CN1184776A - Method for preparing active and elementary selenium - Google Patents
Method for preparing active and elementary selenium Download PDFInfo
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- CN1184776A CN1184776A CN97107038A CN97107038A CN1184776A CN 1184776 A CN1184776 A CN 1184776A CN 97107038 A CN97107038 A CN 97107038A CN 97107038 A CN97107038 A CN 97107038A CN 1184776 A CN1184776 A CN 1184776A
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Abstract
The prepn. of active reddish elementary selenium is as follows: the selenium compounds or greyish black elementary selenium is reduced by adding reducing agent, then add protein or polypeptide to form protein state or polypeptide state elementary selenium after separation, active reddish elementary selenium is obtd.. This kind of active reddish elementary selenium is high in bioavailability and low in acute toxicity.
Description
The present invention relates to a kind of chemical preparation process, the preparation method of a kind of active elementary selenium of more specifically saying so.
The preparation method of simple substance selenium is a lot, as vacuum distillation method, and thick selenolite gas oxidation-ammonia reduction method, oxidizing fire method, Selenium hydride thermal decomposition method, the methods such as organic intermediate product of generation selenium.But preparation condition in these methods such as temperature, pressure are had relatively high expectations, the raw material of employed participation reaction mostly is the negative electrode mud of refined matte, the residual mud of vitriol works, waste materials such as copper metallurgy flue dust, the simple substance selenium of producing is generally used industries such as glass, pottery, dyestuff, metallurgy.The simple substance selenium of producing is divided into unbodied red powdery simple substance selenium or grey black simple substance selenium and crystallization shape gray selenium.
Selenium is the necessary trace element of human life activity, and its biological effect shows as the enhancing immune function of human body, and delaying human body caducity is anticancer, protect liver, removes free radical, regulates hormone metabolism, the antagonism heavy metal.The selenium of some inorganic states such as Na
2SeO
3With the selenium such as the selenium yeast of organic biological effect is preferably arranged all, but life entity is also shown higher acute toxicity, limited the utilization of these selenium compounds.Also have some selenium compounds such as grey black simple substance selenium, trimethylammonium selenium can not penetrate in the selenium metabolic pool, thereby can not show the biological effect of selenium, also can not show tangible acute toxicity.
Generally speaking, the people can take in the selenium element from diet, drinking-water.In addition, selenium compound such as Na
2SeO
3, selenium yeast, the Kappa-selenocarrageenan can be used as foodstuff additive and is added in the food, or adds in the human body with tablet form, and the selenium element absorbs by digestive tube and enters in the body metabolism process usually.The selenium element in the food or the selenium element of interpolation must can utilize for human body.The compound of these additional human body selenium elements, biological effect is clear and definite, but acute toxicity is also bigger, has limited their use.
People generally believe that grey black simple substance selenium does not have biological utilisation.
The purpose of this invention is to provide a kind of preparation method of red elemental selenium of energy stable existence, the red elemental selenium that makes thus has biological effect preferably, and acute toxicity is lower.
The objective of the invention is to be achieved through the following technical solutions.
Realize the present invention can have five by way of.
One, a kind of preparation method of the property talked about red elemental selenium is in the system of protein or polypeptide existence, prepares simple substance selenium with the conventional chemical method, can obtain the red elemental selenium of protein attitude or polypeptide attitude, isolates active and elementary selenium at last.
Two, a kind of preparation method of active and elementary selenium may further comprise the steps:
A, preparation selenium compound or ash, black simple substance selenium solution,
B, adding protein or polypeptide, protein or polypeptide are that the formation active and elementary selenium is necessary,
C, adding reductive agent start reaction,
D, isolate red elemental selenium;
Reductive agent can with+6 valencys ,+4 valencys, 0 valency selenium be reduced into 0 valency or-divalent selenium.
Selenium or its compound and reductive agent mol ratio are 1: 1～120, the scope more higher or lower than this proportional also can generate active and elementary selenium, but practical value is little, and proper scope is 1: 1～12, and the mass ratio of selenium and protein or polypeptide is 1: 1～10
7, higher or lower also more passable than this proportional, but its practical value not quite, proper scope is 1: 100～5 * 10
6, the ratio between selenium and reductive agent, protein, the polypeptide is to realizing that the present invention concerns not quite.
Three, a kind of preparation method of active and elementary selenium may further comprise the steps:
A, at SeSO
3 2-Add protein or polypeptide in the solution, protein or polypeptide are that the formation active and elementary selenium is necessary,
PH＜7 of b, adjustment reaction system,
C, formation protein attitude or polypeptide attitude red elemental selenium,
D, isolate red elemental selenium,
The mass ratio of selenium and protein or polypeptide is 1: 1～10
7, higher or lower also more passable than this proportional, but its practical value not quite, proper scope is 1: 100～5 * 10
6, but the mass ratio of selenium and protein or polypeptide is to realizing that the present invention concerns not quite.
Four, a kind of preparation method of active and elementary selenium may further comprise the steps:
A, preparation selenium compound solution,
B, adding reductibility protein or reductibility polypeptide,
C, reaction are started by reductibility protein or reductibility polypeptide,
D, formation protein attitude or polypeptide attitude red elemental selenium,
E, isolate red elemental selenium,
Reductibility protein or reductibility polypeptide can with+6 valencys ,+4 valencys, 0 valency selenium be reduced into 0 valency or-divalent selenium.
The mass ratio of selenium compound and reductibility protein or reductibility polypeptide is 1: 1～10
5, higher or lower also more passable than this proportional, but practical value is little, and proper scope is 1: 100～5 * 10
4
Five, a kind of preparation method of active and elementary selenium is characterized in that may further comprise the steps:
A, plant tissue, the microorganism that will contain reducing substances and protein or polypeptide are placed in the selenium compound solution and soak,
B, generation protein attitude or polypeptide attitude red elemental selenium,
C, isolate red elemental selenium,
Reducing substances can with+6 valencys ,+4 valencys, 0 valency selenium be reduced into 0 valency or-divalent selenium.
In the culture system, the selenium concentration of nutrient solution is 10PPM～10
5PPM, proper scope is 10PPM～10
4PPM is in 10PPM～10
5Outside the PPM scope, also can prepare active and elementary selenium, but its practical value not quite.
The plant tissue in various sources, the contained reducing substances of microorganism, protein or polypeptide differ greatly, but this does not influence the generation of active and elementary selenium.
In five kinds of methods of invention, protein or polypeptide are meant the polypeptide product that the protein that extracts or polypeptide and protein further are decomposed to form from plant, animal, microorganism.Protein and polypeptide can be the polypeptide product of 1.5-diphosphoribulose carboxylase/oxygenase and hydrolysis thereof or soy bean protein hydrolysate, oxyphorase.
Plant tissue is meant soybean or corn, and microorganism is meant yeast.
Selenium compound is Na
2SeO
3Or Na
2SeO
4
Reductive agent is vitamins C or dredges basic ethanol.
Reductibility protein or polypeptide are metallothionein(MT) or 1.5-diphosphoribulose carboxylase/oxygenase and hydrolysate thereof.
The reaction conditions gentlenesses such as acidity temperature of preparation active and elementary selenium are participated in the selenium compound that reacts in the inventive method, and reductive agent is easy to get, and physico-chemical property is relatively gentleer, the reaction easy handling.Particularly introduced protein-based or polypeptides matter in reaction system, obtained protein attitude or polypeptide attitude red elemental selenium, this protein attitude or polypeptide attitude red elemental selenium are stable, and biological activity is arranged.The red elemental selenium uniformly distributing is in protein or polypeptide.Both can exist with aqueous solution form, and also can exist with the state of dehydration, isolated red elemental selenium has stability preferably, through evidence biological activity and lower acute toxicity is preferably arranged all.
In the present invention, the participation of protein or polypeptide is a key factor, easily assembles to the conversion of grey black simple substance selenium as the red elemental selenium of no protein or polypeptide participation formation to become the active simple substance selenium of lifeless matter.The active and elementary selenium of the present invention's preparation or the red elemental selenium of protein attitude or polypeptide attitude still keep red simple substance state after handling through modes such as pyroprocessing, do not transform to grey black simple substance selenium.Protein or polypeptide source wide range, and polyose or nucleic acid material are just inoperative to forming the stable state red elemental selenium.
The present invention has found the existence condition and the production approach of an active elementary selenium by selecting appropriate reductive agent and protein, to solving the acute toxicity problem that selenium utilizes, has opened up new research direction.
Simple substance selenium by the present invention's preparation mainly contains following characteristics.
1, the red elemental selenium that obtains of usual method is muddy and unstable, easily transforms and lose biological utilisation to grey black simple substance selenium, and the red elemental selenium physicochemical property that the present invention makes are stable, and biological utilisation is good.
2, active and elementary selenium can cause erythrocyte hemolysis at the external red corpuscle that enters, and its effect degree is much smaller than Na
2SeO
2Grey black simple substance selenium does not cause cell haemolysis.
3, active and elementary selenium can bring out the liver homogenate lipid peroxidation, and its degree can not show a candle to Na
2SeO
3, grey black simple substance selenium does not bring out the liver homogenate lipid peroxidation.
4, active and elementary selenium can with the gsh limited response, and Sodium Selenite and gsh vigorous reaction, grey black simple substance selenium does not react with gsh.
5, active and elementary selenium toxicity is lower than Na
2SeO
3, grey black simple substance selenium lifeless matter usability nontoxicity.
6, by experiment, active and elementary selenium can resist CCl
4The acute liver damage that brings out significantly suppresses gross tumor volume, weight, prolong tumor-bearing mice lifetime, suppress tumor metastasis, improve immune indexes, significantly suppress D-semi-lactosi inductive anti-oxidative damage, significantly improve mean lifetime, half survival time and the highest mean lifetime of fruit bat.
By the following examples, the invention will be further described.
Embodiment 1:
With 10mg Na
2SeO
3Reach the 20g soy bean protein hydrolysate with 1 liter of dissolved in distilled water, add 50 milligrams of vitamins Cs, adjust system PH=5～6, left standstill 8～12 hours, promptly obtain stable protein attitude red elemental selenium.With centrifugal 1 hour of the above-mentioned red protein attitude simple substance selenium 18000r/min that obtains, remove supernatant liquor, add distilled water suspension red elemental selenium in the centrifuge tube, centrifugal with similarity condition, 5 times repeatedly, obtain Deproteinated active and elementary selenium, suspend with 150ml distilled water.
Embodiment 2:
Take by weighing 10mg Na
2SeO
3And the thin basic ethanol of 7mg, be mixed with 1 premium on currency solution, adjust PH=5～6, generate simple substance selenium, add 40mg Na again
2SeO
3 2-, be heated to 70～80 ℃, stirred 10 minutes, generate SeSO
3 2-Add the 20g oxyphorase, transfer PH=4～5, generate protein attitude red elemental selenium.Separation method is with embodiment 1.
Embodiment 3:
Take by weighing 10mg Na
2SeO
3, prepare 1 premium on currency solution, add 20g 1.5-diphosphoribulose carboxylase/oxygenase, adjust system PH=3～4, generate stable protein attitude simple substance selenium, separate with embodiment 1.
Embodiment 4:
Take by weighing 5g soybean dry seeds, be soaked in the Na that the 40ml selenium concentration is 10 μ g/g
2SeO
3In the solution, can generate the red elemental selenium of soy-protein attitude.
Claims (10)
1, a kind of preparation method of active and elementary selenium is characterized in that preparing simple substance selenium with the conventional chemical method in the system of protein or polypeptide existence, can obtain the red elemental selenium of protein attitude or polypeptide attitude, isolates active and elementary selenium at last.
2, a kind of preparation method of active and elementary selenium is characterized in that may further comprise the steps:
A, preparation selenium compound or ash, black simple substance selenium solution,
B, adding protein or polypeptide, protein or polypeptide are that the formation active and elementary selenium is necessary,
C, adding reductive agent start reaction,
D, isolate red elemental selenium;
Reductive agent can with+6 valencys ,+4 valencys, 0 valency selenium be reduced into 0 valency or-divalent selenium.
3, a kind of preparation method of active and elementary selenium is characterized in that may further comprise the steps:
A, at SeSO
3 2-Add protein or polypeptide in the solution, protein or polypeptide are that the formation active and elementary selenium is necessary,
PH＜7 of b, adjustment reaction system,
C, formation protein attitude or many colloidal state red elemental selenium,
D, isolate red elemental selenium;
4, a kind of preparation method of active and elementary selenium is characterized in that may further comprise the steps:
A, preparation selenium compound solution,
B, adding reductibility protein or reductibility polypeptide,
C, reaction are started by reductibility protein or reductibility polypeptide,
D, formation protein attitude red elemental selenium or polypeptide attitude red elemental selenium,
E, isolate red elemental selenium,
Reductibility protein or reductibility polypeptide can with+6 valencys ,+4 valencys, 0 valency selenium be reduced into 0 valency or-divalent selenium.
5, a kind of preparation method of active and elementary selenium is characterized in that may further comprise the steps;
A, plant tissue, the microorganism that will contain reducing substances and protein or polypeptide are placed in the selenium compound solution and soak,
B, generation protein attitude or polypeptide attitude red elemental selenium,
C, isolate red elemental selenium,
Reducing substances can with+6 valencys ,+4 valencys, 0 valency selenium be reduced into 0 valency or-divalent selenium.
6,, it is characterized in that protein or polypeptide are meant the polypeptide product that the protein that extracts or polypeptide and protein further are decomposed to form from plant, animal, microorganism according to the preparation method of claim 1 or 2 or 3 or 4 or 5 described a kind of active and elementary seleniums.
7, the preparation method of a kind of active and elementary selenium according to claim 6 is characterized in that protein and polypeptide are meant the polypeptide product of 1.5-diphosphoribulose carboxylase/oxygenase and hydrolysis thereof or soy bean protein hydrolysate, oxyphorase.
8, the preparation method of a kind of active and elementary selenium according to claim 2 is characterized in that reductive agent is vitamins C or dredges basic ethanol, and selenium compound is Na
2SeO
3Or Na
2SeO
4
9, the preparation method of a kind of active and elementary selenium according to claim 4 is characterized in that selenium compound is Na2SeO3 or SeO
2, reductibility protein or polypeptide are metallothionein(MT) or 1.5-diphosphoribulose carboxylase/oxygenase and hydrolysate thereof.
10, the preparation method of a kind of active and elementary selenium according to claim 5 is characterized in that selenium compound is Na2SeO3 or Na
2SeO
4, plant tissue is meant soybean or corn, microorganism is meant yeast.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107038A CN1059638C (en) | 1997-05-06 | 1997-07-08 | Method for preparing active and elementary selenium |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106962 | 1997-05-06 | ||
| CN97106962.X | 1997-05-06 | ||
| CN97107038A CN1059638C (en) | 1997-05-06 | 1997-07-08 | Method for preparing active and elementary selenium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184776A true CN1184776A (en) | 1998-06-17 |
| CN1059638C CN1059638C (en) | 2000-12-20 |
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ID=25744298
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97107038A Expired - Lifetime CN1059638C (en) | 1997-05-06 | 1997-07-08 | Method for preparing active and elementary selenium |
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| Country | Link |
|---|---|
| CN (1) | CN1059638C (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323939C (en) * | 2004-12-17 | 2007-07-04 | 宁波大学 | Preparation method of nano selenium sol |
| CN100389058C (en) * | 2005-04-19 | 2008-05-21 | 北京天天硒旺纳米生物技术有限公司 | Load type nano selenium and preparation method |
| CN102160647A (en) * | 2011-02-25 | 2011-08-24 | 徐梦泽 | Method for producing bioactive-selenium-enriched food |
| CN102511701A (en) * | 2011-12-26 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for removing inorganic selenium in liquid environment |
| CN103070349A (en) * | 2013-03-04 | 2013-05-01 | 河南工业大学 | Steamed bread rich in nano-selenium and preparation process thereof |
| CN103249670A (en) * | 2010-12-17 | 2013-08-14 | 通用电气公司 | Selenium separation and recovery from bioreactor sludge |
| CN104095242A (en) * | 2014-07-15 | 2014-10-15 | 广州大学 | Composite zinc selenium polypeptide compound and preparation method thereof |
| US9072669B2 (en) | 2011-07-25 | 2015-07-07 | The Hong Kong Polytechnic University | Pleurotus tuber-regium polysaccharide functionalized nano-selenium hydrosol with anti-tumor activity and preparation method thereof |
| RU2557992C1 (en) * | 2013-12-30 | 2015-07-27 | Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук | Antioxidant agent of nanostructured selenium with hepatoprotective effect and methods for producing and using it |
| CN105154474A (en) * | 2015-09-18 | 2015-12-16 | 宜春学院 | Biological preparation method of red nano selenium |
| CN105668527A (en) * | 2016-04-05 | 2016-06-15 | 中南大学 | Method for preparing red selenium |
| CN106219501A (en) * | 2016-07-26 | 2016-12-14 | 温彩珑 | A kind of selenium nano-particle and preparation method thereof |
| CN107043789A (en) * | 2017-03-25 | 2017-08-15 | 广州聚禅现代农业研究院有限公司 | A kind of method that octopus residue protein zymolyte regulation and control prepare nanometer selenium |
| RU2700267C2 (en) * | 2017-04-19 | 2019-09-16 | Екатерина Владимировна Бородулина | Method for preparation of selenium bionanocomposites |
| CN110367544A (en) * | 2019-07-11 | 2019-10-25 | 广州大学 | A kind of nano granules of selenium and preparation method thereof based on polypeptide |
-
1997
- 1997-07-08 CN CN97107038A patent/CN1059638C/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323939C (en) * | 2004-12-17 | 2007-07-04 | 宁波大学 | Preparation method of nano selenium sol |
| CN100389058C (en) * | 2005-04-19 | 2008-05-21 | 北京天天硒旺纳米生物技术有限公司 | Load type nano selenium and preparation method |
| CN103249670A (en) * | 2010-12-17 | 2013-08-14 | 通用电气公司 | Selenium separation and recovery from bioreactor sludge |
| CN102160647A (en) * | 2011-02-25 | 2011-08-24 | 徐梦泽 | Method for producing bioactive-selenium-enriched food |
| US9072669B2 (en) | 2011-07-25 | 2015-07-07 | The Hong Kong Polytechnic University | Pleurotus tuber-regium polysaccharide functionalized nano-selenium hydrosol with anti-tumor activity and preparation method thereof |
| CN102511701A (en) * | 2011-12-26 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for removing inorganic selenium in liquid environment |
| WO2013097309A1 (en) * | 2011-12-26 | 2013-07-04 | 苏州硒谷科技有限公司 | Method for removing inorganic selenium in liquid environment |
| CN103070349A (en) * | 2013-03-04 | 2013-05-01 | 河南工业大学 | Steamed bread rich in nano-selenium and preparation process thereof |
| RU2557992C1 (en) * | 2013-12-30 | 2015-07-27 | Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук | Antioxidant agent of nanostructured selenium with hepatoprotective effect and methods for producing and using it |
| CN104095242A (en) * | 2014-07-15 | 2014-10-15 | 广州大学 | Composite zinc selenium polypeptide compound and preparation method thereof |
| CN104095242B (en) * | 2014-07-15 | 2016-04-13 | 广州大学 | A kind of composite zinc selenium polypeptide compound and preparation method thereof |
| CN105154474A (en) * | 2015-09-18 | 2015-12-16 | 宜春学院 | Biological preparation method of red nano selenium |
| CN105154474B (en) * | 2015-09-18 | 2018-08-10 | 宜春学院 | The biological preparation method of red nano selenium |
| CN105668527A (en) * | 2016-04-05 | 2016-06-15 | 中南大学 | Method for preparing red selenium |
| CN106219501A (en) * | 2016-07-26 | 2016-12-14 | 温彩珑 | A kind of selenium nano-particle and preparation method thereof |
| CN107043789A (en) * | 2017-03-25 | 2017-08-15 | 广州聚禅现代农业研究院有限公司 | A kind of method that octopus residue protein zymolyte regulation and control prepare nanometer selenium |
| RU2700267C2 (en) * | 2017-04-19 | 2019-09-16 | Екатерина Владимировна Бородулина | Method for preparation of selenium bionanocomposites |
| CN110367544A (en) * | 2019-07-11 | 2019-10-25 | 广州大学 | A kind of nano granules of selenium and preparation method thereof based on polypeptide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1059638C (en) | 2000-12-20 |
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