(s) important(s) d'un point de vue nutritionnel ayant une solubilité supérieure et une meilleure bioabsorption. La composition est préparée par réaction d'un chélate d'hydroxyde d'acides aminés métalliques avec un radical acide important d'un point de vue nutritionnel, selon un rapport molaire approprié tel que le nouveau chélate formé conserve sa structure d'acides aminés métalliques mais est lié pour former des ions d'ammonium quaternaire liés à un radical/des radicaux important(s) d'un point de vue nutritionnel obtenu(s) par dissociation ionique d'un acide/d'acides important(s) d'un point de vue nutritionnel.
PCT/IN2004/000063 2003-03-19 2004-03-17 Chelates d'acides amines metalliques comprenant un radical/des radicaux anionique(s) important(s) d'un point de vue nutritionnel WO2004082592A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102258126A (zh) * 2011-08-19 2011-11-30 长沙微安生物科技有限公司 精氨酸螯合物在动物饲料添加剂中的应用
CN101062913B (zh) * 2007-06-05 2013-01-23 重庆大学 羟基脯氨酸-锌螯合物的制备方法
CN103772485A (zh) * 2014-01-23 2014-05-07 上海旭新化工科技有限公司 L-丙氨酰-l-谷氨酰胺铬盐的合成方法
EP3216782A4 (fr) * 2014-11-07 2018-07-18 NPA - Núcleo De Pesquisas Aplicadas LTDA. Composés d'acides aminés de fer, procédé de préparation de composés d'acides aminés de fer, compositions contenant des composés d'acides aminés de fer et leurs utilisations

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516925A (en) * 1994-08-23 1996-05-14 Albion International, Inc. Amino acid chelates having improved palatability
WO2003016332A2 (fr) * 2001-08-16 2003-02-27 Albion International, Inc. Amelioration de la solubilite des chelates d'acides amines de fer et des proteinates de fer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516925A (en) * 1994-08-23 1996-05-14 Albion International, Inc. Amino acid chelates having improved palatability
WO2003016332A2 (fr) * 2001-08-16 2003-02-27 Albion International, Inc. Amelioration de la solubilite des chelates d'acides amines de fer et des proteinates de fer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101062913B (zh) * 2007-06-05 2013-01-23 重庆大学 羟基脯氨酸-锌螯合物的制备方法
CN102258126A (zh) * 2011-08-19 2011-11-30 长沙微安生物科技有限公司 精氨酸螯合物在动物饲料添加剂中的应用
CN103772485A (zh) * 2014-01-23 2014-05-07 上海旭新化工科技有限公司 L-丙氨酰-l-谷氨酰胺铬盐的合成方法
EP3216782A4 (fr) * 2014-11-07 2018-07-18 NPA - Núcleo De Pesquisas Aplicadas LTDA. Composés d'acides aminés de fer, procédé de préparation de composés d'acides aminés de fer, compositions contenant des composés d'acides aminés de fer et leurs utilisations

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