CN1944457A - Glutathione calcium chelate and its preparing method, use and composition - Google Patents
Glutathione calcium chelate and its preparing method, use and composition Download PDFInfo
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- CN1944457A CN1944457A CN 200610036501 CN200610036501A CN1944457A CN 1944457 A CN1944457 A CN 1944457A CN 200610036501 CN200610036501 CN 200610036501 CN 200610036501 A CN200610036501 A CN 200610036501A CN 1944457 A CN1944457 A CN 1944457A
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Abstract
The present invention relates to glutathione calcium chelate and its preparation process, and features that under the protection of N2 or Ar, calcium chloride solution and glutathione solution in the calcium chloride and glutathione molar ratio of 1/3 to 1 are mixed and reacted, and the resultant is concentration crystallized and vacuum dried to obtain the product. The present invention also relates to the use and composition of glutathione calcium chelate. The glutathione calcium chelate of the present invention has high water solubility, high absorption rate, no irritation to gastrointestinal tract and no toxic side effect, and may be used for treating calcium deficiency caused diseases and as health food.
Description
Technical field
The present invention relates to a kind of calcium chelate, relate to a kind of glutathione calcium chelate specifically, also relate to its preparation method, purposes and composition in addition.
Background technology
Calcium constituent is one of macroelement of needed by human, has many important physical functions.Result according to the national for the third time nutrient profile investigation of Chinese Medical Association and Chinese Soclety of Nutrition sees that owing to food habits, living habit, the inferior many reasons of age level, calcium constituent is still one of nutritive element that lacks most in the population of China.Along with the raising of living standards of the people and the enhancing of health care consciousness, people more and more recognize and replenish the importance of calcium nutritious prod to health.
Studies show that the calcium ion that enters human body is wanted to form inner complex in small bowel homopolypeptide, dipeptides or the acid of nitrogen base earlier, advance people's cell paste by cytolemma then, the chelating chain disconnects, and calcium ion combines with various enzymes, and it is sour and absorbed by organism to form calcic nitrogen base.According to incompletely statistics, on the domestic market more than 200 kind of calcium-supplementing preparation arranged at present, form from the calcium source, be broadly divided into following a few class according to the kind difference: first kind calcium preparation is based on inorganic salt, comprise inorganic calcium, lime carbonate, calcium chloride, secondary calcium phosphate, various fresh bone meal, shell, oyster and pearl powder etc., major part can not directly be absorbed by body; The second class calcium preparation mainly is an organic acid salt, comprises organic calcium, calglucon, calcium lactate, calcium acetate, calcium maleate, citrate of lime etc., and specific absorption is about 30%; The 3rd class calcium preparation: comprise new organic calcium class, trihydroxy-butyric acid calcium (huge energy calcium), L-calcium lactate, amino acid calcium (mainly containing L-calcium aminosuccinic acid and Calcium glycinate) etc., assimilated efficiency reaches about 70%, and have certain additional effect, therefore certain market application foreground is arranged.But these a few class calcium preparations mostly are the salts substances that is insoluble in water, and its anionic existence has hindered being absorbed of calcium.Therefore though China's product category of replenishing the calcium is numerous; but the less effect that can really reach high absorption and have no side effect; thereby caused the trust crisis of human consumer to various supplementary calcium foods, healthcare products, senior nutrition; therefore the novel calcium-supplementing preparation of how developing a kind of real high assimilated efficiency, having no side effect becomes researcher important research project and task.
Gsh (Glutathione) belongs to the small-molecule peptide thing that contains sulfydryl, is a kind of active substance with important physiological function.It is the tripeptides by L-glutamic acid, halfcystine and glycine be combined into, chemistry γ by name-L-glutamy-L-cysteinyl-glycine, and molecular formula is C
10H
18O
6N
3S, relative molecular mass are 307.33.Gsh is distributed in the body widely, in a lot of important biological phenomenas, play a part direct or indirect, as the activity of the transportation of synthetic, the material of protein and DNA, metabolism, cytoprotective, enzyme etc.Owing to have sulfydryl and special γ-peptide bond in its molecular structure; gsh has many important physical functions such as detoxifcation, protection radiation, protection liver, vision protection, antianaphylaxis, anti-ageing, skin maintenance skin care, is widely used in as medicine material, function food additive etc. and produces and all respects of life.
At present, the research for gsh and calcium-supplementing preparation has both at home and abroad obtained very big progress respectively, but the someone proposes the two in conjunction with thinking and the method for producing a kind of brand-new high efficiency calcium-enriching preparation as yet.
Summary of the invention
The objective of the invention is to utilize gsh to develop the calcium chelate that a kind of body absorption rate is high and have no side effect.Another purpose provides the preparation method of this calcium chelate.Another purpose is its purposes of exploitation.A purpose provides the pharmaceutical composition of this calcium chelate again.
The present invention reacts under the protection of rare gas element by solution and the calcium chloride solution with gsh; obtain glutathione calcium chelate; this calcium chelate good water solubility; the specific absorption height; stimulating gastrointestinal not, no side effects can be used for preparing calcium-supplementing preparation; by being combined into composition, thereby realized purpose of the present invention with excipient substance.
Glutathione calcium chelate of the present invention is characterized in that being prepared by following step:
(1) at N
2Or under the protection of Ar, controlled temperature is at 30 ℃～80 ℃, is 1: 1～1: 3 according to the mol ratio of calcium chloride and gsh, and calcium chloride solution and glutathione solution are mixed, and with pH value scope to 5～8 of HCl conditioned reaction liquid, leaves standstill after fully reacting;
(2) ethanolic soln that adds in the above-mentioned reaction solution that leaves standstill with the mixing solutions evaporating, concentrating and crystallizing, separates, and gets precipitation;
(3) with above-mentioned precipitation drying, obtain product.
The massfraction of calcium chloride solution can be 10%～40% in the step (1), and described calcium chloride can be bought from the market, and the molecular formula of described gsh is C
10H
17O
6N
3S, relative molecular mass are 307.33, and structural formula is represented by formula (1):
Formula (1)
Described gsh can be bought from the market, the massfraction of glutathione solution can be 10%～30%, the massfraction of described HCl can be 0.5%～1%, and the described reaction times can be 1～4 hour, and described time of repose can be 10～15 hours.
The massfraction of the described ethanolic soln of step (2) can be 25%～45%, add-on is 2～5 times of reaction solution volumes, described evaporation concentration is preferably under 100 ℃～120 ℃ carries out, described separation can be adopted ordinary method, preferably centrifugation, speed can be 2000～5000r/min.
The described drying of step (3) can adopt usual method, as spraying, vacuum-drying etc., best 60～75 ℃ of vacuum-drying 1～6h.
The preparation method of glutathione calcium chelate of the present invention is characterized in that as mentioned above.
Glutathione calcium chelate of the present invention can be used to prepare the medicine and the protective foods of the illness that the treatment calcium deficiency causes through experimentation on animals proof.
The composition of glutathione calcium chelate of the present invention is characterized in that containing the glutathione calcium chelate of significant quantity and contains one or more pharmaceutically acceptable carriers.
During the oral administration administration, at first make pharmaceutically acceptable carrier of glutathione calcium chelate and one or more, as mixing such as vehicle, disintegrating agent, tamanori, lubricant, antioxidant, Drug coating, tinting material, perfume compound, tensio-active agents, be made into form administrations such as granule, capsule, tablet; Can injection liquid during non-oral administration, form administration such as infusion solution or suppository.When preparing above-mentioned preparation, can use conventional preparation technique.
A kind of stable water-soluble chelate structure of glutathione calcium chelate of the present invention, belong to polypeptide conjugates, water-soluble and fat-soluble good, oral post-absorption is effective, in small intestine, entered in the body by abundant the absorption with the chelated calcium absorpting form of little peptide, can not combine and influence absorption, not need to cooperate vitamins D with oxalic acid in the food, phytic acid etc.
3Promote to absorb, avoided vitamins D
3The danger of poisoning.Simultaneously; after calcium ion is absorbed by transhipment in vivo; gsh is brought into play its a series of physiological action in vivo; make the product of the present invention can high efficiency calcium-enriching; can bring into play simultaneously the treatment and the prophylactic effect of gsh again; therefore glutathione calcium chelate of the present invention is applicable to that the infant growth that causes because of calcium deficiency is slow; senile osteoporosis disease; hypertension; senile dementia; fracture; chronic hepatitis; the assisting therapy of diseases such as chronic nephritis; also has detoxifcation simultaneously; the protection radiation; the protection liver; vision protection; antianaphylaxis; anti-ageing; effects such as skin maintenance skin care can be used as protective foods; medicated premixs etc. are widely used in production and the life.
The animal model of having issued with U.S. food and Drug Administration about the treatment osteoporosis agents is a standard, with the rat is experimental animal model, 50 of rats are divided into experimental group and control group, in the feed of the rat of experimental group, add the glutathione calcium chelate of the present invention of 2000mg/kg, lime carbonate in the feed of the rat of control group, through behind 12 months contrast culture experiments, measure the average calcium content of bone of control group and experimental group, average bone density and calcium absorptivity.The results are shown in Table 1.
Table 1 rats with osteoporosis medication effect relatively
| Average calcium content of bone (mg/g) | Average bone density (g/cm 2) | Calcium absorptivity (%) | |
| The control group experimental group | 136.67 157.24 | 0.249 0.261 | 27.26 81.69 |
As seen body to the specific absorption of gsh inner complex of the present invention apparently higher than lime carbonate.
Embodiment:
Following examples are to further specifying of inventing, but the invention is not restricted to following examples.Gsh used among the embodiment is all given birth to worker's biotechnology company limited from Shanghai.
Embodiment 1:
Prepare massfraction 40%CaCl respectively
2With massfraction 30% gsh (GSH) aqueous solution, feeding shielding gas N
2Condition under, get CaCl respectively
2Solution 2.8g, GSH solution 30.7g mixes two solution (CaCl wherein
2Be 0.01mol, GSH is 0.03mol), the temperature of regulating the control reaction is 80 ℃, reaction times is 4 hours, with massfraction is the pH value to 8 that 1% rare HCl regulates mixed solution, fully left standstill 15 hours after the reaction, the ethanolic soln 170mL that in mixed solution, adds massfraction 45%, at 120 ℃ of following evaporating, concentrating and crystallizings, supernatant liquor is abandoned in back centrifugation under the 5000r/min condition, and centrifugal gained precipitation is placed 75 ℃ of vacuum-drying 1h, promptly obtain glutathione calcium chelate, according to above-mentioned experimentation on animals, prove that this product has efficient absorption, significantly improve the effect of bone mineral content and bone density, have the osteoporotic effect of improvement.
Embodiment 2:
Prepare massfraction 10%CaCl respectively
2With the aqueous solution of massfraction 10%GSH, under the condition that feeds shielding gas Ar, get CaCl respectively
2Solution 11.1g, GSH solution 30.7g mixes two solution (CaCl wherein
2For 0.01mol, GSH are 0.01mol); The temperature of regulating the control reaction is at 30 ℃, and the reaction times is 1 hour, is the pH value to 5 that rare HCl of 0.5% regulates mixed solution with massfraction, leaves standstill 10 hours after fully reacting; Adding the ethanolic soln 83.6mL of massfraction 25% in mixed solution, is 100 ℃ of following evaporating, concentrating and crystallizings in temperature, and supernatant liquor is abandoned in back centrifugation under the 2000r/min condition; After centrifugal gained precipitation placed 60 ℃ of vacuum-drying 6h, promptly obtain glutathione calcium chelate, according to above-mentioned experimentation on animals, prove that this product has efficient absorption, significantly improves the effect of bone mineral content and bone density, has the osteoporotic effect of improvement.
Embodiment 3:
Prepare massfraction 25%CaCl respectively
2With the aqueous solution of massfraction 17%GSH, wherein CaCl
2Solution, GSH solution; Feeding shielding gas N
2Condition under, get CaCl respectively
2Solution 4.4g, GSH solution 27.1g mixes two solution (CaCl wherein
2For 0.01mol, GSH are 0.015mol), the temperature of regulating the control reaction is at 50 ℃, reaction times is 2.5 hours, regulate the pH value to 6.5 of mixed solution with rare HCl of massfraction 0.7%, fully left standstill 12 hours after the reaction, the adding massfraction is 30% ethanolic soln 94.5mL in mixed solution, is 105 ℃ of following evaporating, concentrating and crystallizings in temperature, supernatant liquor is abandoned in back centrifugation under the 3000r/min condition; After centrifugal gained precipitation placed 65 ℃ of vacuum-drying 4h, promptly obtain glutathione calcium chelate, according to above-mentioned experimentation on animals, prove that this product has efficient absorption, significantly improves the effect of bone mineral content and bone density, has the osteoporotic effect of improvement.
Embodiment 4:
Prepare massfraction 30%CaCl respectively
2With the aqueous solution of massfraction 25%GSH, under the condition that feeds shielding gas Ar, get CaCl respectively
2Solution 3.7g, GSH solution 24.6g mixes two solution (CaCl wherein
2For 0.01mol, GSH are 0.02mol); The temperature of regulating the control reaction is at 65 ℃, and the reaction times is 3 hours, and the pH value to 7 with rare HCl of massfraction 0.8% regulates mixed solution fully left standstill 13 hours after the reaction; Adding the ethanolic soln 113.2mL of massfraction 45% in mixed solution, is 115 ℃ of following evaporating, concentrating and crystallizings in temperature, and supernatant liquor is abandoned in back centrifugation under the 3500r/min condition; After centrifugal gained precipitation placed 70 ℃ of vacuum-drying 3h, promptly obtain glutathione calcium chelate, according to above-mentioned experimentation on animals, prove that this product has efficient absorption, significantly improves the effect of bone mineral content and bone density, has the osteoporotic effect of improvement.
Embodiment 5: the preparation of glutathione calcium chelate oral capsule
Get glutathione calcium chelate 20mg of the present invention, cooperate soyflour 150mg, ground rice 200mg, Star Dri 5 10mg, sucrose 15mg, behind an amount of dissolved in distilled water, granulation, drying incapsulate.
Claims (6)
1. glutathione calcium chelate is characterized in that being prepared by following step:
(1) at N
2Or under the protection of Ar, controlled temperature is at 30 ℃～80 ℃, is 1: 1～1: 3 according to the mol ratio of calcium chloride and gsh, and calcium chloride solution and glutathione solution are mixed, and with pH value scope to 5～8 of HCl solution conditioned reaction liquid, leaves standstill after fully reacting;
(2) ethanolic soln that adds in the above-mentioned reaction solution that leaves standstill with the mixing solutions evaporating, concentrating and crystallizing, separates, and gets precipitation;
(3) with above-mentioned precipitation drying, obtain product.
2. a kind of glutathione calcium chelate according to claim 1, the massfraction that it is characterized in that the calcium chloride solution described in the step (1) is 10%～40%, the massfraction of described glutathione solution is 10%～30%, the massfraction of described HCl solution is 0.5%～1%, the described reaction times is 1～4 hour, described time of repose is 10～15 hours, the massfraction of the described ethanolic soln of step (2) is 25%～45%, add-on is 2～5 times of reaction solution volumes, described evaporation concentration is carried out under 100 ℃～120 ℃, described separation is centrifugation, speed is 2000～5000r/min, and the described drying of step (3) is 60～75 ℃ of vacuum-drying 1～6h.
3. the preparation method of a glutathione calcium chelate is characterized in that comprising the steps:
(1) at N
2Or under the protection of Ar, controlled temperature is at 30 ℃～80 ℃, is 1: 1～1: 3 according to the mol ratio of calcium chloride and gsh, and calcium chloride solution and glutathione solution are mixed, and with pH value scope to 5～8 of HCl solution conditioned reaction liquid, leaves standstill after fully reacting;
(2) ethanolic soln that adds in the above-mentioned reaction solution that leaves standstill with the mixing solutions evaporating, concentrating and crystallizing, separates, and gets precipitation;
(3) with above-mentioned precipitation drying, obtain product.
4. the preparation method of a kind of glutathione calcium chelate according to claim 3, the massfraction that it is characterized in that the calcium chloride solution described in the step (1) is 10%～40%, the massfraction of described glutathione solution is 10%～30%, the massfraction of described HCl solution is 0.5%～1%, the described reaction times is 1～4 hour, described time of repose is 10～15 hours, the massfraction of the described ethanolic soln of step (2) is 25%～45%, add-on is 2～5 times of reaction solution volumes, described evaporation concentration is carried out under 100 ℃～120 ℃, described separation is centrifugation, speed is 2000～5000r/min, and the described drying of step (3) is 60～75 ℃ of vacuum-drying 1～6h.
5. the medicine of the illness that causes in preparation treatment calcium deficiency of claim 1 or 2 glutathione calcium chelate and the application in the protective foods.
6. the pharmaceutical composition of glutathione calcium chelate is characterized in that containing the claim 1 or 2 the glutathione calcium chelate of significant quantity and contains one or more pharmaceutically acceptable carriers.
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| CNB2006100365010A CN100486990C (en) | 2006-07-14 | 2006-07-14 | Glutathione calcium chelate and its preparing method, use and composition |
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| CNB2006100365010A CN100486990C (en) | 2006-07-14 | 2006-07-14 | Glutathione calcium chelate and its preparing method, use and composition |
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| CN1944457A true CN1944457A (en) | 2007-04-11 |
| CN100486990C CN100486990C (en) | 2009-05-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626867A (en) * | 2013-06-19 | 2014-03-12 | 中国海洋大学 | Preparation process for zinc fish-skin collagen polypeptide chelate |
| CN105394775A (en) * | 2015-11-07 | 2016-03-16 | 青岛海大众创海洋科技有限公司 | Nano peptide active calcium |
| CN105726459A (en) * | 2016-02-17 | 2016-07-06 | 北京乳凝创智生物技术研发中心（有限合伙） | Application of polypeptide chelated calcium in preparing transdermic absorbent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154358A (en) * | 1996-01-12 | 1997-07-16 | 常达正 | Method for prepn. and application of calcium amino-acidic |
| CN1144533C (en) * | 1998-03-25 | 2004-04-07 | 广西大学 | Composite amino-acid calcium compensating agent and its producing method |
| US20030228347A1 (en) * | 2000-09-12 | 2003-12-11 | Clark George H. | Amino acid chelate for the effective supplementation of calcium magnesium and potassium in the human diet |
| CN1566086A (en) * | 2003-06-18 | 2005-01-19 | 吴琼 | Amino acid calcium chelate, preparation and application thereof |
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2006
- 2006-07-14 CN CNB2006100365010A patent/CN100486990C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626867A (en) * | 2013-06-19 | 2014-03-12 | 中国海洋大学 | Preparation process for zinc fish-skin collagen polypeptide chelate |
| CN103626867B (en) * | 2013-06-19 | 2015-08-12 | 中国海洋大学 | A kind of preparation technology of zinc fish-skin collagen polypeptide chelate |
| CN105394775A (en) * | 2015-11-07 | 2016-03-16 | 青岛海大众创海洋科技有限公司 | Nano peptide active calcium |
| CN105394775B (en) * | 2015-11-07 | 2018-06-08 | 青岛海大众创海洋科技有限公司 | Nano peptide active calcium |
| CN105726459A (en) * | 2016-02-17 | 2016-07-06 | 北京乳凝创智生物技术研发中心（有限合伙） | Application of polypeptide chelated calcium in preparing transdermic absorbent |
| CN105726459B (en) * | 2016-02-17 | 2019-05-10 | 北京乳凝创智生物技术研发中心（有限合伙） | Application of the polypeptide chelate calcium in transdermal formulation preparation |
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| CN100486990C (en) | 2009-05-13 |
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