CN1709907A - Decarboxamidation grain protein-chrominium element chelate and preparation method - Google Patents
Decarboxamidation grain protein-chrominium element chelate and preparation method Download PDFInfo
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- CN1709907A CN1709907A CNA2005100504292A CN200510050429A CN1709907A CN 1709907 A CN1709907 A CN 1709907A CN A2005100504292 A CNA2005100504292 A CN A2005100504292A CN 200510050429 A CN200510050429 A CN 200510050429A CN 1709907 A CN1709907 A CN 1709907A
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- chromium
- grain protein
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- decarboxamidation
- chrominium
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- 239000013522 chelant Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 40
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims description 62
- 235000007164 Oryza sativa Nutrition 0.000 claims description 39
- 235000018102 proteins Nutrition 0.000 claims description 39
- 235000009566 rice Nutrition 0.000 claims description 39
- 235000013339 cereals Nutrition 0.000 claims description 35
- 108010073032 Grain Proteins Proteins 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 14
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
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- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- 239000000284 extract Substances 0.000 claims description 9
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- 238000001914 filtration Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 6
- 229940046374 chromium picolinate Drugs 0.000 claims description 6
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 claims description 6
- HPCCGRCEBFBZQP-UHFFFAOYSA-N chromium;pyridine-3-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CN=C1 HPCCGRCEBFBZQP-UHFFFAOYSA-N 0.000 claims description 6
- DTGBCAFLVSFZRF-UHFFFAOYSA-N 2-aminoacetic acid;chromium Chemical compound [Cr].NCC(O)=O DTGBCAFLVSFZRF-UHFFFAOYSA-N 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical group [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 5
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- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 4
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
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- 206010019708 Hepatic steatosis Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 206010029240 Neuritis Diseases 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229960000359 chromic chloride Drugs 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
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- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Coloring Foods And Improving Nutritive Qualities (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
This invention has disclosed a manufacturing method to a chelate of decarboxamidation corny protein-chrome. Count by weight per cent, chromium content of chelate is 0.5 to 1.5 percent; This method is utilizing chemical activity of chemical groups of decarboxamidation corny protein-chrome, compound protein with chromium, make decarboxamidation corny protein-chrome including active Ce3 + ion, by centrifugal separation, filtrate or spray drying to get solid state powder.The technological process of this method are simple, the production cost is cheap, apt to popularize implementation.
Description
Technical field
The present invention relates to a kind of Decarboxamidation grain protein-chrominium element chelate and preparation method thereof.
Background technology
Chromium is one of trace element of needed by human, and the contribution of human physiological functions is mainly showed in the following areas:
1) Cr
3+Ion is the integral part in glucose tolerance factor (GIF) active centre, is bringing into play important physiological function in human body.Cr
3+Ion can assist Regular Insulin to keep NGT, makes that the glycogen resultant velocity increases in the body, and the blood sugar mobility improves, thereby makes glucose transfer to other tissue fast and be utilized from liver.Simultaneously, Cr
3+The collaborative Regular Insulin of ion participates in the metabolism of lipid, protein and nucleic acid, improves the blood fat situation, has significant lipopenicillinase and decreasing cholesterol effect.
2) the scarce chromium of human body can produce glucose, fat, protein metabolism disturbance, gives rise to diseases as diabetes, atherosclerosis, coronary heart disease, peripheral neuritis, myopia etc.Mending chromium is one of convenient way that reduces hyperinsulinism, hyperglycemia and hyperlipidemia level, prevent diabetes.And mending chromium can also the improvement symptom relevant with carbohydrate metabolism and lipid metabolism, as fatty liver, obesity and acne etc., even can promote the human development, builds up health and myopia prevention in advance.
3) along with people's growth in the living standard, the sickness rate surge of diabetes has become the third-largest disease global, harm humans health.Cr
3+Be in very important status at aspects such as the generation of diabetes, development, prevention, treatments.Aspect treating diabetes, organochromium compounds has complementary effect.
Chromium has at occurring in nature+6 ,+3 and+2 three kinds of valence states, wherein CR
6+Bio-toxicity is big, Cr
2+Stable inadequately, the crowd that all is not suitable for mends chromium.The trivalent inorganic chromium is cheap, and security is higher, and solubility is good, but specific absorption is low in vivo, only is 0.4～3% even lower.Chromium supplementing agent adopts the trivalent organic chromium more at present, as nicotinic acid chromium, chromium picolinate, chelating amino acids chromium, yeast chromium etc.The biological absorption of organic chromium is higher, reaches as high as 25～30%, and validity is more than ten times of inorganic chromium, and its shortcoming is to cost an arm and a leg.
Human body does not still have clear conclusions at present in the world to the demand aspect of trace element chromium.According to the dietary recommendations continued amount (RDA) that the U.S. formulated in 1989, adult's cr intake should be 50～200 μ g/d.But the investigation of the U.S. shows that the chromium amount that many people take in is lower than the lower limit of dietary recommendations continued amount from diet, that is to say that most people are in poor chromium state, and it is more serious that its elderly and diabetics lack the chromium phenomenon.
The content of chromium in cereal kind skin is higher than internal layer, thereby more smart its chromium content of grain processing is littler.Micronutrient levels such as chromium is lower in whole meal flour and the commodity rice, and the chromium element is very high at flour and rice processing and refining process turnover rate.The chromium constituent content is respectively 130 μ g/kg and 80 μ g/kg in China's wheat and the early rice brown rice, and chromium element average content is about 30 μ g/kg in flour and the commodity rice.
China resident is accustomed to edible based on the product after the cereal retrofit.Long-term edible purified diet can make the chromium element transition that stores in the body drain, and health is produced detrimentally affect even causes disease.On the basis that does not change the human diet structure, application safety is effectively mended the chromium goods, is the effective way of improving human health, preventing and treating diabetes.Mend chromium and can take medicine to mend forms such as chromium and food benefit chromium, the high cost that its Chinese traditional medicine is mended chromium is conspicuous.Protein is one of major ingredient of cereal foods, is rich in the amino acid of needed by human body.Simultaneously, grain protein contains a large amount of activity chemistry groups, can generate the protein chromic salts with the trivalent chromic ion reaction, and this provides scientific basis for developing safe food benefit chromium goods.
Summary of the invention
The purpose of this invention is to provide a kind of Decarboxamidation grain protein-chrominium element chelate and preparation method thereof.
Decarboxamidation grain protein-chrominium element chelate, by weight percentage, the content of chromium element in inner complex is 0.5～1.5%.
The preparation method of Decarboxamidation grain protein-chrominium element chelate may further comprise the steps:
1) the grain protein powder is placed deionized water be made into 5～15% suspension, when stirring, add concentrated hydrochloric acid and regulate pH value to 1～4, under 120～126 ℃, 0.11～0.15MPa condition, carry out deacylated tRNA amine and react 5～30min;
2) when stirring, with saturated alkaline solution regulating step 1) the pH value of the suspension that obtained is to the iso-electric point of deacylated tRNA amine grain protein, carries out centrifugation or filtering separation then, acquisition deacylated tRNA amine grain protein solid;
3) with deacylated tRNA amine grain protein solid dispersed in deionized water, under 50～90 ℃, agitation condition, extract water-soluble deacylated tRNA amine grain protein, adopt centrifugation or filter separation method to collect supernatant liquor;
4) chromic salts that the chromium element wt is accounted for deacylated tRNA amine grain protein solid weight 0.5～1.5% adds above-mentioned supernatant liquor, under 120～126 ℃, 0.11～0.15MPa condition, react 5～30min, after the cooling, centrifugation or filtering separation, after deionized water washes repeatedly or dialyses, naturally cool shine dry, be lower than oven dry or spraying drying under 80 ℃ of temperature, be ground to less than 300 orders, obtain water content less than 10% powder.
Grain protein is gluten powder, rice protein powder or zein.Chromic salts is inorganic chromate salt or organic chromic salts, and inorganic chromate salt is chromium chloride, chromium nitrate, chromium sulphate or their hydrate, and organic chromic salts is nicotinic acid chromium, chromium picolinate or glycine chromium.Basic solution is NaOH, NaHCO
3, Na
2CO
3The aqueous solution or ammoniacal liquor.The whizzer centrifugal speed is 3000～5000g, and the centrifugation time is 10～20min.The dispersion agent that spraying drying adopts is sorbitan mono-laurate, anhydrous sorbitol monopalmitate, anhydrous sorbitol tristearate or Witconol AL 69-66.
Advantage of the present invention is:
1) utilize the chemically reactive of deacylated tRNA amine grain protein hydrophilic radical and trivalent chromium elements compounding and form inner complex, production technique is simple;
2) utilize pressure kettle or autoclave to be the response controller tool, under 120～126 ℃, 0.11～0.15MPa condition preparation deacylated tRNA amine grain protein and with the inner complex of trivalent chromium element, production cost is low;
3) Decarboxamidation grain protein-chrominium element chelate and gastrointestinal tract mucous affinity height have improved Cr greatly
3+Ion has also reduced the environment residual quantity simultaneously in the intravital specific absorption of people; Have only deacylated tRNA amine grain protein in gi tract by digestion, after the hydrolysis, Cr
3+Ion just can discharge and bring into play its physiological function, otherwise Cr
3+From still with deacylated tRNA amine grain protein mortise, be difficult for causing side effect, improved Cr
3+The ionic safety in utilization;
4) the Decarboxamidation grain protein-chrominium element chelate powder is easy to mix with flour, forms homodisperse system, and is easy to use.
Embodiment
It is gluten powder, rice protein powder or zein that the present invention uses protein.
Gluten powder also claims vital wheat gluten, is a kind of natural plant protein matter of extracting for the raw material deep processing with the whole meal flour.Suitable gluten powder can be selected from the commerical prod of protein content 〉=75% (butt), buys gluten powder as can be from Shanghai prosperous flavor Food Co., Ltd, sky, Henan Province hat vegetable-protein company limited, the happy health food in Tongcheng City, Anhui Province company limited.
Rice protein powder is a kind of highly purified rice protein product of producing from rice meal, rice slag or rice are poor, its protein content 〉=80% (butt).From rice meal, the technology of extracting rice protein during rice slag or rice are poor is known, as in following document, stating, the document is incorporated herein by reference: " Wang Zhangcun; Yao Huiyuan: Extraction of Rice Protein from Rice Dregs. research grain and fodder industry; 2003; (8): 37-38. " in addition, Chinese patent 03134973.0 discloses " extracting the method for rice protein from rice ", Chinese patent 03134972.2 discloses " alkaline process extracts the method for rice protein ", and Chinese patent 200410039303.0 discloses " being raw material extraction rice protein and the processing method of making Starch rice with the rice ".Suitable rice protein powder also can be selected from the commerical prod of protein content 〉=80% (butt), as buying rice protein powder from Guilin Red Star bio tech ltd.
The technology of extracting zein from Zein powder (also claiming corn gluten meal) makes known, as in following document, stating, the document is incorporated herein by reference: " Zhang Zhong; Qi Aiyun: zein extraction process and Study on Functional; grain and fodder industry; 2004 (9): 21-23. " Chinese patent 00101222.3 discloses the technology of " using preparing alcohol-soluble corn protein membrane from corn gluten ", has wherein described the method for extracting zein from Zein powder.
The preparation of Decarboxamidation grain protein-chrominium element chelate is carried out in two steps, the first step is added hydrochloric acid in grain protein solution or suspension, under high temperature, condition of high voltage, make the reaction of grain protein generation high pressure sex change and deacylated tRNA amine, make N in the protein and glutamine deamidate and generate aspartic acid and L-glutamic acid, thereby the electric density of protein macromolecule is increased, and solvability improves.Deacylated tRNA amine grain protein has a large amount of carboxyls, can with metal ion-chelant.The adding mode of hydrochloric acid and the requirement of usage quantity are not very strict, generally speaking, can directly pour an amount of dilute hydrochloric acid under agitation condition, can drip concentrated hydrochloric acid gradually yet, and the pH value is controlled at 1～4, and the present invention recommends pH to be controlled at about 2.
Second step added chromic salts in the solution of deacylated tRNA amine grain protein, made the Cr in the solution under high temperature, condition of high voltage
3+The carboxyl generation ionic reaction of ion and deacylated tRNA amine grain protein.Said chromic salts is inorganic chromate salt or organic chromic salts, and inorganic chromate salt is chromium chloride, chromium nitrate, chromium sulphate or their hydrate, and organic chromic salts is nicotinic acid chromium, chromium picolinate or glycine chromium.Consider cost, the present invention recommends to use chromium chloride, chromium nitrate, chromium sulphate or their hydrate, and its consumption should make the chromium element wt be equivalent to 0.5～1.5% of Decarboxamidation grain protein-chrominium element chelate weight, and recommendation is 1.0%.After chromic salts added deacylated tRNA amine grain protein solution, at room temperature promptly can be observed white precipitate and occur, high temperature of the present invention, reaction under high pressure condition can be accelerated the formation of Decarboxamidation grain protein-chrominium element chelate.
Prevent that chromic salts from deacylated tRNA amine grain protein solution hydrolysis taking place is one of key of the present invention.Chromic salts pressed powder or aqueous solution of chromium salt directly can be added in the deacylated tRNA amine grain protein solution, under high temperature, condition of high voltage, react then.In the occasion of using aqueous solution of chromium salt, if the aqueous solution of chromium salt storage time surpasses 1 day, should in aqueous solution of chromium salt, splash into an amount of diluted acid, purpose is to make aqueous solution of chromium salt stable.
Adopting high temperature, the deacylated tRNA amine reaction of condition of high voltage control grain protein and the preparation of Decarboxamidation grain protein-chrominium element chelate is one of key of the present invention.Pressure kettle can be adopted in small serial production of the present invention, autoclave should be adopted and produce in enormous quantities.For preventing the acid volatilization corrosion that atmosphere caused, pressure kettle or autoclave domestic demand are equipped with Corrosion resistant linings or coating.The reaction of deacylated tRNA amine and the preparation of Decarboxamidation grain protein-chrominium element chelate of grain protein can be adopted the heating of gas range naked light, also can adopt the electric furnace heating.
The separation of deacylated tRNA amine grain protein and the separating technology of Decarboxamidation grain protein-chrominium element chelate can be suited measures to local conditions, and select for use filter cloth filtration, whizzer or pressure filter to separate.
Decarboxamidation grain protein-chrominium element chelate is a pressed powder, separates back application deionized water and washes repeatedly, to remove remaining free chromium ion.Can be naturally after cleaning finishes cool shine dry, being lower than oven dry or spraying drying under 80 ℃ of temperature, be ground to less than 300 orders, obtain water content less than 10% white powder.
For guaranteeing the security of Decarboxamidation grain protein-chrominium element chelate as aliment chrome complement agent, Decarboxamidation grain protein-chrominium element chelate after the present invention recommends to clean places dialysis tubing, adopt deionized water to dialyse, the Decarboxamidation grain protein-chrominium element chelate with dialysis carries out drying, grinding, packing then.
As select spraying drying for use, then needing will be through cleaning or the Decarboxamidation grain protein-chrominium element chelate slurrying of dialysis treatment, and adds dispersion agent.Being applicable to that dispersion agent of the present invention has strict requirement, should be food grade, and its consumption should be within the allowance of foodstuff additive.The dispersion agent of recommending to use is sorbitan mono-laurate, anhydrous sorbitol monopalmitate, anhydrous sorbitol tristearate or Witconol AL 69-66.The purpose that adds dispersion agent is the viscosity that reduces slurry, and the spraying drying of high concentration slurry is implemented easily, thereby reduces energy consumption for drying.Be applicable to that spray drying device of the present invention is routinely, technical is well-known.
Further specify the present invention below in conjunction with specific examples.
Embodiment 1:
With gluten powder, chromium trichloride is the preparation method of feedstock production deacylated tRNA amine aleuronat-chromium element inner complex, may further comprise the steps:
1) takes by weighing the 20g gluten powder and place beaker, with the suspension that is made into 5% in the deionized water, in induction stirring, add concentrated hydrochloric acid and make the suspension acidifying, regulate pH of suspension value to 1, suspension is placed in the pressure kettle, under 120 ℃, 0.11MPa condition, carry out deacylated tRNA amine reaction 5min, be cooled to room temperature;
2) when stirring, the pH to pH=4.5 with saturated NaOH solution adjusting deacylated tRNA amine aleuronat suspension carries out centrifugation 10min then under the 3000g condition, incline and fall supernatant liquor, obtains deacylated tRNA amine aleuronat solid;
3) with deacylated tRNA amine aleuronat solid dispersed in the 400ml deionized water, under 50 ℃, high-speed stirring condition, extract water-soluble deacylated tRNA amine aleuronat, centrifugation 20min under the 5000g condition collects supernatant liquor; Remaining deacylated tRNA amine aleuronat solid is scattered in the 400ml deionized water again, extracts water-soluble deacylated tRNA amine aleuronat under the same conditions.The supernatant liquor of twice resulting separation is merged (weight of water-soluble deacylated tRNA amine aleuronat is 6.7g);
4) take by weighing 0.15g CrCl
3(containing chromium element 0.05g), the supernatant liquor of adding step 3) gained stirs until CrCl
3All dissolvings, under 126 ℃, 0.15MPa condition, react 30min, after the cooling, adopt funnel to filter, obtain deacylated tRNA amine aleuronat-chromium element inner complex solid, place dialysis tubing,, change water every day once with deionized water dialysis 3 days, the product of will dialysing filters, under 70 ℃ of temperature, dry, be ground to particle diameter, pack less than 300 orders.The chromium constituent content is 0.75% in the product.
Embodiment 2:
With rice protein powder, chromium nitrate is the preparation method of feedstock production deacylated tRNA amine rice protein powder-chromium element inner complex, may further comprise the steps:
1) takes by weighing the 20g rice protein powder and place beaker, with the suspension that is made into 15% in the deionized water, in induction stirring, add concentrated hydrochloric acid, regulate pH of suspension value to 3, suspension is placed the autoclave internal heating, under 126 ℃, 0.15MPa condition, carry out deacylated tRNA amine reaction 30min, be cooled to room temperature;
2) when stirring, use saturated NaHCO
3Solution is regulated the pH value of deacylated tRNA amine rice protein suspension to pH=4.2, adopts the funnel filtering separation to obtain deacylated tRNA amine rice protein solid;
3) with deacylated tRNA amine rice protein solid dispersed in the 400ml deionized water, under 90 ℃, high-speed stirring condition, extract water-soluble deacylated tRNA amine rice protein, centrifugation 15min under the 4000g condition collects supernatant liquor; Remaining deacylated tRNA amine rice protein solid is scattered in the 400ml deionized water again, extracts water-soluble deacylated tRNA amine rice protein under the same conditions.The supernatant liquor of twice resulting separation is merged (weight of water-soluble deacylated tRNA amine rice protein is 4.2g);
4) take by weighing 0.23g Cr (NO
3)
3(containing chromium element 0.05g) powder is made into 2% solution with deionized water, adds the supernatant liquor of step 3) gained, stirs until Cr (NO
3)
3All dissolvings are reacted 20min, after the cooling under 124 ℃, 0.13MPa condition, the employing funnel filters, and uses deionized water rinsing 5 times when filtering, and obtains deacylated tRNA amine rice protein-chromium element inner complex solid, natural at normal temperatures airing is ground to particle diameter less than 300 orders, pack.The chromium constituent content is 1.1% in the product.
Embodiment 3:
With zein, chromium sulphate is the preparation method of the beautiful corn protein of feedstock production deacylated tRNA amine-chromium element inner complex, may further comprise the steps:
1) takes by weighing the 20g zein and place beaker, with the suspension that is made into 10% in the deionized water, in induction stirring, add concentrated hydrochloric acid, regulate pH of suspension value to 2, suspension is placed the autoclave internal heating, under 126 ℃, 0.15MPa condition, carry out deacylated tRNA amine reaction 10min, be cooled to room temperature;
2) when stirring, use saturated Na
2CO
3Solution is regulated the pH value of deacylated tRNA amine corn protein suspension to pH=4.6, carries out centrifugation 15min then under the 4000g condition, inclines and falls supernatant liquor, obtains deacylated tRNA amine corn protein solid;
3) with deacylated tRNA amine corn protein solid dispersed in the 400ml deionized water, under 90 ℃, high-speed stirring condition, extract water-soluble deacylated tRNA amine corn protein, centrifugation 15min under the 4000g condition collects supernatant liquor; Remaining deacylated tRNA amine corn protein solid is scattered in the 400ml deionized water again, extracts water-soluble deacylated tRNA amine corn protein under the same conditions.The supernatant liquor of twice resulting separation is merged (weight of water-soluble deacylated tRNA amine corn protein is 5.6g);
4) take by weighing 0.19g Cr
2(SO
4)
3(containing chromium element 0.05g) powder, the supernatant liquor of adding step 3) gained stirs until Cr (NO
3)
3All dissolvings are reacted 5min under 124 ℃, 0.13MPa condition, after the cooling, adopt funnel to filter, and when filtering with deionized water rinsing 5 times, obtain deacylated tRNA amine corn protein-chromium element inner complex solid;
5) the resulting deacylated tRNA amine of step 4) corn protein is scattered in the 300ml water, adds 0.017g anhydrous sorbitol tristearate, fully stir, make to mix, spraying drying under 200 ℃ of inlet temperature, 95 ℃ of conditions of air outlet temperature, pack.The chromium constituent content is 0.88% in the product.
Embodiment 4:
With gluten powder, CrCl
36HO
2Preparation method for feedstock production deacylated tRNA amine aleuronat-chromium element inner complex:
With the saturated NaOH solution of aqueous ammonia to replace adjust pH, use 0.26g CrCl
36HO
2Replace 0.15g CrCl
3Carry out chelatropic reaction, all the other conditions are with example 1.
Embodiment 5:
With rice protein powder, nicotinic acid chromium is the preparation method of feedstock production deacylated tRNA amine rice protein-chromium element inner complex:
Replace 0.23g Cr (NO with the 0.40g nicotinic acid chromium
3)
3Carry out chelatropic reaction, all the other conditions are with example 2.
Embodiment 6:
With zein, chromium picolinate is the preparation method of feedstock production deacylated tRNA amine corn protein-chromium element inner complex:
Replace 0.19g Cr with the 0.40g chromium picolinate
2(SO
4)
3Carry out chelatropic reaction, replace the anhydrous sorbitol tristearate as spray-dired dispersion agent with Witconol AL 69-66, with all the other conditions with example 3.
Embodiment 7:
With zein, glycine chromium is the preparation method of feedstock production deacylated tRNA amine corn protein-chromium element inner complex:
Replace 0.19g Cr with 0.27g glycine chromium
2(SO
4)
3Carry out chelatropic reaction, replace the anhydrous sorbitol tristearate as spray-dired dispersion agent with sorbitan mono-laurate, with all the other conditions with example 3.
Embodiment 8:
With zein, Cr (NO
3)
39HO
2Preparation method for feedstock production deacylated tRNA amine corn protein-chromium element inner complex:
With 0.38g Cr (NO
3)
39HO
2Replace 0.19g Cr
2(SO
4)
3Carry out chelatropic reaction, anhydrous sorbitol monopalmitate and replace the anhydrous sorbitol tristearate as spray-dired dispersion agent, with all the other conditions with example 3.
Embodiment 9:
Take by weighing 25kg whole meal flour, 5g deacylated tRNA amine wheat grain protein-chromium element inner complex, uniform mixing in agitator, packing by the preparation of embodiment 1 method.The chromium constituent content is about 1.5mg/kg in the flour at this moment.
Embodiment 10:
Take by weighing execute example 9 methods preparations contain chromium flour 500g, water 250g, yeast 5g, place washbasin, manual and face is modulated dough, normal temperature bottom fermentation 1h.The dough of fermentation is made steamed bun, proof 30min at normal temperatures, steam in the pot of packing into then, make the steamed bun that contains the chromium element to water boiling back 15min.
The invention provides a kind of Decarboxamidation grain protein-chrominium element chelate and preparation method thereof and usage.The raw material sources that the present invention relates to are abundant, and preparation method and technical process are simple, and low production cost is easy to promotion and implementation.The Decarboxamidation grain protein-chrominium element chelate that makes based on the present invention, can be applicable to the benefit chrome additive of flour and various flour foods, provide human body necessary chromium element, have effects such as reducing hyperinsulinism, hyperglycemia and hyperlipidemia level, have auxiliaring effect aspect the diabetes preventing and treating.The addition of the Decarboxamidation grain protein-chrominium element chelate that the present invention makes in flour and flour foods is extremely low, can not change color and luster, outward appearance and the taste of flour foods, can not exert an influence to resident's diet formula.
Claims (7)
1. a Decarboxamidation grain protein-chrominium element chelate is characterized in that, by weight percentage, the content of chromium element in inner complex is 0.5～1.5%.
2. the preparation method of a Decarboxamidation grain protein-chrominium element chelate as claimed in claim 1 is characterized in that, it may further comprise the steps:
1) the grain protein powder is placed deionized water be made into 5～15% suspension, when stirring, add concentrated hydrochloric acid and regulate pH value to 1～4, under 120～126 ℃, 0.11～0.15MPa condition, carry out deacylated tRNA amine and react 5～30min;
2) when stirring, with saturated alkaline solution regulating step 1) the pH value of the suspension that obtained is to the iso-electric point of deacylated tRNA amine grain protein, carries out centrifugation or filtering separation then, acquisition deacylated tRNA amine grain protein solid;
3) with deacylated tRNA amine grain protein solid dispersed in deionized water, under 50～90 ℃, agitation condition, extract water-soluble deacylated tRNA amine grain protein, adopt centrifugation or filter separation method to collect supernatant liquor;
4) chromic salts that the chromium element wt is accounted for deacylated tRNA amine grain protein solid weight 0.5～1.5% adds above-mentioned supernatant liquor, under 120～126 ℃, 0.11～0.15MPa condition, react 5～30min, after the cooling, centrifugation or filtering separation, after deionized water washes repeatedly or dialyses, naturally cool shine dry, be lower than oven dry or spraying drying under 80 ℃ of temperature, be ground to less than 300 orders, obtain water content less than 10% powder.
3. the preparation method of Decarboxamidation grain protein-chrominium element chelate according to claim 2 is characterized in that said grain protein is gluten powder, rice protein powder or zein.
4. the preparation method of Decarboxamidation grain protein-chrominium element chelate according to claim 2, it is characterized in that said chromic salts is inorganic chromate salt or organic chromic salts, inorganic chromate salt is chromium chloride, chromium nitrate, chromium sulphate or their hydrate, and organic chromic salts is nicotinic acid chromium, chromium picolinate or glycine chromium.
5. the preparation method of Decarboxamidation grain protein-chrominium element chelate according to claim 2 is characterized in that, said basic solution is NaOH, NaHCO
3, Na
2CO
3The aqueous solution or ammoniacal liquor.
6. the preparation method of Decarboxamidation grain protein-chrominium element chelate according to claim 2 is characterized in that said centrifugation, and its centrifugal speed is 3000～5000g, and the centrifugation time is 10～20min.
7. the preparation method of Decarboxamidation grain protein-chrominium element chelate according to claim 2, it is characterized in that the dispersion agent that said spraying drying adopts is sorbitan mono-laurate, anhydrous sorbitol monopalmitate, anhydrous sorbitol tristearate or Witconol AL 69-66.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101946897A (en) * | 2010-08-11 | 2011-01-19 | 绵阳崴尼达化工有限公司 | Method for producing water-soluble chromium picolinate |
| US9700546B2 (en) | 2006-04-12 | 2017-07-11 | Interhealth Nutraceuticals, Inc. | Trivalent chromium compounds, compositions and methods of use |
| CN111990650A (en) * | 2020-08-13 | 2020-11-27 | 自然资源部第三海洋研究所 | Preparation method and application of squid natural melanin chelated chromium (III) salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1118246C (en) * | 1998-10-22 | 2003-08-20 | 汤革三 | High-chromium hydrolysable animal protein |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9700546B2 (en) | 2006-04-12 | 2017-07-11 | Interhealth Nutraceuticals, Inc. | Trivalent chromium compounds, compositions and methods of use |
| CN101946897A (en) * | 2010-08-11 | 2011-01-19 | 绵阳崴尼达化工有限公司 | Method for producing water-soluble chromium picolinate |
| CN111990650A (en) * | 2020-08-13 | 2020-11-27 | 自然资源部第三海洋研究所 | Preparation method and application of squid natural melanin chelated chromium (III) salt |
| CN111990650B (en) * | 2020-08-13 | 2023-03-10 | 自然资源部第三海洋研究所 | Preparation method and application of squid natural melanin chelated chromium (III) salt |
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| CN112544814B (en) * | 2020-11-27 | 2023-10-20 | 广西壮族自治区畜牧研究所 | Chicken feed based on plant metal ion chelating liquid and application thereof |
| CN114029038A (en) * | 2021-11-19 | 2022-02-11 | 哈尔滨学院 | High ion adsorption amount milky white zein colloid nano-particles |
| CN114029038B (en) * | 2021-11-19 | 2024-01-26 | 哈尔滨学院 | Milky zein colloid nano particle with high ion adsorption capacity |
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