CN102731614B - A kind of collagen tripeptide chelating calcium and preparation method thereof - Google Patents
A kind of collagen tripeptide chelating calcium and preparation method thereof Download PDFInfo
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Abstract
There is the chelated calcium preparation technology of collagen tripeptide of calcium-enriching function, relate to protective foods preparation method.Preparation method's following steps: (one), by calcium hydroxide and collagen tripeptide with weight ratio 7:0.5 ~ 7:4 proportioning, collagen tripeptide at twice equivalent adds and mixes with calcium hydroxide, evenly; Solid-liquid ratio is 6:10 ~ 6:400; Said process control temperature is at 40 DEG C ~ 100 DEG C, and the reaction times is 90 minutes; (2) by above-mentioned mixed solution vacuum filtration, de-taste process is carried out; Collect filtrate concentrating; (3) dry, obtain product.Collagen tripeptide and calcium sequestration capacity is the invention enables greatly to promote.Collagen tripeptide chelating calcium preparation technology of the present invention simplifies equipment, shortens preparation time, Simplified flowsheet thus save human and material resources and time, reduces preparation cost.
Description
Technical field
The present invention relates to protective foods and preparation method, particularly relate to a kind of method of collagen tripeptide chelating calcium and preparation thereof.
Background technology
Calcium is one of mineral element that people's in-vivo content is maximum, is also one of most active element in body.Calcium has multiple important physiological function, participate in the normal function of the histoorgan of reconciling each system, and play an important role with Various Tissues cell, biomacromolecule level in body, calcium maintains the necessary composition of N&M regular excitation, is also ensure bone growth and maintain the necessary material of sclerotin hardness.But calcium deficiency belongs to global health problem, especially in the special populations such as the elderly, children, women, even if in Japan and many western industrialization country, calcium deficiency is ubiquity too.Implement planned replenishing the calcium, the body constitution and health level improving crowd is had very important significance.
Also exist a feast for the eyes at present on the market, miscellaneous calcium supplementing product, first-generation calcium-supplementing preparation is the inorganic calciums such as calcium carbonate, higher containing calcium concn, but solvability is poor, the absorption in body needs to consume hydrochloric acid in gastric juice, and needs to consume involved enzyme in human body and make carrier by VITAMIN and could be absorbed, therefore specific absorption is low, this kind of calsium supplement can increase the burden of kidney simultaneously.Second on behalf of organic calcium, is calcium ion, but inhalation effects factor is many, and side effect is large, mainly there is the low and toxicity problem in various degree of calcium contents.The third generation is calcium amino acid chelate, calcium and the whole molecule of organic group complete by intestinal absorption, there is stable chemical nature, biological value advantages of higher, the more important thing is VITAMIN, the impact of unsaturated fatty acids isoreactivity composition is less, can reduce the antagonism with other trace element and major element in vivo.Wherein small-peptide chelated calcium is identical with normal physiological calcium absorption, more easily absorbs than calcium amino acid chelate.
At present, calcium amino acid chelate needs dehydrated alcohol precipitation and recrystallizing technology to carry out the purifying of calcium amino acid chelate in process of production, and man-hour is long, and cost is high.Often select calcium chloride as calcium source in small-peptide chelated calcium preparation process, need artificial adjust ph, introduce non-active ingredients, and for improving purity, chelating calcium and ionized calcium must be separated, complex process by alcohol precipitation.
Collagen tripeptide is called for short CTP (Collagentripeptide), and the molecular weight be made up of three amino acid is at the small-molecular peptides of about 200 ~ 500Dalt, and molecular-weight average is about 280Dalt.Research shows: tripeptides can be absorbed by the body without the need to decomposing, and due to the interaction between its three amino acid compositions, makes it have the activity stronger compared with single amino acids; Collagen tripeptide can infiltrate in keratoderma, epidermal area, skin corium and hair/hair follicle, has and promotes the several functions such as collagen and hyaluronic acid synthesis, check melanin generation, moisturizing, slim, moisturizing, preventing osteoporosis.
Collagen mainly extracts from ox and Zhu Deng animal tissues for a long time.Can the people that make of mad cow disease and foot and mouth disease in recent years start the substitute considering to use ox, pig collagen.With free of contamination fish-skin for collagen tripeptide prepared by raw material have that security is high, cell agglutinating value(of coal) is good, transparent, odorless and the feature such as non-stimulated.
China Patent No. be 200910151023.1 and the patent No. be 200910063282.9 individually disclose the chelated calcium method of Preparation of amino acid, but to there is shortcoming in aforesaid method be: need dehydrated alcohol to precipitate and recrystallizing technology, production unit is complicated, and preparation time is long.China Patent No. 200610036501.0 discloses glutathione calcium chelate preparation technology, needs artificially to regulate pH in preparation process; Alcohol precipitation is needed to be separated chelating calcium and ionized calcium.
At present, very large progress is obtained to the research of collagen both at home and abroad, but not yet someone proposes collagen tripeptide to be combined with calcium-supplementing preparation and produces a kind of thinking and countermeasure with bioactive high efficiency calcium-enriching preparation completely newly.
Summary of the invention
The object of this invention is to provide a kind of collagen tripeptide chelating calcium and preparation method thereof, the invention provides a kind of collagen tripeptide be combined with calcium-supplementing preparation produce a kind of completely newly there is bioactive high efficiency calcium-enriching preparation, the present invention also provides a kind of preparation technology with bioactive high-efficient calcium replenishing agent completely newly.
A kind of collagen tripeptide chelating calcium of the present invention, by calcium hydroxide and collagen tripeptide with weight ratio 7: 0.5 ~ 7: 4 proportioning, through the product made by mixing, de-taste process, vacuum filtration, concentrated, drying.
The chelated calcium preparation method of a kind of collagen tripeptide of the present invention, operates in accordance with the following steps:
(1) with calcium hydroxide and collagen tripeptide for raw material, the weight ratio of collagen tripeptide and calcium hydroxide is 7: 0.5 ~ 7: 4, and collagen tripeptide at twice equivalent adds and mixes with calcium hydroxide, mixing; Take water as liquid, above-mentioned raw materials adds in liquid, and feed liquid weight ratio is 6: 10 ~ 6: 400; Said process control temperature is at 40 DEG C ~ 100 DEG C, and the reaction times is 90 minutes;
(2) above-mentioned mixed solution is carried out vacuum filtration, suction filtration condition is 0.04MPa; Collect filtrate, with 30% gac at 40 DEG C of temperature, water-bath 30 minutes, carries out de-taste process; Then the filtrate of de-taste process is carried out vacuum filtration, suction filtration condition is 0.04Mpa; Collect filtrate concentrating;
(3) above-mentioned concentrated solution is carried out drying, obtain product.
Vacuum concentration condition described in (two) step is 40 DEG C ~ 50 DEG C.
Described in (three) step, drying can be vacuum-drying or spraying dry.
Collagen tripeptide chelating calcium designed by invention be with small molecules fish skin collagen tripeptides and calcium hydroxide under given conditions chelating form.
The present invention and the patent No. be 200910151023.1 and the patent No. be compared with the chelated calcium method of 200910063282.9 Preparation of amino acid, maximum difference is not need dehydrated alcohol to precipitate and recrystallizing technology, simplifies corresponding production unit, shortens preparation time.The present invention, compared with the patent No. 200610036501.0 glutathione calcium chelate preparation technology and existing peptide chelating calcium preparation technology, selects calcium hydroxide to prepare collagen tripeptide chelating calcium, without the need to artificially regulating pH in preparation process as calcium source; Chelating calcium and ionized calcium is separated without the need to alcohol precipitation; Equivalent adds collagen tripeptide at twice, and collagen tripeptide and calcium sequestration capacity are promoted greatly.Collagen tripeptide chelating calcium preparation technology of the present invention simplifies equipment, shortens preparation time, Simplified flowsheet thus save human and material resources and time, reduces preparation cost.
Accompanying drawing explanation
Fig. 1 is the impact effect schematic diagram of collagen tripeptide chelating calcium to mouse femur calcium contents.
Note: in figure, * represents to compare with blank group to have the significance of difference, P < 0.05
In figure, * * represents to compare with blank group to have difference pole significance, P < 0.01
Embodiment
The present invention is described in detail to use best embodiment below.
Embodiment 1:
Be to mix collagen tripeptide and calcium at 7: 2 according to mass ratio, solid-liquid ratio is 6: 40, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 5.75%.
Calcium described in all embodiments is calcium hydroxide.
Embodiment 2:
Be to mix collagen tripeptide and calcium at 7: 2 according to mass ratio, solid-liquid ratio is 6: 120, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 6.48%.
Embodiment 3:
Be to mix collagen tripeptide and calcium at 7: 2 according to mass ratio, solid-liquid ratio is 6: 400, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 9.34%.
Embodiment 4:
Be to mix collagen tripeptide and calcium at 7: 3 according to mass ratio, solid-liquid ratio is 6: 40, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 6.40%.
Embodiment 5:
Be to mix collagen tripeptide and calcium at 7: 3 according to mass ratio, solid-liquid ratio is 6: 120, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 7.70%.
Embodiment 6:
Be to mix collagen tripeptide and calcium at 7: 3 according to mass ratio, solid-liquid ratio is 6: 400, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 13.00%.
Embodiment 7:
Be to mix collagen tripeptide and calcium at 7: 4 according to mass ratio, solid-liquid ratio is 6: 40, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 5.98%.
Embodiment 8:
Be to mix collagen tripeptide and calcium at 7: 4 according to mass ratio, solid-liquid ratio is 6: 120, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 7.75%.
Embodiment 9:
Be to mix collagen tripeptide and calcium at 7: 4 according to mass ratio, solid-liquid ratio is 6: 400, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 13.27%.
Embodiment 10:
Be to mix collagen tripeptide and calcium at 7: 3 according to mass ratio, solid-liquid ratio is 6: 400, and control temperature is 60 DEG C, and the reaction times is 90min.After abundant reaction, controlling pressure is that 0.04MPa carries out vacuum filtration, collects filtrate, adds 30% granulated active carbon after concentration to be 4% sodium hydroxide solution and concentration be 4% hydrochloric acid soln activation, in 40 DEG C, and water-bath 30min.Controlling pressure is that 0.04MPa carries out vacuum filtration, and collect filtrate, vacuum concentration, is placed in 70 DEG C by concentrated solution, vacuum-drying 1 ~ 2h, namely obtains collagen tripeptide chelating calcium.Now in collagen tripeptide chelating calcium, calcium contents is 14.42%.
Collagen tripeptide chelating calcium of the present invention, according to " function of health food assessment process and method of inspection specification ", take kunming mice as laboratory animal, male and female half and half, maximum gavage amount method (MTD) is adopted to test, dose design is 10.0g/kg.bw, gavage 3 times in 24 hours, Continuous Observation two weeks.Mouse is all without dead, and body weight increases to some extent, there was no significant difference compared with blank group.Therefore the true border of collagen tripeptide chelating calcium of the present invention is nontoxic.
Collagen tripeptide chelating calcium of the present invention is a kind of stable water-soluble calcium inner complex, and belong to little peptide binding substances, specific absorption is high, absorbs in small intestine with the form of small-peptide chelated calcium, avoids combining with the oxalic acid in food, phytic acid etc. and affects and absorb.Collagen tripeptide chelating calcium is absorbed by transhipment in human body, supplement calcium and collagen nutrition, and collagen tripeptide also can play distinctive biological activity in vivo, make product of the present invention can high efficiency calcium-enriching, the distinctive physiological function of collagen tripeptide can be played again simultaneously, can be widely used in production and life as protective foods and additive etc.
To wean 20 days, 12 ~ 15g, kunming mice is animal subject, be divided into Normal group, model group, experimental group, except Normal group is fed conventional feed, all the other each group low calcium feed of all feeding, to cause calcium deficiency model, Normal group, model group is with the process of gavage distilled water comfort, experimental group gavage collagen tripeptide chelating calcium 2.4mg/g, result display model group femur calcium contents is starkly lower than Normal group and has the significance of difference, display modeling success.Experimental group femur calcium contents, higher than model group and Normal group, carries out statistical study with Normal group, and its result shows, and difference has pole significance.Specifically see accompanying drawing 1.Femur calcium contents is high, illustrates that collagen tripeptide chelating calcium not only easily absorbs, and the calcium utilization absorbed is higher, can be deposited on bone, make bone strong.Normal group in experimentation, model group, experimental group does not have the significance of difference in body weight.Visible collagen tripeptide chelating calcium of the present invention has the effect of obvious supplement calcium.
Select 50 ~ 70 years old, climacteric the women more than more than 10 years 154, get rid of and take oestrogenic hormon, steroid hormone, anticonvulsant drug, the people of the medicine of thiazide diuretics or other influences calcium metabolism, 127 experimenters enter data statistics, be divided into control group and intervention group, intervention group takes 1.2g collagen tripeptide chelating calcium every day, and control group takes placebo.The DPX-L type Dual-energy X-rays absorptionmetry adopting GELunar company of the U.S. to produce measures 1st ~ 4 lumbar spine bmds, and through the tracing observation of a year, result was as shown in table 1.Before research, intervention group is close with control group bone density, and through the follow-up study discovery of a year, its lumbar spine bmd of menopausal women taking collagen tripeptide chelating calcium group every day will apparently higher than the lumbar spine bmd of control group menopausal women taking placebo.This research experimenter is that the women in more than 10 years climacteric is as research object, because its body inner estrogen level obviously declines, calcium content of bone runs off more obvious, with collagen tripeptide chelating calcium, it is intervened, after 1 year, its bone density loss degree is starkly lower than control group, has the significance of difference compared with control group.Visible collagen tripeptide chelating calcium of the present invention has the effect of supplement calcium.
Table 1127 experimenter's lumbar spine bmd (BMD) tracing detection result
Above embodiment is the one of the present invention's more preferably embodiment, and the usual change that those skilled in the art carry out within the scope of the technical program and replacing should be included in protection scope of the present invention.
Claims (2)
1. there is the chelated calcium preparation technology of collagen tripeptide of calcium-enriching function, it is characterized in that, operate in accordance with the following steps:
(1) with calcium hydroxide and collagen tripeptide for raw material, the weight ratio of collagen tripeptide and calcium hydroxide is 7: 0.5 ~ 7: 4, and collagen tripeptide at twice equivalent adds and mixes with calcium hydroxide, mixing; Take water as liquid, above-mentioned raw materials adds in liquid, and feed liquid weight ratio is 6: 10 ~ 6: 400; Said process control temperature is at 40 DEG C ~ 100 DEG C, and the reaction times is 90 minutes;
(2) above-mentioned mixed solution is carried out vacuum filtration, suction filtration condition is 0.04MPa; Collect filtrate, with 30% gac at 40 DEG C of temperature, water-bath 30 minutes, carries out de-taste process; Then the filtrate of de-taste process is carried out vacuum filtration, suction filtration condition is 0.04Mpa; Collect filtrate concentrating;
(3) above-mentioned concentrated solution is carried out drying, obtain product.
2. a kind of chelated calcium preparation technology of collagen tripeptide with calcium-enriching function as claimed in claim 1, is characterized in that, described in (three) step, drying can be vacuum-drying or spraying dry.
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| CN107712910A (en) * | 2017-09-22 | 2018-02-23 | 西安交通大学 | A kind of gelatin small peptide or collagen tripeptide chelating calcium and magnesium and preparation method thereof |
| CN111990649A (en) * | 2020-08-13 | 2020-11-27 | 自然资源部第三海洋研究所 | Preparation method of water-soluble melanin chelated calcium salt of squid |
| CN117946207B (en) * | 2024-03-26 | 2024-06-25 | 北京青颜博识健康管理有限公司 | Mineral-containing high-purity collagen tripeptide and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683008A (en) * | 2005-03-14 | 2005-10-19 | 山东轻工业学院 | Collagen polypeptide preparation for supplementing calcium and its preparing method |
| CN1887902A (en) * | 2006-07-28 | 2007-01-03 | 北京华美天意科技开发有限公司 | Amino acid short peptide chelate and its prepn |
| CN101773663A (en) * | 2009-01-12 | 2010-07-14 | 顾凌洁 | New application of collagen chelate |
| CN101870995A (en) * | 2009-04-21 | 2010-10-27 | 陈栋梁 | Process for preparing collagen tripeptide |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683008A (en) * | 2005-03-14 | 2005-10-19 | 山东轻工业学院 | Collagen polypeptide preparation for supplementing calcium and its preparing method |
| CN1887902A (en) * | 2006-07-28 | 2007-01-03 | 北京华美天意科技开发有限公司 | Amino acid short peptide chelate and its prepn |
| CN101773663A (en) * | 2009-01-12 | 2010-07-14 | 顾凌洁 | New application of collagen chelate |
| CN101870995A (en) * | 2009-04-21 | 2010-10-27 | 陈栋梁 | Process for preparing collagen tripeptide |
Non-Patent Citations (1)
| Title |
|---|
| 胶原三肽粗钙吸收动物实验研究;倪萌 等;《中国食品工业》;20101015(第10期);第80页倒数第1段 * |
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