Soluble calcium stabilised in an anionic-cationic polymer and fructans

Abstract

The present invention provides processes that promote the solvation of calcium ions in macromolecular matrices. Processes in which the relationship, concentration, physicochemical conditions at each stage and preparation methods allow to obtain a stabilized soluble product, based on calcium salts and polymers. The present invention does not result in the deposition of crystals of the salts used, and exceeds the commercial calcium formulations so they are of great utility for their application in the food, pharmaceutical and/or cosmetic industry.

Claims

1. A method for a preparation of a stabilized soluble calcium complex including a) a source of calcium present in an amount of 0.05 mg to 15 mg per gram of a sample, b) a cationic polymer present in a mass ratio to the calcium source of between 0.25 and 12.5, c) an anionic hydrocolloid, and d) a source of a soluble fiber, the method comprising the steps of: a) preparing a first solution containing from 0.05 g to 5 g of a source of calcium, 1 mL of phosphoric acid, and 8 mL of water; b) preparing a second solution containing from 0.01 g to 4 g of a cationic polymer and 20 mL of 1% glacial acetic acid; c) producing a third solution by combining the solutions obtained in steps a) and b), maintaining the third solution at a temperature of between 1 C. to 70 C., and maintaining the mass proportions of the source of calcium and cationic polymer between 0.25 and 12.5; d) maintaining the pH of the solution of subsection c) at a pH of between 1.0 and 6.5, under conditions of rest for 1 to 24 hours, and under a controlled temperature of 5 C. to 20 C.; e) dispersing the solution of step d) in an anionic hydrocolloid selected from: arabic gum, guar gum, sodium or potassium alginate, propylene glycol alginate, mesquite gum, xanthan gum, locust bean gum, casein, or pectin; f) adding a source of soluble fiber selected from: agave fructans, inulin, or a mixture thereof; g) conditioning the solution of step f) to be supplied in liquid form, reducing the volume of the solution by atomization in a spray dryer to a final concentration of total solids of from 30 g to 35 g per 100 ml of solution.

2. The method according to claim 1, wherein the source of calcium is selected from: tribasic calcium phosphate, calcium carbonate, calcium orthophosphate, or calcium oxide.

3. The method according to claim 1, wherein the cationic polymer is chitosan, potassium of animal or vegetable origin.

4. The method according to claim 1, wherein the anionic hydrocolloid is preferably selected from alginate, arabic gum or mixtures thereof, being present in an amount of from 0.01 g to 50 g with 0.25 g to 12 g of the calcium-chitosan complex.

5. The method according to claim 1, wherein the source of soluble fiber is added in the proportion of: 10 g of fructan, 10 g of inulin, 5 g of fructans and 5 g of inulin, 7.5 g fructans and 2.5 g of inulin, or 2.5 g fructans and 7.5 g inulin.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows an infrared electromagnetic spectrum of chitosan (-Q), Arabic gum molecular weight (-GA), and tribasic calcium phosphate (-CP). Molecules used in the formation of soluble calcium using chitosan, Arabic gum, fructans and/or inulin.

(2) FIG. 2 shows the infrared electromagnetic spectrum of the soluble complex of 1.5 parts of tribasic calcium phosphate; 1 part of chitosan; 20 parts of Arabic gum; and 10 parts of fructans; and/or 5 parts of fructans and 5 parts of inulin, described in example 1.

(3) FIG. 3 shows the average infrared electromagnetic spectrum of the soluble complex of 2.5 parts of tribasic calcium phosphate; 1 part of chitosan; 20 parts of Arabic gum; and 10 of fructans; or 5 parts of fructans and 5 parts of inulin, described in example 2.

(4) FIG. 4 shows the infrared electromagnetic spectrum of the soluble complex of 5.0 parts of tribasic calcium phosphate; 1 part of chitosan; 20 parts of Arabic gum; 10 parts of fructans; or 5 parts of fructans and 5 parts of inulin, described in example 3.

(5) FIG. 5 shows an electron micrograph (2500) of the soluble complex of 1.5 parts of tribasic calcium phosphate; 1 part of chitosan; 20 parts of Arabic gum; and 10 parts of fructans; 5 parts of fructans and 5 parts of inulin, described in Example 1 or 7.5 parts of fructans and 2.5 parts of inulin, soluble in water.

(6) FIG. 6 shows an electron micrograph (2500) of the soluble complex of 2.5 parts of tribasic calcium phosphate-chitosan; 20 parts of Arabic gum; and 10 parts of fructans; 5 parts of fructans and 5 parts of inulin, described in Example 2, soluble in water.

(7) FIG. 7 shows an electron micrograph (2500) of the soluble complex of 5.0 parts of tribasic calcium phosphate-chitosan; 20 parts of Arabic gum; and 10 parts of fructans; or 5 parts of fructans and 5 parts of inulin, described in Example 2, soluble in water.

(8) FIG. 8 shows the major steps for the preparation of soluble calcium, purpose of this invention.

DETAILED DESCRIPTION OF THE INVENTION

(9) The following is a more detailed description of some aspects of the invention in order to allow a greater understanding thereof; but without this in any way limiting the same.

(10) The method according to the invention for the preparation of a stabilized soluble calcium complex comprises the following steps:

(11) Preparing a solution of tribasic calcium phosphate between 0.19 g to 5 g, particularly 0.5 to 3 g, but preferably 1 g in 1 ml of phosphoric acid. Adding 8 mL of water to the solution.

(12) Preparing a chitosan solution between 0.01 g and 4 g, preferably 0.4 g of chitosan is dispersed in 20 mL of 1% acetic acid.

(13) The solution obtained in step number one is mixed with the solution of step number two. The temperature is maintained between 1 C. to 70 C., preferably 30 C. Maintain the mass proportions between tribasic calcium phosphate and chitosan between 0.25 and 12.5, preferably 2.5.

(14) Maintaining the solution obtained between 1.0 and 6.5 pH units, preferably at a pH of 3.5. Keeping the solution at rest for 1 to 24 hours, preferably for 12 hours. Controlling the temperature between 5 C. to 40 C., preferably at 4 C.

(15) Dispersing in an anionic food-grade hydrocolloid solution, for example: Arabic gum, guar gum, sodium or potassium alginate, propylene glycol alginate, mesquite gum, xanthan gum, locust bean gum, casein, or pectin. Alginate and Arabic gum from 0.01 g to 50 g. Preferably 20 g of Arabic gum or alginate or the mixture of both polymers in the described relationships or vice versa, with 0.25 g to 12 g of the calcium phosphate-chitosan complex previously described.

(16) Adding 10 g of fructans and/or 10 g of inulin, preferably 5 g of fructans and 5 g of inulin, or more preferably 7.5 g of fructans and 2.5 g of inulin or 2.5 g of fructans and 7.5 g of inulin. The obtained solution is conditioned to be supplied in liquid form. The total solids concentration in the solution is in the range of 30 g to 35 g per 100 mL solution. To reduce the volume, the solution is dried in a spray dryer.

(17) In addition, to provide in more detail other aspects of the invention the following non-limiting examples are provided.

Example 1

(18) Three parts of tribasic calcium phosphate are mixed with 10 parts phosphoric acid. The obtained mixture is mixed with 89 parts of water. The tribasic calcium phosphate is integrated with the aid of a mixer for 5 min. 100 parts of this example may be mixed with 80 parts of the solution prepared in Example 3. Add sufficient amount of a strong base to adjust the pH to 3.5 in the obtained solution. The prepared solution contains 666.7 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 2 show evidence of calcium stabilization at a ratio of 1.5 with respect to the cationic polymer used.

(19) FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

Example 2

(20) Three parts of calcium carbonate are mixed with 12 parts of phosphoric acid. The obtained mixture is mixed with 87 parts of water. The calcium carbonate is integrated with the aid of a mixer for 5 min. 100 parts of this example may be mixed with 80 parts of the solution prepared in Example 3. Add sufficient amount of a strong base to adjust the pH to 3.5 in the obtained solution. The prepared solution contains 666.7 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 2 show evidence of calcium stabilization at a ratio of 1.5 with respect to the cationic polymer used. FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

Example 3

(21) 3 parts of chitosan are mixed in 98 parts of a solution of 1 part acetic acid and 99 parts of water. The solution of Example 1 is integrated with the aid of a mixer for 5 min. According to Example 1: 16.5 parts of the obtained solution are mixed with 13 parts of the dispersion obtained from this example. Add sufficient amount of a strong base to adjust the pH to 3.5. The solution obtained contains 671 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 2 show evidence of calcium stabilization at a ratio of 1.5 with respect to the cationic polymer used. FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

Example 4

(22) Based on Example 1. Mix 33 parts with 13 parts of the solution of Example 3. The solution of Example 1 is mixed with the aid of a mixer for 15 min. Add sufficient amount of a strong base to adjust the pH to 3.5. The solution can be integrated by heating to 60 C. Condition the obtained solution below 25 C. The solution obtained contains 860.8 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 3 show evidence of calcium stabilization at a ratio of 2.5 to the cationic polymer used. FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

Example 5

(23) According to Example 2. Mix 33 parts of the solution obtained with 13 parts of the solution obtained in Example 3. The solution of Example 2 is mixed with the aid of a mixer for 15 min. Add enough of a strong base to adjust the pH to 3.5. The solution can be integrated by heating to 60 C. Condition the obtained solution below 25 C. The solution obtained contains 860.8 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 3 show evidence of calcium stabilization at a ratio of 2.5 to the cationic polymer used. FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

Example 6

(24) 66 parts of the solution obtained in Example 1 are added in 13 parts of the solution obtained from Example 3. Heat the solution to 50 C. The solution of example one, is integrated with the aid of a mixer for 15 min. Adjust the pH of the dispersion to 3.5 units with a strong base. Condition the obtained solution below 25 C. The solution obtained contains 1000 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 4 show evidence of calcium stabilization at a ratio of 5.0 to the cationic polymer used. FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

Example 7

(25) 66 parts of the solution obtained in Example 2 are mixed with 13 parts of the solution obtained from Example 3. Heat the solution to 50 C. The solution of Example 2 is integrated with the aid of a mixer for 15 min. Add sufficient amount of a strong base to adjust the pH to 3.5. Condition the solution obtained at 20 C. The solution obtained contains 1000 mg of calcium in solution. The electromagnetic spectra shown in FIG. 1 and FIG. 4 show evidence of calcium stabilization at a ratio of 5.0 to the cationic polymer used. FIG. 2 contains chitosan, Arabic gum, fructans and inulin.

(26) Examples 8 to 15, cited below, explain the calcium composition and the different ratios of the matrices used to contain soluble calcium.

Example 8

(27) Mix 5 parts of fructans with 50 parts of water. The solution obtained contains 10% total apparent solids per 100 mL of solution.

(28) Mix 2.5 parts of inulin and 2.5 parts of fructans with 50 parts of water. The solution contains 10% total apparent solids per 100 m of solution.

(29) Mix 1.25 parts of inulin and 3.75 parts of fructans with 50 parts of water. The solution contains 10% total apparent solids per 100 m of solution.

(30) Mix 3.75 parts of inulin and 1.25 parts of fructans with 50 parts of water. The solution contains 10% total apparent solids per 100 m of solution.

(31) Mix 5 parts of inulin with 50 parts of water. The solution obtained contains 10% total apparent solids per 100 mL of solution.

Example 9

(32) 20 parts of Arabic gum are dispersed in 85 parts of water. The dispersion is conditioned for use in any of the examples, product of the invention. For example, mix 29.5 parts of the dispersion obtained in Example 1 with 100 parts of this example. Add 50 parts of the solution obtained in Example 8, subsection c). A fluid solution is obtained. The solution may be dried in the usual manner to produce a fine powder. The product contains calcium and soluble fiber. The product can be applied in liquid or solid dosage form.

Example 10

(33) Based on Example 1. Mix 29.5 parts with 23.6 parts of Example 3. Add 100 parts of solution of Example 9. Finally, add 50 parts of solution of Example 8, part a) or e). The solution contains 3.4% tribasic calcium phosphate, 2.6% cationic polymer. 75.2% anionic polymer and 18.8% fructans or inulin. The percentages are on a dry basis. The evidence of calcium stabilization is observed in FIG. 2, electromagnetic spectrum vs. FIG. 5, electron micrograph (2,500) where calcium is stabilized in the matrix of chitosan, Arabic gum, fructans or inulin, as noted in example 8, subsection (a) or (e).

Example 11

(34) Based on Example 2. Mix 29.5 parts with 23.6 parts of Example 3. Add 100 parts of solution from Example 9. Finally, add 50 parts of solution from Example 8 (b). The solution contains 3.3% tribasic calcium phosphate, 1.32% calcium ion, 2.7% cationic polymer. 75.2% of anionic polymer and 9.4% of fructans and 9.4% of inulin. The percentages are on a dry basis. The electromagnetic spectra shown in FIG. 2 and the electron micrograph, shown in FIG. 5 (2500), show evidence of calcium stabilization at a ratio of 1.5 with respect to the cationic polymer used. A fluid solution is obtained. The solution can be dried in the usual manner, for example in a spray dryer, to produce a fine powder. The product contains calcium and soluble fiber. The product can be applied in liquid or solid form.

Example 12

(35) Based on Example 4, mix 46 parts with 100 parts of Example 9. Add 50 parts of Example 8, subsection d). A fluid solution is obtained. The solution may be dried in the usual manner to produce a fine powder. The product contains calcium and soluble fiber. The product can be applied in liquid or solid form. The composition of the components, product of this invention is 3.75% tribasic calcium phosphate, 1.5% soluble calcium. 1.4% cationic polymer, 75.8% anionic polymer, 14.2% inulin and 4.7% fructans. The electromagnetic spectra shown in FIG. 3 and the electron micrograph, shown in FIG. 6 (2500), show evidence of soluble calcium at a ratio of 2.5 with respect to the cationic polymer used.

Example 13

(36) Based on Example 5, mix 46 parts with 100 parts of Example 9. Add 50 parts of Example 9, subsection c). A fluid solution is obtained. The solution may be dried in the usual manner to produce a fine powder. The product contains calcium and soluble fiber. The product can be applied in liquid or solid form. The composition of the components, product of this invention is 3.75% tribasic calcium phosphate, 1.5% soluble calcium. 1.4% cationic polymer, 75.8% anionic polymer, 4.7% inulin and 14.2% fructans. The electromagnetic spectra shown in FIG. 3 and the electron micrograph, shown in FIG. 6 (2500), show evidence of calcium stabilization at a ratio of 2.5 with respect to the cationic polymer used.

Example 14

(37) Based on Example 6, mix 79 parts with 100 parts of Example 9. Add 50 parts of Example 8, subsection d). A fluid solution is obtained. The solution may be dried in the usual manner to produce a fine powder. The product contains calcium and soluble fiber. The product can be applied in liquid or solid form. The composition of the components, product of this invention is 3.75% tribasic calcium phosphate, 1.5% soluble calcium. 1.4% cationic polymer, 75.8% anionic polymer, 14.2 inulin and 4.7% fructans. The electromagnetic spectra shown in FIG. 4 and the electron micrograph, shown in FIG. 7 (2500), show evidence of calcium stabilization at a ratio of 5.0 to the cationic polymer used.

Example 15

(38) Based on Example 7, mix 79 parts with 100 parts of Example 9. Add 50 parts of Example 8, part e). A fluid solution is obtained. The solution may be dried in the usual manner to produce a fine powder. The product contains calcium and soluble fiber. The product can be applied in liquid or solid form. The composition of the components, product of this invention is 3.75% tribasic calcium phosphate, 1.5% soluble calcium. 1.4% cationic polymer, 75.8% anionic polymer, 18.9% inulin. The electromagnetic spectra shown in FIG. 4 and the electron micrograph, shown in FIG. 7 (2500), show evidence of calcium stabilization at a ratio of 5.0 to the cationic polymer used.