BRPI1002480A2 - cell wall containing mineral complexes, preparation processes, compositions containing them and use of these mineral complexes - Google Patents

Abstract

MINERAL COMPLEXES CONTAINING CELL WALL, PREPARATION PROCESSES, COMPOSITIONS CONTAINING THEM AND USE OF THESE MINERAL COMPLEXES. This invention relates to novel mineral complexes prepared by the reaction between the cell wall of Saccharomices yeast and particularly Saccharomices cerevisiae yeast and mineral sources selected from iron, zinc, copper, manganese, magnesium, calcium, chromium and cobalt. Mineral complexes are characterized by having coordinated metal centers on a cell wall and can be efficiently used as mineral supplements for animal and human nutrition.

Description

"MINERAL COMPLEX CONTAINING CELL WALL, PREPARATION PROCESSES, COMPOSITIONS CONTAINING THEM AND USE OF THESE MINERAL COMPLEXES"

FIELD OF INVENTION

This invention relates to novel mineral complexes prepared by the reaction between the yeast cell wall Saccharomices and mineral sources selected from iron, zinc, copper, manganese, magnesium, calcium, chromium and cobalt. Mineral complexes are characterized by having metallic centers coordinated to the cell wall and can be used as mineral supplements for animal and human nutrition.

BACKGROUND OF THE INVENTION

Mineral supplementation in organisms is fundamental to the good development of the species, since adequate levels of essential minerals are hardly attained only by food intake. A mineral is considered essential if (i) the mineral concentration does not vary for individuals of the same species, (ii) its removal from the organism results in reproducible physiological and structural abnormalities, (iii) the addition of the mineral prevents or reduces the abnormality caused by (iv) deficiency-induced abnormalities are accompanied by specific biochemical changes and (v) these biochemical changes can be prevented or eliminated by the addition of the mineral. The three main functions of minerals are to act directly or indirectly (i) in the supply of energy, (ii) assist in the growth and maintenance of body tissues and (iii) regulate metabolic processes.

Animals obtain essential minerals from two sources: (1) food and water intake and (2) dietary supplementation, which is the most widely used form. Mineral deficiencies are caused by (i) insufficient amounts of minerals in food, (ii) deficiencies in the body of another mineral or nutrient, such as vitamins, amino acids and lipids, which reduce absorption, (iii) any condition that increases the speed passage of minerals through the intestine, such as diarrhea and (iv) the presence of an antagonistic metabolite that increases the requirements of certain minerals. For these reasons, supplementation should preferably be done with mineral supplements that are more bioavailable and have less side effects on animal organisms.

One of the most well-known forms of minerals for mineral supplementation today are chelates, substances characterized by presenting organic binders coordinated to a metallic center by at least two functional groups. Chelates may be prepared using the; various ligands, which must have the characteristics necessary for their formation, and amino acids are one of the most used ligands for this purpose. Amino acid chelates are cyclic neutral compounds that usually have five-membered rings formed by the interaction between the amino acid carboxyl and amino groups with the metal center. Amino acid chelates have adequate stability constants so that they can be absorbed by the body and are therefore successfully used as mineral sources for supplementation in animals, humans and plants.

Chelates can also be prepared with peptides in place of free amino acids. In this case, the peptides may be in the form of low molecular weight dipeptides, tripeptides or tetrapeptides, obtained by enzymatic hydrolysis of proteins in the presence of endopeptidases and exopeptidases. When chelates are prepared from proteins, protein hydrolysates or even low molecular weight peptides, they are termed as proteinates and their characterization is very difficult due to the complexity of the matrix used, characterized by having a great diversity of structures present in the mixture of proteins. peptides used in their preparation.

When amino acid, peptide or protein chelates are not neutral and have at least one metal-bound inorganic anion, they may also be appropriately referred to as mineral complexes or metal complexes.

There are several documents in the literature describing the preparation of chelates and amino acid complexes. In US Patent Document No. 4,599,152, the author teaches how to prepare amino acid chelates from metal centers selected from iron, zinc, manganese, magnesium, copper or calcium. In this paper, the author shows that chelates can be prepared by an electrolyte process in the absence of inorganic counterions. In another document, filed under US Patent No. 4,830,716, the author shows how to prepare amino acid chelates of selected metal ions from calcium, iron, magnesium, manganese or zinc by reacting amino acids and oxides, hydroxides or carbonates of metals of interest. In another document, filed under US Patent No. 6,352,714, the authors show how to prepare mineral proteinates that are used as animal nutrition supplements from a protein hydrolyzate prepared from chromium-tanned leather scraps.

In addition to minerals, the diet of humans and animals can also be supplemented with other supplements that help the proper functioning of organisms. Among these supplements, we highlight the cell wall, one of the products of Saccharomices cerevisiae yeast fractionation, due to its prebiotic activity. This class of compounds comprises non-digestible ingredients that stimulate growth and preferably the activity of a limited number of microorganisms capable of providing a healthy intestinal environment to the host. Non-digestible carbohydrates, such as plant cell wall and yeast, are classified in this group because they are made up of glycomananoprotein complexes, in particular mannanoligosaccharides, capable of binding to the bacteria fimbria and inhibiting their colonization in the gastrointestinal tract. In addition, they can also be used as nutrients by other bacteria. The yeast cell wall can be obtained from mechanical processes, such as treating aqueous suspensions of yeast under high pressure or in a ball mill. The cell wall obtained in these cases is isolated after separation of the yeast extract formed by one of the available industrial processes such as centrifugation. However, the cell wall is most commonly obtained from yeast hydrolysis or autolysis and preferably through the autolysis of Saccharomices cerevisiae yeast, which is produced in large quantities as a byproduct in sugarcane processing plants during sugar and alcohol manufacturing process. There are documents in the literature describing yeast autolysis to obtain cell wall and concomitantly yeast protein extract. In the documents filed in the form of patents and patent applications under the numbers KR 9509943, JP 10179084, US 4,285,976, FR 1427068, RU 2238315, RU 2229243 and RU 2005/107594, the authors show how to produce cell wall from yeast autolysate. after separation by centrifugation. In these processes, the pH is maintained at values ranging from 6.0-8.0 and temperatures ranging from 40-50 ° C. Autolysis is performed at times ranging from 4-30 h and preferably at times ranging from 6-20 h and more preferably at times ranging from 8-16 h in the presence of sodium chloride or ethanol as promoters.

In a document filed under US Patent Application No. 2002/061345, the authors teach how to prepare a supplement formed by hydrolysis of yeast composed of free oligosaccharides present in the yeast cell wall. The authors claim the use of the composition as a dietary supplement for the treatment of intestinal problems and animal growth. In another document filed under patent number JP 2001008636, the authors teach how to prepare compositions formed by combining yeast and betaine cell wall for use in preventing infectious diseases. In other documents filed under US Patent No. 6,045,834 and WO 09953772 the authors show how to prepare compositions prepared by combining cell wall and clays for use as mycotoxin adsorbents in animal diets. In another document filed under US Patent No. 6,919,082, the authors teach a characteristic odor-free composition characterized as a yeast-derived cell wall for use in the treatment of individuals with constipation and allergic diseases. Of particular interest to this invention, however, is the ability of the cell wall to promote increased absorption of minerals in animals. This feature of the cell wall has already been demonstrated in documents filed as patent applications under the numbers JP2004292382, JP5292916, JP 2003277273 and JP2002255832. These documents claim compositions comprising as active ingredients the cell wall from yeast or polysaccharides obtained from yeast cell wall and its applications - such as the use of specific cell wall fractions to increase calcium absorption for treatment. of individuals with osteoporosis.

Despite the benefits already shown for mineral supplementation in the form of amino acid chelates, where higher bioavailability values are observed compared to inorganic analogs or by the joint administration of minerals with an efficient absorption promoter such as yeast cell wall , it is of great interest to describe differentiated products from existing ones.

Thus, one of the aims of this invention is to describe a new class of products and, more particularly, a new class of chelated metal complexes. The new products differ from the compounds described in the literature, as they have the yeast cell wall as one of the constituent ligands, unlike those described in the state of the art, which are formed by the coordination between the metallic center and the ligands selected from among the compounds. amino acids, peptides, proteins and other multidentified organic compounds such as EDTA and the like. The new mineral complexes are prepared by reacting mineral sources selected from iron, zinc, copper, manganese, magnesium, calcium, chromium and cobalt and yeast cell wall and can be prepared with different levels of mineral of interest. This versatility, which is of great interest in the preparation of mineral supplements to obtain products with different levels of a given mineral, is the result of the presence of the cell wall as one of the binders of the new complexes, and is not observed for analogous products. The products object of the invention therefore have advantages over the products described in the prior art.

In addition, the mineral complexes of this invention have the characteristics required to be incorporated into human and animal diets, providing a perfect statistical distribution coefficient in animal feed, which is much desired and not always achieved when using other forms of minerals. . This advantage of the novel mineral complexes object of the invention is especially interesting when animal diets are supplemented in herds, which involve significantly large amounts of feed.

OBJECTIVES OF THE INVENTION

The aim of this invention is to describe new mineral complexes formed by the reaction between mineral sources selected from iron, zinc, copper, manganese, magnesium, calcium, chromium and cobalt and the yeast cell wall. The products of interest are in the form of coordinated cell wall complexes and can be efficiently used as mineral supplements for the diet of humans and animals.

DESCRIPTION OF THE INVENTION

The cell wall used as the raw material in this invention is composed of glucomannanoproteins, oligosaccharides and free sugars and is preferably used after separation from yeast extract without further treatment. However, previously chemically modified cell walls may also be used in the presence of acids, bases or enzymes when preparing materials with a higher content of reactive protein groups. In other cases, the cell wall may be contaminated with small amounts of yeast protein extract that has not been completely eliminated after the yeast fractionation process.

Regardless of how the cell wall is used, the reactive groups present in its structure that will react with metals and form the mineral complexes of interest are those from the protein portion of the material. More specifically, the reactive sites are derived from carboxyl-containing branched chain amino acids, which form alkaline carboxylate groups and other basic sites. Examples of basic sites on the cell wall are nitrogen atoms found in the amino, guanidine and imidazole groups of the amino acids lysine, guanidine and histidine, respectively. Other basic sites present in the cell wall are nitrogen atoms of the alpha-amino groups of free amino acids adsorbed on the cell wall or insoluble glucomannanopeptides formed during the yeast fractionation process through autolysis or hydrolysis processes.

Mineral sources used as precursors for the preparation of mineral complexes are selected from amino acid metal complexes or amino acid chelates. When metal amino acid complexes are used, compounds derived from divalent metals such as iron (11), zinc, copper, manganese, cobalt, magnesium and calcium are characterized by having an amino acid and an inorganic anion attached to the metal center. In other cases, mineral complexes of monosubstituted amino acids with other organic binders, usually selected from carboxylic acids such as acetic acid or hydroxylated carboxylic acids, such as gluconic acid, tartaric acid, citric acid, among others, may also be used as precursors. However, when the precursors are in the form of amino acid mineral complexes, monosubstituted complexes with inorganic ligands such as chloride or hydrogen sulfate are preferably used. In either case, and regardless of the mineral of interest, the end products are formed in this case by replacing the inorganic or organic anions of the metal precursors with the basic groups in the cell wall. After the process, mineral complexes are formed containing in their structure cell wall-bound amino acids chelates. When the metal precursors are neutral amino acid chelates, characterized by having two amino acids linked to the metal center for the case of bivalent minerals, after the process also formed mineral complexes characterized as cell wall linked amino acid chelates. In this case, chelates are attached to the cell wall through the interaction of the empty valence orbitals of the metals with any of the basic sites mentioned above.

When the precursors selected are transition metal chelates such as iron (ll), zinc, copper, manganese and cobalt, the reaction to form new cell wall complexes may involve their empty molecular orbitals that are capable of receiving electrons and forming new bonds without the loss of one of the ligand amino acids, in which case the metals are coordinated by more than two ligands. Binding may also occur by replacing one of the ligands with one of the reactive groups present in the cell wall. When the interest is in the incorporation of alkaline earth metals, binding to reactive cell wall groups occurs only by substitution of one of the ligand amino acids, as these metals do not have empty orbitals available as transition metals to accommodate other ligands. In other cases, when monosubstituted amino acid metal complexes are used, the bonding occurs by substitution of the inorganic or organic groups present in the precursor.

When the interest is in the preparation of cell-walled chromium mineral complexes, inorganic chromium salts such as chromium (III) basic chloride or sulfate may be used as a metal precursor. Species characterized by having up to two amino acids attached to the metal center and at least one inorganic anion or three amino acids may also be used, when the selected precursor is a chromium neutral amino acid chelate. However, chromium is preferably incorporated into the cell wall using chromium in the form of sulfates or chloride and preferably in the form of basic chromium (III) sulfate.

The preparation of cell wall mineral complexes of other metals can also be made using inorganic salts of the mineral of interest such as chloride or sulfate, or their oxides, hydroxides and carbonates as precursors. However, the mineral complexes of interest are preferably prepared using metallic amino acid complexes or neutral amino acid chelates. Examples of amino acids constituting chelates ου metal complexes used as precursors are glycine, lysine, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, aspartic acid, glutamic acid, valine, trioenine, isotroenine, histidine, tryptophan and glutamine. However, metal complexes and neutral chelates formed of glycine, aspartic acid or mixtures thereof are preferably used. Complex precursors and neutral chelates may be readily available on the market or even synthesized by those skilled in the art using the various means described in the literature, if desired.

The preparation of the products object of this invention can be made by the use of neutral chelates or metal complexes in the form of aqueous solutions of known concentration or with the same isolates in their solid forms. The products of interest are prepared by adding the mineral source to an aqueous suspension containing the cell wall at concentrations ranging from 5-30% and preferably at cell wall concentrations ranging from 10-25% and more preferably. , range from 15-20% to the weight of the suspension. In other processes, the cell wall as a solid or as a concentrated suspension is added in a solution or suspension containing the neutral chelate or metal complex of interest. Thus, it is clear that regardless of the order of addition of the raw materials products characterized as mineral complexes containing cell wall as binder are obtained, which can be used as mineral supplements for the fortification of animal and human diets. The amount of mineral source to be used may vary according to the target mineral concentration in the final product. We note that depending on the mineral to be used, which can be selected from iron, zinc, copper, manganese, magnesium, calcium, chromium and cobalt, the final mineral content incorporated into the cell wall may range from 0.1-9%. Above all, we observed that it is possible to obtain mineral complexes with different contents of the same mineral, depending on the process used to obtain them. When preparing products with chromium embedded in the cell wall, it is of interest that the concentrations of this mineral are low, preferably ranging from 0.1 to 2%, although larger amounts are also obtainable.

Reactions for the preparation of the final products are carried out at reaction times ranging from 20-180 minutes and preferably from 30-60 minutes. Reactions for the preparation of the products are performed at room temperature, but they can also be carried out at temperatures up to 50 ° C without changing the quality of the final products. Product isolation can be done by separation processes such as filtration or centrifugation and subsequent drying using vacuum rotary dryers. However, the compositions of interest may be obtained by direct solvent removal, in which case the products are preferably obtained by a continuous drying process, commonly known as spray drying.

Within another aspect, this invention contemplates compositions prepared by combining at least one of the new cell wall mineral complexes with other sources of the same mineral, which are selected from their inorganic salts such as chlorides, sulfates, oxides and hydroxides, mineral chelates and mineral complexes, the latter being preferably selected from chelates and amino acid complexes. The combination of cell wall mineral complexes with other mineral sources to obtain the compositions of interest can be done immediately after the reaction to prepare cell wall complexes prior to the final product isolation step or by subsequent combination of the selected components. . In such cases, compositions having mineral contents ranging from 3-20% may be obtained, and compositions having mineral contents ranging from 5-15% and more preferably from 7-10% are preferably prepared.

In another aspect, this invention contemplates compositions prepared with different minerals, and at least one of the components of these compositions is one of the novel cell wall mineral complexes object of this invention. In such cases, compositions having at least two minerals may be prepared, although other minerals may also be incorporated, if of interest.

Within another aspect, this invention contemplates a method of treating animals or humans for the purpose of mineral supplementation of their diets using as supplements the products object of this invention. When the treatment is done in humans, the products are preferably administered in tablet form. When treated in animals such as cattle, pigs, poultry, goats, sheep, felines, canines and horses, the form of administration depends on the animal to be treated, although in all cases supplementation is by oral administration. In general, supplementation is done by adding the products of this invention into the animal feed until the desired mineral levels are obtained. When supplementation is in dogs and cats, the administration of the products object of this invention may also be in the form of tablets containing the mineral complexes alone or in combination with or in combination with other supplements, such as vitamins. For oral administration in the form of coated or uncoated tablets, the composition of the invention may be combined with a pharmaceutically acceptable inert carrier such as lactose, starch, sucrose, glucose, cellulose derivatives, magnesium stearate, dicalcium phosphate, calcium sulfate, mannitol, sorbitol and the like. In addition, where desired or necessary, suitable binders, lubricants, disintegrating agents and coloring agents may also be incorporated into the mixture. Suitable binders include starch, gelatin, natural sugars such as glucose or beta-lactose, corn sweeteners, natural and synthetic gums such as acacia, tragacanth or sodium alginate, carboxymethylcellulose, polyethylene glycol, waxes and the like. Lubricants that may be used in such dosage forms include sodium oleate, sodium stearate, magnesium stearate, sodium benzoate, sodium acetate, sodium chloride and the like. Disintegrants include, without limitation, starch, cellulose derivatives agar, bentonite, xanthan gum and the like. Mentioned below are merely illustrative examples of preparation and use of the products and compositions of interest of this invention, once again emphasizing that they do not impose any limitation on the scope of the invention other than those set forth in the appended claims. Thus, the examples should not be construed as limiting this invention, as various variations can be practiced or performed by those skilled in the art in a variety of ways, it being understood that the above example is for the purpose of description rather than limitation.

EXAMPLES

Example 1

A zinc-containing mineral complex was prepared by dissolving 500 g of zinc bis (glycinate) in 2.5 liters of drinking water and adding to this solution 5.0 kg of cell wall. The mixture was stirred for 1h at room temperature, and the product was filtered and dried. A yield of 4.8 kg of a cell wall mineral complex containing 3.0% zinc was obtained.

Example 2

A copper-containing mineral complex was prepared by adding 2.0 kg of an aqueous copper bis (aspartate) solution with a copper content of 5% to 20 liters of a suspension containing 2.0 kg of cell wall. The mixture was kept under stirring for 1 h at room temperature. The product was spray-dried in 2.4 kg yield and a copper content of 4.5% was obtained.

Example 3

An iron-containing mineral complex was prepared by adding 10 kg of an aqueous solution containing 4.5 kg of iron mono (gluconate) mono (glycinate) to 50 kg of a suspension containing 10 kg of cell wall. The reaction mixture was stirred for 1.5 h at room temperature and the final product was filtered and oven dried at 105 ° C. Yield: 11.5 kg of a cell wall-containing iron mineral complex with an iron content of 6.0%.

Example 4

A magnesium-containing mineral complex was prepared by adding 175 kg of cell wall in 1000 kg of a solution containing 350 kg of magnesium bis (glycinate). The mixture was stirred for 20 minutes and filtered. The product (300 g) was oven dried and had a magnesium content of 2.5%.

Example 5

A mineral composition having 10% iron was prepared by combining for 2 h in a 500 part rotary mixer of a cell wall iron complex prepared according to Example 3 and 285 parts 17% iron bis (glycinate) .

Example 6

A zinc-containing mineral complex was prepared by dissolving 550 g of zinc glycine sulfate ([Zn (gly)) 2.SO4 in 2.5 liters of drinking water and adding 5.0 kg of cell wall to this solution. stirring for 1 h at room temperature, and the product was filtered and dried, yielding 4.8 kg of a cell wall mineral complex containing 3.2% zinc.

Example 7

A calcium-containing mineral complex was prepared by suspending 130 g of calcium oxide in 2.5 liters of drinking water and then adding 5.0 kg of cell wall. The mixture was stirred for 2 h at 80 ° C, and the product was filtered and dried. It was obtained in yield of 4.8 kg of a cell wall mineral complex containing 5.0% calcium.

Example 8

A chromium-containing mineral complex was prepared by dissolving 25 g of 33% alkaline chromium sulfate in 2.5 liters of drinking water and then adding 5.0 kg of cell wall. The mixture was stirred for 1h at room temperature, and the product was filtered and dried. It was obtained in 5 kg yield of a cell wall mineral complex containing 1000 ppm (0.1%) of chromium.

Example 9

A mineral composition having 2.6% zinc, 1.3% magnesium and 0.1% copper was prepared by combining 30 parts of the zinc complex prepared according to Example 1, 40 parts of the prepared magnesium complex. according to Example 4, 2 parts of the copper complex prepared according to Example 2 and 5 parts of zinc sulfate heptahydrate.

Example 10

The mineral composition prepared according to Example 9 was used at a ratio of 0.5% w / w for the preparation of a poultry feed.

Claims (15)

1. MINERAL COMPLEXES, characterized by comprising a metallic center coordinated to a cell wall. 2. MINERAL COMPLEXES, characterized in that it comprises a metallic center coordinated to a cell wall and at least one amino acid. MINERAL COMPLEXES according to claim 2, characterized by amino acids selected from glycine, lysine, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, aspartic acid, glutamic acid, valine, threonine, isotreonine, histidine tryptophan, serine and glutamine and preferably glycine, aspartic acid or mixtures thereof. MINERAL COMPLEXES according to claims 1 and 2, characterized by a cell wall resulting from yeast fractionation and preferably yeast fractionation by autolysis or hydrolysis of Saccharomices yeast and preferably Saccharomices eerevisiae yeast. MINERAL COMPLEXES according to claim 4, characterized by a chemically modified cell wall in the presence of acids, bases or enzymes. MINERAL COMPLEXES according to Claims 1 and 2, characterized by metal centers selected from iron, zinc, copper, manganese, cobalt, chromium, magnesium or calcium. PREPARATION PROCESSES for obtaining mineral complexes according to claims 1 and 2, characterized by reacting in aqueous phase adequate amounts of a mineral source and cell wall and further drying of the resulting product. Preparation processes according to claim 7, characterized by the reaction of a mineral source selected from neutral amino acid chelates, amino acid metal complexes, inorganic salts, oxides, hydroxides or mixtures thereof. PREPARATION PROCESSES according to claim 8, characterized by neutral amino acid chelates selected from bisglycinates, bislisinates, bisalaninates, bisphenylalaninates, bisleucinates, bisisoleucinates, bisprolinates, bishhydroxyprolinates, bispyrionates, bismethionates bisatosinates, bisotonates bisatosinates bishistidinates, bistriptophanates, biserinates, bisglutaminates, or mixtures thereof and preferably bisglycinates, bisaspartates or mixtures thereof. Preparation processes according to claim 8, characterized by metal complexes consisting of a metal center bonded to at least one naturally occurring amino acid and at least one counter ion selected from hydroxyl, hydrogen sulfate or chloride. Preparation processes according to Claim 8, characterized by inorganic salts selected from chlorides, sulphates or mixtures thereof. MINERAL COMPOSITIONS, characterized in that they comprise at least one mineral complex described in one of claims 1 to 6 in combination with other mineral sources. MINERAL COMPOSITIONS according to claim 12, characterized by mineral sources selected from amino acid chelates, amino acid mineral complexes, inorganic mineral salts such as chlorides, sulfates, oxides, hydroxides or mixtures thereof. Use of a mineral complex according to one of Claims 1 to 13, characterized in that it is used as a mineral supplement or as an integral part of a food or feed for mineral supplementation in animals and humans. Method according to one of Claims 1 to 13, characterized in that at least one mineral complex is administered in an effective amount and in a nutritionally acceptable form for mineral supplementation in animals and humans.