CN101715869A - Novel method for preparing selenate food protein - Google Patents
Novel method for preparing selenate food protein Download PDFInfo
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- CN101715869A CN101715869A CN200910218245A CN200910218245A CN101715869A CN 101715869 A CN101715869 A CN 101715869A CN 200910218245 A CN200910218245 A CN 200910218245A CN 200910218245 A CN200910218245 A CN 200910218245A CN 101715869 A CN101715869 A CN 101715869A
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Abstract
The invention discloses a novel method for preparing selenate food protein, comprising the following steps of: dissolving food protein into solution containing selenate; adjusting the pH and then freezing and drying; heating the freezed and dried selenate-food protein mixture for 1-5 days under the condition of drying to perform selenate reaction; dialyzing, freezing and drying to obtain the selenate food protein; and the like. The invention has the advantages of safe selenate products and avoidance of environmental pollution due to no use of organic solvent during preparation; and simple process, controllable conditions, low production cost and easy realization of industrial production. The selenate food protein in the invention can be used as organic selenium supplement with high efficiency, low mammalian toxicity to be applied to food, health products or feed and can provide selenium element necessary to human bodies or animals. In addition, selenate food protein has immunity adjusting function and good oxidation resistance and antitumor activity, and has profound significance in developing anticancer drugs or cosmetic.
Description
Technical field
The present invention relates to a kind of under with an organic solvent condition not the new method of preparation selenate food protein.
Background technology
Selenium has been confirmed as a kind of important trace element of needed by human by the United Nations's health organization.Studies show that, multiple disease, all relevant as Keshan disease, diabetes, angiocardiopathy, cataract, aging etc. with the scarce selenium of body, the domestic and international for many years biological function to selenium has carried out big quantity research, especially the relation of selenium and tumour makes the research of selenium from the trophic function to drug therapy become very active field in the current selenizing.In addition, selenium is effective anti-oxidants, can remove free radical, and serum total cholesterol, triglyceride and MDA are reduced, and simultaneously, selenium also plays the adjusting body's immunity, helps improving body immunity.General people mainly comes from food to the demand of selenium, and Se content is generally on the low side in the common food.Like this, on the basis that does not change the human diet structure, application safety is effectively mended selenium product, is to improve human health, the effective way of prevention selenium deficiency associated diseases.Regional nearly 700,000,000 populations of China 2/3 are in and lack the selenium state.According to the investigation of Chinese Soclety of Nutrition, China adult takes the photograph selenium quantity not sufficient 27 microgram/skies.Therefore, develop the important content that effective selenium hardening agent has become China's se-rich health food products exploitation.
Strengthening selenium in food is the effective way of Selenium Supplement.The hardening agent of selenium can be divided into inorganic selenium and organic selenium two classes at present.It is bigger that most of inorganic selenium has toxicity, the shortcoming that safe range is narrow.And compare with inorganic selenium, organic selenium has the little and biologically active advantages of higher of toxicity.Biologically active as common inorganic Selenium supplement agent sodium selenite is low, and absorption difference, minimum lethal dose are less relatively, makes it be subjected to bigger restriction in each Application for Field.Developed country simply inorganic salt form as the nutrition fortifier of selenium.At present, developed countries such as Japan, the U.S. have forbidden adding inorganic seleniums such as sodium selenite in food.Like this, preparation safely, organic selenium compounds is an important content of selenizing research efficiently.
The source of occurring in nature albumen is abundanter, and protide has more hydroxyl and amino, and selenylation reaction takes place easily.Yet the research for selenizing albumen is less, be applied in the food still less.About the preparation method of selenic acid albumen, so far, mainly be the selenic acidization that realizes albumen by the method for chemical synthesis.Chinese patent (publication number: 1011858642A) proposed a kind of synthetic method of glucosamine lysine selenium salt for example.This method obtains glucosamine lysine selenium salt with the lysine reaction after making aminoglucose hydrochloride with aminoglucose hydrochloride and the sour agent of bundle (methyl alcohol and sodium methoxide) reaction again in methanol solution.People such as Mao Jianwei disclose a kind of preparation method of organic selenium methionine, and (Chinese patent, publication number: CN1560034A), this method is that selenium and a large amount of chlorine reactions are made selenic chloride, then selenic chloride and methionine is reacted in organic solvent.But, used poisonous organic solvents such as toxic gases such as chlorine or methyl alcohol in the above-mentioned reaction, can influence the foodsafety of organic selenium methionine like this.Chinese patent (publication number: CN 1680312A) proposed the synthetic method of another kind of selenomethionine.This method is raw material with the methionine, earlier with iodomethane reaction and after treatment alpha-amido butyrolactone hydrochloride, then under nitrogen protection with sodium methyl-hydroselenide heating reflux reaction in ethanolic solution.Foul smelling and the bigger organic reagents of toxicity such as iodomethane have been used in this reaction on the one hand; On the other hand, this reaction is to take place under the condition of nitrogen protection, and severe reaction conditions can increase industrial production cost.Chinese patent CN1711914A discloses a kind of glycosyl grain protein-selenium compound and preparation method thereof.The preparation key technology of this method is condition control glycosylations such as employing HTHP, and then carries out the selenic acid reaction.For this reason, need to use high-pressure reaction vessel in this reaction, and need carry out corrosion-inhibiting coating, can increase production cost like this, also be unfavorable for industrialization the reactor inwall.
In a word, in the current selenic acid protein Preparation process, have the situation of using toxic gas or organic solvent, and selenic acid albumen mainly is to use in food, health food or medicine, residual like this reagent may influence its application.In addition, these preparation method's severe reaction conditions, technology are complicated, are unfavorable for suitability for industrialized production.
Summary of the invention
The objective of the invention is to the problem and shortage that exists in the present selenate food protein technology of preparing, propose a kind of in the new method of preparation selenate food protein under with an organic solvent the condition not fully.This method has technological process and realizes suitability for industrialized production, non-environmental-pollution simply, easily, characteristics such as the Se content height of selenate food protein and safety.In this selenate food protein technology of preparing, characteristics the most attractive are exactly to adopt the mode of dry heat to realize the selenic acid reaction.
In order to realize above-mentioned target, the present invention specifically finishes by following process:
(1) food protein with 1-2% is dissolved in the water, and next adds the selenite of 0.1-0.2mol/L in food protein solution, regulates pH;
(2) behind the above-mentioned food protein of freeze drying-selenite solution, under the condition of 50-110 ℃ dry heat, carry out selenic acid reaction 1-5 days;
(3) for guaranteeing the security of selenate food protein, after reaction finishes, food protein-selenite water-soluble and in water dialysis last freeze drying obtained selenate food protein to remove the unreacted selenite in 2 days.
Food protein described in the above-mentioned preparation method can be animal food albumen such as egg albumen, cow's milk protein, vegetable protein such as soybean protein, peanut protein, leaf protein, buckwheat albumen, sesame protein, cottonseed protein or edibility algae, mycoprotein;
Selenate described in the above-mentioned preparation method is selenous acid, selenous acid or its esters, also can be selenium dioxide or the selenium trioxide product after water-soluble;
Dry technology described in the above-mentioned preparation method except that freeze drying, if when preparation amount is big also available devices be conventional, technical be many weeks dry technologies such as spray-drying.
The present invention compared with prior art, advantage is as follows:
1, pollution-free.Do not use any organic solvent among the present invention, can not pollute environment.
2, safety.The preparation method of selenic acid albumen is different with so far method among the present invention, the selenic acidization of instant food albumen realizes under drying regime, promptly need not any poisonous or harmful organic solvent, the food-safety problem of having avoided residual organic reagent to cause.
3, effect is remarkable.When the present invention utilized selenate to exist, the method for dry heat carry out selenic acidization to food protein, and by changing the selenate food protein that conditions such as reaction temperature, reaction time have obtained different selenium contents, wherein the highest Se content can reach 2.88%.
4, raw material sources are abundant, and the preparation method is easy.Food protein class source is abundant, and common have animal food albumen such as egg albumen, cow's milk protein, vegetable protein such as soybean protein, peanut protein, leaf protein, buckwheat albumen, sesame protein, cottonseed protein or edibility algae, mycoprotein.In addition, the used reagent of the preparation of selenate food protein is common reagent, and is cheap, and the preparation condition of selenate food protein operates easily, and production equipment is less demanding, and production cost is low, realizes suitability for industrialized production easily.
5, the Se content height and the safety of the controlled and selenate food protein of reaction condition (reaction temperature, pH, heat time heating time).
6, of far-reaching significance.Selenate food protein among the present invention can be used as efficiently, organic Selenium supplement agent of low toxicity is applied in food, health products or the feed, provides human body or animal essential selenium element.In addition, selenate food protein has immunoregulation effect and good anti-oxidant, active anticancer, and exploitation cancer therapy drug or cosmetics etc. are had profound significance.
Description of drawings
Fig. 1 is the caseic infrared spectrum comparison diagram of casein and selenic acidization.A, casein; B, the selenic acid casein.
Fig. 2 is the electrophoresis comparison diagram of egg white albumen and selenic acid egg white albumen.Sample 1-5 is the selenic acid egg white albumen that selenate makes under the different dry heating conditions when existing; Sample 6-10 is the egg white albumen of no selenate and dry heat.OVA is an ovalbumin among the figure, and Otf is an ovotransferrins.
The specific embodiment
Embodiment 1:
0.5g egg white protein dissolution in the distilled water of 50mL, is stirred 30-60min, in protein solution, add the 0.65g sodium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 80 ℃ dry heat, carried out the selenic acid reaction 1 day then; After reaction finishes, egg white albumen-selenite water-soluble and in water dialysis last freeze drying obtained selenic acid egg white albumen to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through infrared spectrum (IR), at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; In addition, the analysis result of polyacrylamide gel electrophoresis (Native PAGE) shows that the egg white albumen of the translational speed comparison photograph of selenic acid egg white albumen wants fast, and this shows that selenic acidization has increased the negative electrical charge of albumen.By measuring, the Se content of selenic acid egg white albumen is 1.56%.
Embodiment 2:
1g egg white protein dissolution in the distilled water of 80mL, is stirred 30-60min, in protein solution, add the 1.5g sodium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 80 ℃ dry heat, carried out the selenic acid reaction 2 days then; After reaction finishes, egg white albumen-selenite water-soluble and in water dialysis last freeze drying obtained selenic acid egg white albumen to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; In addition, the analysis result of polyacrylamide gel electrophoresis (Native PAGE) shows that the egg white albumen of the translational speed comparison photograph of selenic acid egg white albumen wants fast, and this shows that selenic acidization has increased the negative electrical charge of albumen.By measuring, the Se content of selenic acid egg white albumen is 2.20%.
Embodiment 3:
0.5g egg white protein dissolution in the distilled water of 50mL, is stirred 30-60min, in protein solution, add the 0.65g sodium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 70 ℃ dry heat, carried out the selenic acid reaction 2 days then; After reaction finishes, egg white albumen-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid casein to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; In addition, the analysis result of polyacrylamide gel electrophoresis (Native PAGE) shows that the egg white albumen of the translational speed comparison photograph of selenic acid egg white albumen wants fast, and this shows that selenic acidization has increased the negative electrical charge of albumen.By measuring, the Se content of selenic acid egg white albumen is 1.87%.
Embodiment 4:
0.5g egg white protein dissolution in the distilled water of 50mL, is stirred 30-60min, in protein solution, add the 0.65g sodium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 70 ℃ dry heat, carried out the selenic acid reaction 1 day then; After reaction finishes, egg white albumen-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid casein to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; In addition, the analysis result of polyacrylamide gel electrophoresis (Native PAGE) shows that the egg white albumen of the translational speed comparison photograph of selenic acid egg white albumen wants fast, and this shows that selenic acidization has increased the negative electrical charge of albumen.By measuring, the Se content of selenic acid egg white albumen is 1.38%.
Embodiment 5:
0.5g egg white protein dissolution in the distilled water of 50mL, is stirred 30-60min, in protein solution, add the 0.8g potassium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 100 ℃ dry heat, carried out the selenic acid reaction 2 days then; After reaction finishes, egg white albumen-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid casein to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; In addition, the analysis result of polyacrylamide gel electrophoresis (Native PAGE) shows that the egg white albumen of the translational speed comparison photograph of selenic acid egg white albumen wants fast, and this shows that selenic acidization has increased the negative electrical charge of albumen.By measuring, the Se content of selenic acid egg white albumen is 2.15%.
Embodiment 6:
The 1g casein is dissolved in the distilled water of 80mL, stirs 30-60min, in protein solution, add the 1.5g sodium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 90 ℃ dry heat, carried out the selenic acid reaction 1 day then; After reaction finishes, casein-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid casein to remove the unreacted selenite in 2 days.Gained selenic acid casein is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; By measuring, the caseic Se content of selenic acidization is 2.07%.
Embodiment 7:
The 0.5g casein is dissolved in the distilled water of 50mL, stirs 30-60min, in protein solution, add the 1.5g sodium selenite; After regulating the above-mentioned casein of pH postlyophilization-selenite solution, under the condition of 60 ℃ dry heat, carried out the selenic acid reaction 1 day then; After reaction finishes, casein-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid casein to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; By measuring, the caseic Se content of selenic acidization is 1.62%.
Embodiment 8:
The 0.5g lactalbumin is dissolved in 50mL distilled water, stirs 30-60min, in lactoalbumin soln, add 0.65 sodium selenite; After regulating the above-mentioned lactalbumin of pH constant volume freeze drying-selenite solution, under the condition of 90 ℃ dry heat, carried out the selenic acid reaction 1 day then; After reaction finishes, lactalbumin-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid lactalbumin to remove the unreacted selenite in 2 days.The selenic acid lactalbumin is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; By measuring, the Se content of selenic acid lactalbumin is 2.88%
Embodiment 9:
With the distilled water of 1g lactalbumin in 80mL, stir 30-60min, in protein solution, add the 1.5g sodium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 90 ℃ dry heat, carried out the selenic acid reaction 2 days then; After reaction finishes, lactalbumin-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid lactalbumin to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; By measuring, the Se content of selenic acid lactalbumin is 2.47%.
Embodiment 10:
With the distilled water of 0.5g lactalbumin in 60mL, stir 30-60min, in protein solution, add the 1.0g potassium selenite; After regulating the above-mentioned albumen of pH postlyophilization-selenite solution, under the condition of 90 ℃ dry heat, carried out the selenic acid reaction 2 days then; After reaction finishes, lactalbumin-selenite water-soluble and in water dialysis last freeze drying obtained the selenic acid lactalbumin to remove the unreacted selenite in 2 days.Gained selenic acid albumen is analyzed through IR, at 890cm
-1The place can be observed the stretching vibration absworption peak of Se=O; By measuring, the Se content of selenic acid lactalbumin is 2.15%.
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (5)
1. the new preparation process of a selenate food protein is characterized in that comprising the steps:
(1) food protein with 1-2% is dissolved in water, stirs 30-60min, and adds the selenate of 0.1-0.2mol/L in food protein solution, constant volume behind the adjusting pH;
(2) behind the above-mentioned food protein of freeze drying-selenate solution, under 50-110 ℃ dry heat condition, carried out the selenic acid reaction 1-5 days;
(3) after reaction finishes, food protein-selenate mixed-powder is water-soluble, and in water, dialyse 2 days to remove unreacted selenate; Last freeze drying obtains the selenate food protein powder.
2. the method for claim 1 is characterized in that in the step (1), and the selenic acid reaction of food protein is to take place when selenic acid or selenous acid or its esters exist.
3. the method for claim 1 is characterized in that in the step (2), and the selenic acidization of food protein is to take place under 50-110 ℃ of condition.
4. the method for claim 1 is characterized in that in the step (3), the selenic acid reaction of food protein is to take place under the condition of dry heat.
5. the method for claim 1 is characterized in that in the step (3), the selenic acid reaction time of food protein is 1-5 days.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479003A (en) * | 2014-12-25 | 2015-04-01 | 天津科技大学 | Selenous acidized beta-lactoglobulin, preparation method and application |
| CN110250318A (en) * | 2019-07-23 | 2019-09-20 | 湖南硒宝宝健康产业有限责任公司 | A kind of preparation method of selenium-rich soybean protein |
-
2009
- 2009-11-25 CN CN200910218245A patent/CN101715869A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479003A (en) * | 2014-12-25 | 2015-04-01 | 天津科技大学 | Selenous acidized beta-lactoglobulin, preparation method and application |
| CN110250318A (en) * | 2019-07-23 | 2019-09-20 | 湖南硒宝宝健康产业有限责任公司 | A kind of preparation method of selenium-rich soybean protein |
| CN110250318B (en) * | 2019-07-23 | 2022-11-25 | 湖南硒宝宝健康产业有限责任公司 | Preparation method of selenium-rich soybean protein |
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Open date: 20100602 |