MX2008006077A - Salts of mineral nutrients stabilized with amino acids and/or ammonium salts, products and food supplements that contain them and methods for obtaining same - Google Patents

Abstract

Salts of mineral nutrients stabilized with amino acids and/or ammonium salt, product and food supplement in which they are included and procedures of obtention, where the salts are obtained with anions of organic acids or inorganic anions and metallic cations associated with amino acids and/or ammonium salt, in which the invention introduces its general structure:{ [Ac]n-âÇ¢Men+âåÉn [Amino acid and/ or ammonium salt]}âÇ¢x H2O WhereâåÉrepresents a covalent dative bond, These new compounds have better taste and more solubility in water, making them more bioavailable.

Description

SALTS OF MINERAL NUTRIENTS STABILIZED WITH AMINO ACIDS AND / OR AMMONIUM SALT, PRODUCTS AND FOOD SUPPLEMENT THAT CONTAIN THEM AND PROCEDURES FOR OBTAINING Field of the Invention The present invention relates to the field of chemistry and more specifically to chemistry applied to the food industry and dietary supplements. The invention provides new compounds which are mineral salts stabilized by amino acids and / or ammonium salts, with a greater solubility in water, with improved organoleptic characteristics and with a higher bioavailability. Description of the State of the Technique The importance of an adequate diet that succeeds in supplying the requirements of essential minerals for both animals and humans is well documented in the literature. There are numerous works that show the problems caused by the deficiency of essential minerals and how they are reversed by the intake of the same. Minerals are indispensable for cellular metabolic processes either as co-factors of enzymes, forming part of electron transport chains, etc.

They constitute a group of nutrients (approximately 30) that does not supply energy to the organism but with important regulatory functions in addition to its structural function as it forms part of many tissues. They are constituents of bones and teeth, control the composition of extra and intra-cellular fluids and are part of enzymes and hormones, essential molecules for life. Within them, two large groups can be distinguished: macroelements, so-called because they have to be contributed in greater quantity by the diet or because they are in greater proportion in the corporal tissues: calcium, phosphorus, magnesium, sulfur, potassium, sodium and chlorine. Others, such as cobalt, copper, iron, chromium, fluorine, iodine, manganese, selenium and zinc, are also necessary, but in smaller amounts, so they are called microelements or trace elements. In the same way, it is important to provide adequate levels of amino acids. Amino acids are the basis of proteins. The foods we eat provide us with proteins. But such proteins are not normally absorbed in such a constitution but, after their cleavage ("hydrolysis" or rotu-ra), caused by the digestion process, they cross the intestinal wall in the form of amino acids and short chains of peptides, as which is called "hepatic whole circulation." These substances are initially incorporated into the bloodstream and, from there, are distributed to the tissues that need them to form proteins, consumed during the life cycle. HE knows that of the 20 known protein amino acids, eight are indispensable (or essential) for human life and two are "semi-indispensable". These ten amino acids are those that need to be incorporated into the body in their daily diet and, even more so, at times when the body needs them most: in dysfunction or disease. The most problematic essential amino acids are tryptophan, lysine and methionine. Its lack in populations where cereals or tubers are the basis of food is typical. Deficiencies in essential amino acids affect children much more than adults. It should be noted that, if only one of them is missing (essential amino acid) it will not be possible to synthesize any of the proteins in which said amino acid is required. This can lead to different types of malnutrition, depending on the limiting amino acid. It is important to emphasize that if for a correct nutrition, a diet must present the adequate levels of essential metals, many of the ways in which these metals are found in nature can not be used, since most of the compounds that contain the metals do not present it in such a way that they can be absorbed, distributed, and used efficiently. The salts of mineral nutrients of organic or mineral acids that are used to combat the deficiency syndromes In humans, animals or vegetables have the limitations for their use the metallic taste that limits their acceptance and / or a low solubility in water that limit their absorption or bio-availability. The absorption of the essential elements depends in most cases on the solubility of the salts that are used. Thus, as a rule, the greater the solubility, the greater the absorption. The other factor that matters is the biical behavior of the element once it is absorbed. This means that the element must comply with the same metabolic routes as those known for the salts considered as reference. The products formed between the salts of organic or mineral acids that are produced with amino acids and / or ammonium salts generate a product with a more pleasant taste and with an increased solubility. Different complex compounds of essential metals and amino acids have been developed in the past in a ratio of 1: 1 in order to increase the bioavailability of said metals after ingestion (see US Patents 3,941,818, 3,925,433, 3,950,372, 4,021,569, and 4,067,994 ). In said patents, the complexes formed form chelates. Chelate is a very simple term that refers to the formation of rings that include the metal center in coordination compounds. The formation of this type of compounds occurs when a binder with more than one "tooth" is coordinated to the same metal center. The salts of the present invention are not compounds that are side by side as the aforementioned systems, but stabilized by a dative link and have very high solubilities, (solutions of more than 50% by weight, or 400 grams per liter of water), which It allows the addition to the food in a simple way and without modifying the aqueous volumes of the same. Compendium of the Invention It is therefore an object of the present invention to obtain products of mineral salts of organic or inorganic acids associated with an amino acid and / or ammonium salts that have a formula or general structure:. { [Ac] n ~ - Men + - n [amino acid / ammonium salt]} • x H20 where < - represents a covalent dative union and that present better flavor and greater solubility in water, which makes them more bio-available. Another object of the present invention is to provide salts of mineral nutrients stabilized with amino acids and / or ammonium salt the metal "Men + is selected from the group comprising the following cations: calcium, magnesium, zinc, iron, copper, manganese, sodium , potassium, nickel or cobalt It is yet another object of the present invention to provide salts of mineral nutrients stabilized with amino acids and / or ammonium salt wherein the acid is selected from the group It comprises: fumaric acid, malic acid, hydrochloric acid or sulfuric acid, pure or associated. It is further another object of the present invention salts of mineral nutrients stabilized with amino acids and / or ammonium salt where the amino acid is selected from the group comprising: aminoacetic acid (glycine) and / or usina and the ammonium salt is organic or inorganic. It is also another object of the present invention a food supplement containing mineral salts stabilized by amino acids and / or ammonium salt that has the ability to improve the nutrition and health of humans and animals, by efficiently increasing absorption, distribution and use of minerals. It is also another object of the present invention the mineral nutrient salts stabilized with amino acids and / or ammonium salt where a suitable vehicle such as water, carbonated water, syrups, with natural or synthetic fruit juices, liquid or powder, yoghurts, desserts Dairy, butter, cheeses and margarines. It is also another object of the present invention the mineral nutrient salts stabilized with amino acids and / or ammonium salt where the selected vehicle or form comprises a tablet, dragees, effervescent powder, powder, tablets, candy, rigid or soft capsule for product presentation pharmaceutic, dietary supplement or for veterinary use.

It is also another object of the present invention the mineral nutrient salts stabilized with amino acids and / or ammonium salt that can be part of farinaceous products such as bread, pasta, cookies, bills, dehydrated foods or concentrates such as stews, soups, desserts, jellies , rolled cereals, grains or extruded cereals, cereal bars, whole or derived soybeans, powdered or rolled flour, and oats. It is also another object of the present invention the mineral nutrient salts stabilized with amino acids and / or ammonium salt because when the vehicle used is aqueous, the resulting solution can be used as foliar fertilizer or as fertilizer. It is also another object of the present invention a process for the synthesis of mineral salts stabilized with amino acids and / or ammonium salt, characterized by comprising the following steps: a) from the previously formed salt that is solubilized in an aqueous solution of the amino acid and / or ammonium salt; b) heating and adjusting the pH appropriately; c) the product formed in aqueous solution is obtained, which by evaporation of the water the product can be obtained in the form of a dry powder. The product solution or dry powder can be used.

It is also another object of the present invention a method for the synthesis of copper or iron or manganese salts stabilized with amino acids and / or ammonium salt, characterized by comprising the following steps: a) displacement of the calcium salts formed by the ferrous or ferric or copper or manganese ions by incorporation of the ferrous or ferric or cupric or manganese sulfates respectively; b) calcium sulphate precipitation formed, the ferrous or copper or manganese or manganese salt of the same anion remaining in solution and bound with the amino acid and / or ammonium salt; c) filtrate to separate the precipitated calcium sulfate and the formed product remains in aqueous solution, d) evaporation of the water until the product is obtained in the form of a dry powder. It is also another object of the present invention a method for the synthesis of salts, characterized in that it comprises of the following steps: a) solubilization in the aqueous solution of the amino acid and / or ammonium salt in the established ratio of the general formula, b ) heating of the solution and adjustment of the pH, c) the formed product remains in aqueous solution and can be obtained as a dry powder by evaporation of the water, where the salts are cupric sulfate, zinc sulfate potassium sulfate, sodium sulfate, manganese sulfate, ferrous sulfate, ferric sulfate, sodium chloride, potassium chloride or calcium chloride. Brief Description of the Drawings The figural shows the zinc fumarate sample associated with glycine (Zn biofumarate) and the glycine pattern. Figure 2 shows the sample of zinc fumarate associated with glycine (Zn biofumarate) and the glycine pattern after the ninhydrin reaction. Detailed Description of the Invention Organic anion products have been developed such as fumarate, malicate, gluconate, lactate, as well as inorganic anions, such as sulfates or chlorides, in pure or combined form of cations such as calcium, magnesium, iron, zinc, copper, manganese, sodium, potassium, cobalt and nickel associated with amino acids such as glycine (amino acetic acid) and / or L-Lysine and / or ammonium salt. The salts formed have a markedly greater solubility in water with acceptable taste, when evaluated against the non-associated salt taken as a standard and at the same concentration of the metal ion that it is necessary to supply. These characteristics of the products formed make them very useful for the supply of macro and micronutrients minerals in dietary supplements, medicinal products and in foods or drinks conveniently fortified or fortified.

The general chemical structure of the compounds formed responds to the following scheme:. { [Ac] n- Men + - n [amino acid and / or ammonium salt]} - x H20 where: n takes values from 1 to 3, and x takes values from 0 to 10. The metal Men + can be calcium, magnesium, zinc, iron, copper, manganese, sodium, potassium, cobalt or nickel. The acid can be fumaric acid, lactic acid, gluconic acid, malic acid, hydrochloric acid or sulfuric acid, pure or associated. The amino acid can be aminoacetic acid (glycine) and / or lysine. The ammonium salt can be organic or inorganic. Once the structure of the formed product has been studied, the formation of a product in which the amine nitrogen of the amino acid and / or ammonium salt is bound to the metal by a coordinated dative union is demonstrated (see figures 1 and 2). The functional identification of the coordinated dative union with the amine nitrogen of the amino acid was characterized by the reaction with ninhydrin (see figures 1 and 2). Figure 1 shows the zinc fumarate sample associated with glycine (Zn biofumarate) and the glycine standard. In Figure 2 the same sample is observed after the reaction with ninhydrin. The violet color of the glycine pattern shows that glycine is free. The yellow color corresponds to the reaction of the claimed product with ninhydrin, said reaction demonstrates that the carboxylic group of glycine is free while the amine group is associated with the metal (in this case Zn). If the glycine had been free the color would have been violet. If, on the other hand, both functional groups of glycine (amino and carboxylic) had been bound to the metal (as in the case of the compounds to nuclides), there would have been no reaction with ninhydrin and it would be colorless. The product has the characteristic of not forming a chelate and the obtained salt has better characteristics of solubility and flavor than the salt alone. The object of the present invention is the production of mineral salt products of organic or inorganic acids associated with an amino acid and / or ammonium salt having a general structure:. { [Ac] n "- Men + - n [amino acid and / or ammonium salt]. · - x H20 that have a better taste and greater solubility in water, which makes them more bio-available. a) from the previously formed salt, which is solubilized in an aqueous solution of the amino acid and / or ammonium salt, it is heated and adjusted in a suitable manner.The product formed in aqueous solution is obtained which by evaporation of water, the product can be obtained as a dry powder. The product solution or dry powder can be used; b) the calcium salts formed can be displaced by the ferrous or ferric or cupric or manganese ions by incorporation of the ferrous, ferric, cupric or manganese sulfates respectively. The calcium sulphate formed precipitates, leaving the ferrous, ferric, copper or manganese salt of the same anion in solution and bound with the amino acid and / or ammonium salt. It is filtered to separate the precipitated calcium sulphate and the product formed remains in aqueous solution, which can be obtained by evaporation of the water in the form of a dry powder; c) salts such as cupric sulfate, potassium zinc sulfate, sodium sulfate, manganese sulfate, ferrous or ferric sulfate can also be formed by solubilizing them in the aqueous solution of the amino acid in the established ratio of the general formula, heating the solution and adjusting the pH. The product formed remains in aqueous solution and can be obtained as dry powder by evaporation of water; d) salts such as sodium chloride, potassium chloride, magnesium chloride or calcium chloride can also be formed by solubilizing them in the aqueous solution of the amino acid in the established ratio of the general formula, heating the solution and adjusting the pH. The product formed remains in aqueous solution and can be obtained as dry powder by evaporation of water.

COMPARATIVE SOLUBILITY DATA: Ferrous fumarate (Ref 4094 Merck Index XII, page 686) MW 169.90, Fe ++ content 32.87%, pa Fe 55.47. Solubility in water at 25 ° C: 1.4 grams per liter of water. Allows 0.460 grams Fe ++ (ferrous) per liter of water ferrous fumarate stabilized with two moles of glycine (aminoacetic acid): Contains Ferrous Fumarate 169.90 gr (53.09%). Glycine (2 x 75.07) 150.14 gr (46.91%). Product 320.04 gr (17.45% Fe). Solubility in water at 25 ° C, as ferrous fumarate stabilized with two moles of glycine: 54.6 grams per liter. As ferrous fumarate (53.9%): 29.0 grams / liter. Allows: 9.53 grams Fe ++ (ferrous) per liter of water Increase in solubility per liter: 20.7 times (results from: 9.53 g of Fe / 0.460 g of Fe). The exposed data clearly show the increase in the water solubility of a salt such as ferrous fumarate, which is used as a source of the micronutrient mineral iron in dietary supplementation in fortified foods. Calcium Fumarate 3H20 Manufacturer Ref. Bartek Inc., Canada) MW 208.18 Calcium content 19.25% (pa Ca 40.08) Solubility in water at 25 ° C: 1.22 grams per liter: allows to solubilize 0.234 gram Ca ++ / liter of water calcium fumarate 3H20 stabilized with two moles of glycine (aminoacetic acid) Calcium Fumarate 3H20: 208.18 58.09% 2 glycine: 2 x 75.07 150. , 14 41.91% 358.32 11.18% as calcium. Solubility in water as calcium fumarate stabilized with two moles of glycine: 50. 0 grams / liter As calcium fumarate: 29,045 grams / liter As calcium (19.25%): 5,591 grams calcium / liter Increase in solubility: 23.9 times (results: 5,591 / 0.234 grams) as calcium. Exemplary Embodiments The following specific examples provided herein serve to illustrate the nature of the present invention.

These examples are included for illustrative purposes only and are not to be construed as limitations on the invention claimed herein. Example 1 Preparation of the calcium salt as calcium fumarate with aminoacetic acid (glycine) 5.0% solution. 1. In a 2000-cc beaker, place: purified water: 1800 gr. Weigh calcium hydroxide (minimum 95%): 24.84 gr (correct for purity and humidity). Disperse homogeneously. 2. Weigh aminoacetic acid (98.5% minimum): 47.92 grams and incorporate. Heat in a water bath with agitation. 3. Weigh fumaric acid (99.0% minimum): 37.05 grams, and incorporate. Continue heating in a bain-marie, with agitation, so as to maintain the solution between 60 and 85 ° C, for not less than 30 minutes. 4. Take a sample and adjust the pH of the solution to 5% w / w to 6.5 (6.2 to 6.8) using calcium hydroxide or fumaric acid if necessary. 5. Once the pH is adjusted, the calcium is evaluated, and it must give not less than 0.56 g calcium. 6. The solution obtained is filtered by paper and preferably with a product to aid filtration, obtaining a crystalline solution. 7. The obtained solution can be dried by hot air until dry. The powder can contain no more than 15% as water of crystallization. 8. Approximately 100 to 112 grams of dry product are obtained, according to water of crystallization. 9. In industrial form the solution is prepared in suitable reactors and the solution is dried by spray system. EXAMPLE 2 Preparation of a ferrous salt, such as ferrous fumarate with aminoacetic acid (glycine), 10% solution: 1. In a 2000 cc beaker are placed: Purified water: 900 mL or grams. Weigh calcium hydroxide (minimum 95%): 24.84 gr (correct for purity and humidity). Disperse homogeneously with agitation. 2. Weigh aminoacetic acid (98.5% minimum): 47.92 - we achieve and incorporate. Heat in a water bath with agitation. 3. Weigh fumaric acid (99.0% minimum) 37.05 grams, and incorporate. Continue heating in a bain-marie, with stirring, in order to maintain the solution between 60 and 85 ° C, for not less than 30 minutes. 4. Take a sample and adjust the pH of the solution to 5% w / w to 4.5. 5. Once the pH is adjusted, it is incorporated: ferrous sulphate 7H20 (minimum 19.8% Fe ++): 88.74 gr. The heating is cut, continuing the agitation for not less than 30 minutes. 6. Allow to settle, filter the supernatant with the aid of filtration, obtaining a dark greenish crystalline solution. The solution contains about 1.75% as iron and 10% (9.5 to 10.5%) as a product in solution. 7. The obtained solution can be dried by hot air until dry. The loss by drying at 105-108 ° C must be no greater than 10%. 8. 100 to 115 grams of the dried product are obtained, according to water of crystallization. 9. In Industrial form the solution is prepared in suitable reactors and can be dried by spray system.

Claims (16)

1. CLAIMS 1. Salts of mineral nutrients stabilized with amino acids and / or ammonium salt, where the salts are obtained with anions of organic acids or inorganic anions and metal cations associated with the amino acids and / or ammonium salt, characterized in that the metal cations are bound to the anions by means of an ionic bond and by a covalent dative linkage with the lower group of the amino acid and / or ammonium salt, having as a general formula:. { [Ac] n ~ - Men + - n [amino acid and / or ammonium salt]} • x H20 where: n takes values from 1 to 3 and, x takes values from 0 to 10.
2. 2. Salts of mineral nutrients stabilized with amino acids and / or ammonium salt of claim 1, characterized because the metal "Men + is selected from the group comprising the following cations: calcium, magnesium, zinc, iron, copper, manganese, sodium, potassium, nickel or cobalt
3. 3. Salts of mineral nutrients stabilized with amino acids and / or ammonium salt of claim 1, characterized in that the acid is selected from the group comprising: fumaric acid, alic acid, hydrochloric acid or sulfuric acid, pure or associated
4. 4. Salts of mineral nutrients stabilized with amino acids and / or ammonium salt of claim 1, character - because the amino acid is selected from the group comprising: aminoacetic acid and / or lysine and the ammonium salts, which are organic or inorganic.
5. 5. Salts of stabilized mineral nutrients according to claim 1, characterized in that they are coated or encapsulated.
6. 6. A product for the treatment of deficiency deficiencies in humans, animals and plants, and source of the mineral macro and micro nutrients, characterized in that it comprises the salts according to any of the preceding claims.
7. 7. A nutritional supplement to improve the nutrition and health of humans and animals, by efficiently increasing the absorption, distribution and utilization of minerals, characterized by comprising the mineral salts stabilized by amino acids and / or ammonium salt in accordance with the preceding claims and at least one acceptable vehicle.
8. 8. Food supplement to improve the nutrition and health of humans and animals, by efficiently increasing the absorption, distribution and use of minerals, according to claim 6, characterized in that said vehicle is selected from the group comprising water, carbonated water, syrups, with natural or synthetic fruit juices, liquid or powder, yoghurts, dairy desserts, butter, cheeses and margarines.
9. 9. Food supplement to improve the nutrition and health of humans and animals, by efficiently increasing the absorption, distribution and use of minerals, according to claim 6, characterized in that the vehicle is selected from the group comprising tablets, dragees, effervescent powder, powder, tablets, candy, rigid or soft capsule for presentation of pharmaceutical product, dietary supplement or for veterinary use.
10. 10. Food supplement to improve the nutrition and health of humans and animals, by efficiently increasing the absorption, distribution and use of minerals, according to claim 6, characterized because it is part of farinaceous products such as bread, pasta, cookies, bills, food dehydrated or concentrated as stews, soups, desserts, gelatins, rolled cereals, grains or extruded, cereal bars, whole or derivative soybeans, in powder or laminated flours, and oats.
11. 11. A product to be used as fertilizer or foliar fertilizer, characterized in that it comprises the salts of claim 1 plus an aqueous vehicle.
12. 12. A process for the synthesis of mineral salts stabilized with amino acids and / or ammonium salt, according to claim 1, characterized in that it comprises the following steps: a) solubilize in an aqueous solution of the amino acid and / or ammonium salt, the previously formed salt, in the stated ratio of the general formula of claim 1, b) heating to a temperature between X and Y ° C and adjusting the pH to a value between A and B, and c) obtaining the product formed in aqueous solution.
13. 13. A process according to claim 12, characterized in that the water of said product in aqueous solution is evaporated until obtaining the product as a dry powder.
14. 14. A process for the synthesis of copper or iron or manganese salts stabilized with amino acids, according to claim 1, characterized by comprising the following steps: a) displacement of the calcium salts formed by the ferrous or ferric or cupric ions or manganese by incorporation of the ferrous or ferric or cupric or manganese sulfates respectively; b) precipitation of the calcium sulphate formed, the ferrous or copper or manganese salt of the same anion remaining in solution and bound with the amino acid and / or ammonium salt; c) filtrate to separate the precipitated calcium sulfate so that the formed product remains in aqueous solution; d) evaporation of the water until the product is obtained in the form of a dry powder.
15. 15. Process according to claim 1, characterized in that the salts are selected from the group: cupric sulfate, zinc sulfate potassium sulfate, sodium sulfate, manganese sulfate, ferrous or ferric sulphate.
16. 16. Process according to claim 1, characterized in that the salts are selected from the group comprising sodium chloride, potassium chloride and calcium chloride.