IP Library Granted Patent US 8,563,072
Granted Patent B2
US 8,563,072 · App. 12/988,183 · Granted Oct 22, 2013

Suspension containing hydronium stabilized colloidal silicic acid nanoparticles, formulation obtained from the said diluted suspension, powder obtained from the said de-hydrated suspension, compositions obtained from the said powder, preparation and use

Inventors: Ivo Suvee (Lima, PE); Guillaume Tourgis (Paris, FR)
Assignees: Aquarius Investholding, SARL; Jisbrey, S.A.
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Quick Facts
Patent No.
US 8,563,072
App. No.
12/988,183
Granted
Oct 22, 2013
Kind
B2
Abstract

The present invention relates to hydronium stabilized silicic acid nanoparticles, to the formulation obtained from the said diluted suspension, to the powder obtained from the said dehydrated suspension and to the preparation or dosage form obtained from the said suspension, formulation or powder, to their preparation and their use in all kinds of applications in the domains of food, medicine, pharmaceutics, cosmetics. The present invention provides a stable suspension of colloidal silicic acid nanoparticles having a pH lower than 0.9, a molar silicon concentration between 0.035 and 0.65, a free water concentration of at least 30% (w/v) and a ratio between hydronium ion and Si molar concentrations higher than 2 and preferably inferior to 4. The present invention further provides a method for preparing a stable suspension of colloidal silicic acid nanoparticles, which comprises the steps of providing an aqueous inorganic or organic silicon solution and quick mixing said aqueous inorganic or organic silicon solution with water containing a strong acidic compound at a temperature inferior at 30° C., preferably comprised between 1 and 25° C., to form a suspension of colloidal silicic acid nanoparticles having a pH lower than 0.9, stabilized by hydronium ions, the ratio between hydronium ions and Si molar concentrations being higher than 2 and preferably inferior to 4, for a molar silicon concentration between 0.035 and 0.65 and a free water concentration of at least 30% (w/v).

Claims (67)

1. A stable suspension of colloidal silicic acid nanoparticles having a pH lower than 0.9, a molar silicon concentration between 0.035 and 0.65, a free water concentration of at least 30% (w/v) and a ratio between hydronium ion and Si molar concentrations higher than 2, wherein said nanoparticles are soluble in water, more than 98% of the suspension passes through a 0.1 micron filter but is not filterable on a MW 20.000 filter, and 29 Si NMR for the suspension shows a typical colloidal silica spectrum with a separated low Q2 peak further supplemented with at least one of the following:

i—micro- and macro nutrients

ii—growth activators, fertilizers, biological active compounds for crop production and protection;

iii—hydrophilic and hydrophobic anti-oxidants

iv—enzyme inhibitors, hormones, antibiotics, or other pharmaceuticals; or

v—natural and synthetic food colorants, food sweeteners, food emulgators and food flavourings;

or mixtures thereof.

2. A suspension according to claim 1 , further comprising an organic sulfur compound as stabilizer, in concentrations varying from 0.01 to 25% (w/v).

3. A suspension according to claim 1 , further comprising a secondary stabilizer showing the following characteristics: good water solubility, strong hydronium attracting, and neutralizer of ROS (reactive oxygen species) inducing polymerization.

4. A suspension according to claim 3 wherein the secondary stabilizer, present in concentrations ranging from 0.5% (w/v) to 60% (w/v), is selected from the chemical group glycol poly-ether compounds, sulfated polysaccharides, polymers of carboxylic acid and hydroxyl acids or combinations thereof.

5. A formulation obtained by dilution in an aqueous environment of the suspension according to claim 1 comprising monosilicic acid and/or disilicic acid.

6. A method for preparing a stable suspension of colloidal silicic acid nanoparticles according to claim 1 , which has a final molar silicon concentration Y comprised between 0.035 and 0.65, the method comprising the steps of:

providing an aqueous inorganic or organic silicon solution having a molar silicon of 2Y;

diluting two times the said aqueous inorganic or organic silicon solution in adding it in a aqueous acid solution of which the amount of acid is determinated in order to obtain an acidified Y solution having a pH lower than 0.9 and a ratio between hydronium ions and Si molar concentrations being at least 2;

stirring, during or after the addition, until obtaining the stable suspension of colloidal silicic acid nanoparticles.

7. The method according to claim 6 comprising the following steps:

a) Providing an aqueous inorganic strong alkaline solution,

b) Determination of the final molar silicon concentration Y

c) Diluting the alkaline solution, in purified water, resulting in a molar silicon concentration of 2Y and at a temperature <30 C

d) Titration of the amount of acid needed to neutralize the diluted solution to pH 7.0

e) Calculating the amount of acid needed to further achieve a pH lower than 0.9 and to reach the ratio of at least 2 between the molar concentration of hydronium ions and silicon;

f) Making an appropriate acidified aqueous solution and,

g) Mixing quickly the diluted solution into the appropriate acidified solution until obtaining the said stable colloidal suspension of silicic acid nanoparticles.

8. The method according to claim 6 comprising the following steps:

a) Providing an organic silicon compound,

b) Determination of the desired final molar silicon concentration Y,

c) Taking a volume of the compound to be diluted in acidified water resulting in a silicon concentration of 2Y molar,

d) Adding slowly the volume of the compound under stirring and/or sonication into acidified water at pH 0.9 and continuing until complete hydrolysis,

e) Diluting the obtained solution two times under stirring with acidified water containing the supplementary acid to reach the ratio between hydrogen ions and silicon molar concentrations, the pH of this solution staying lower than 0.9, until obtaining the said stable colloidal suspension of silicic acid nanoparticles.

9. The method according to claim 6 in which strong mineral acids used are selected from the group consisting of: HCl , H 3 PO 4 , H 2 SO 4 and HNO 3 .

10. The method according to claim 7 in which completely solubilized silicates or silicon salts are used as inorganic silicon compounds.

11. The method according to claim 8 in which organic silicon solutions used are aqueous solutions of hydrolysable organic silicon compounds, selected from the group consisting of alkoxy silanes or alkylesters of mono silicic acid (Si(OR) 4 ), Si(OR) 3 OH, Si(OR) 2 (OH) 2 , SiOR(OH) 3 in which R is a lower alkyl compound.

12. The method according to claim 6 comprising a step of addition to the said suspension of a primary stabilizer which is an organic sulfur compound selected from the group consisting of MSM (methylsulfonylmethane) or DMSO (dimethylsulfoxide), in concentrations varying from 0.01 to 25% (w/v), particularly in order to obtain a suspension of colloidal silicic acid nanoparticles stabilized for periods of time of at least 4 weeks.

13. The method according to claim 6 comprising a step of addition of a secondary stabilizer, which is a strong hydronium attracting substance, soluble in water selected from the chemical group glycol, propylene glycol, poly-ether compounds, sulphated polysaccharides, polymers of carboxylic acid and hydroxyl acids or combinations thereof, in order to obtain a suspension of colloidal silicic acid nanoparticles stabilized for periods more than a year.

14. A method for preparing a formulation comprising monosilicic acid and/or disilicic acid comprising the step of dissolving in water or aqueous solution the suspension according to claim 1 .

15. The stable suspension according to claim 1 for use as source of mono- and di-silicic acid for micro-organisms, plants or animals.

16. The suspension according to claim 1 for use in a medical treatment as source of mono and di-silicic acid.

17. The stable suspension according to claim 1 , for use in anticorrosive applications as such or in combination with molybdates or other anti-corrosive compounds upon dilution.

18. A food supplement, nutraceutical, food additive, pharmaceutical preparation, topical formulation, hygienic formulation, concentrated fertilizer and growth regulator, or concentrated plant protection formulation, concentrated bio-available silicon formulation to induce biological processes in plants, animals, humans and micro-organisms comprising the formulation according to claim 1 .

19. The formulation according claim 5 for use in a medical treatment as concentrated bio-available silicon formulation.

20. The formulation according to claim 5 for use to supplement the drinking water of animals or as a fertilizer for plants to increase the concentration of omega 3 fatty acids in the animals or plants.

21. The formulation according to claim 5 for use in a drinking water of humans so as to increase the concentration of omega 3 fatty acids in human organism.

22. A method for preparing a soluble powder containing bio-available silicon, starting with the stable suspension according to claim 1 , comprising the following steps:

a) adding a highly water soluble carrier to the stable suspension of colloidal silicic acid nanoparticles having a pH lower than 0.9, a molar silicon concentration between 0.035 and 0.65, a free water concentration of at least 30% (w/v) and a ratio between hydronium ion and Si molar concentrations higher than 2 in order to absorb and precipitate the colloidal silicic acid nanoparticles and

b) evaporating the free water until obtaining a powder.

23. The method according to claim 22 comprising the step of adding the carrier which comprises the methylsulfonylmethane (MSM) in order to increase the solubilisation of the carrier, preferably up to concentrations of 20% (w/v).

24. The method according to claim 22 wherein the carrier is a protein, polypeptide, protein hydrolysate, a polyamine with a molecular weight lower than 300,000—or mixtures thereof.

25. The method according to claim 22 wherein the carrier is added slowly to the silicic acid suspension under stirring until complete solubilisation of the carrier at a final concentration higher than 2% (w/v), in that the pH is eventually corrected until being less than 0.9, in that the suspension obtained is stabilizated during some hours and in that the free-water of the suspension is evaporated by a quick dehydration technique, such as vacuum evaporation or freeze-drying until obtaining the soluble powder.

26. Powder containing colloidal silicic acid nanoparticles, prepared by the method of claim 22 , having a silicon concentration between 0.05% and 15% (w/w).

27. The powder according to claim 26 containing from 1.5% to 8% (w/w) Si as colloidal silicic acid, from 50% to 75% (w/w) collagen hydrolysate and from 10% to 35% (w/w) methylsulfonylmethane (MSM).

28. The powder according to claim 26 further containing at least one of the following:

i—micro- and macro nutrients selected from the group consisting of:

A) soluble salts and sources of macro- and micro and trace elements, of Ca, K, Na, Mg, Mn, B, Li, Sr, Se, Mo, Fe, Co, Cu, Zn, Ti, Al, Ag, Cr, Si, P, S, N, F, Cl, Br, I or mixtures thereof;

B) nutrients: sugars, fats, proteins, nucleic acids, vitamins, amino acids, plant extracts, glucosamine, chondroitin, hyaluronic acid, carnitine, organic acids, acetyl compounds, . . . and combinations thereof, or mixtures thereof;

ii—growth activators, fertilizers, biological active compounds for crop production and protection;

iii—hydrophilic and hydrophobic anti-oxidants carotenoids, beta-carotene, lutein, lycopene, zeaxanthin, . . . , flavonoids quercetin, hesperetin, luteolin, rutin . . . , accepted food additives, antioxidative enzymes, phenolic acids, lipoic acid, Co-Q10

iv—enzyme inhibitors, hormones, antibiotics, or other pharmaceuticals; or

v—natural and synthetic food colorants, food sweeteners, food emulgators and food flavourings;

or mixtures thereof.

29. A dosage form containing a suspension according to claim 1 or a formulation or powder obtained from a suspension.

30. A dosage form according to claim 29 as capsule, softgel, compressed lozenge, tablet, suppository, gelatin coated pill, cream, gel, lotion, ointment, liminent, plaster, unguent, patch.

31. The suspension according to claim 2 , further comprising MSM (dimethylsulfonylmethane) as stablilizer.

32. The suspension according to claim 4 , wherein the secondary stabilizer is present in concentrations ranging from 20 to 50% (w/v).

33. The suspension according to claim 4 , wherein the secondary stabilizer is PEG.

34. The suspension according to claim 1 , wherein

i) the micro- and macro nutrients are selected from the group consisting of soluble salts and sources of macro- and micro and trace elements, sources, salts, oxides, and complexes of Ca, K, Na, Mg, Mn, B, Li, Sr, Se, Mo, Fe, Co, Cu, Zn, Ti, Al, Ag, Cr, Si, P, S, N, F, Cl, Br, I and mixtures thereof, and nutrients selected from the group consisting of sugars, fats, proteins, nucleic acids, vitamins, amino acids, plant extracts, glucosamine, chondroitin, hyaluronic acid, carnitine, organic acids, acetyl compounds, and combinations thereof, or mixtures thereof; and

2) the hydrophilic and hydrophobic anti-oxidants are selected from the group consisting of carotenoids, beta-carotene, lutein, lycopene, zeaxanthin, flavonoids, quercetin, hesperetin, luteolin, rutin, accepted food additives, antioxidative enzymes, phenolic acids, lipoic acid, Co-Q10.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 22, 2010
From: SUVEE, IVO; TOURGIS, GUILLAUME
To: AQUARIUS INVESTHOLDING, SARL; JISBREY, S.A.
Reel/Frame 025388/0435 →
Priority Claims (1)
WO PCT/EP2008/054643 · Apr 17, 2008 · international
Continuity (1)
Related Publication 20110064798A1 · Mar 17, 2011