CN1600793A - Polysaccharide of selenic acid and preparation method - Google Patents
Polysaccharide of selenic acid and preparation method Download PDFInfo
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Abstract
In the invention, redox method is used to lead selenid radical in polysaccharide ring to generate polysaccharide selenate including mainly cartilage polysaccharide selenate (includes heparin selenate, heparan selenate, chondroitin selenate, hyaluronic glue selenate), sargassum acid selenate, shellglycan selenate. The prepn. process including prepn. of selenic acid, prepn. of solubility polysaccharide liquid, leading-in of selenide radical, filtering, multistep precipitation and drying to produce pure polysaccharide selenate which is polymer selenate that propeties of most stable and most similar to structure of natrural products.
Description
[technical field]: the field that the present invention relates to multidisciplinary intersections such as marine organisms, processing of aquatic products, animal byproducts utilization and field of biological pharmacy; Particularly belong to the by product cartilage that utilizes animal, the by product chitin preparations such as (chitosans) of ocean or fresh water crustaceans biology has the polysaccharide of selenic acid of high reactivity, high-absorbable and high health-care function.
[background technology]: selenium is important trace element in the organism, is the constituent of vivo oxidation reductase enzyme, participates in the decomposition of objectionable impuritiess such as hydrogen peroxide organo-peroxide, prevents that microbial films such as cytolemma, mitochondrial membrane from exempting from the injury of superoxide.Simultaneously, participate in the synthetic of energy i (in vivo) substance A TP, keep electronic conduction ability, suppress blood coagulation, the immunizing power of the generation of enhancing antibody (IgM), raising body, special efficacies such as generation with the heavy metal poisoning of preventing, inhibition cancer.When lacking selenium in the body, can cause the symptoms such as generation of arteriosclerosis, diabetes, cataract, hepatic necrosis, prostatomegaly and cancer.
Along with growth in the living standard, precision work food is more and more, has caused that to lack the selenium phenomenon in people's normal diet more and more serious, also is the important factor that causes the cancer pilosity in recent years.Therefore, selenium-enriched food, the rich selenium medicine of each protective foods company, pharmaceuticals's exploitation have become upsurge.Product and patent about rich selenium also occurred many in recent years.As publication number: CN1038454A, the method for making of westernization carrageenin.This method is to be raw material with the selenium powder, with nitric acid its dissolving is prepared into the selenium liquid that concentration is 0.5-1.0mg/ml, in it being joined the carrageenin that concentration is 0.5-5%, add Kappa-carrageenin or Lambda carrageenin sol solution again, carry out selenylation reaction, after through the ethanol precipitating, obtain the crude product selenocarrageenan.The selenocarrageenan selenium content of this method preparation is lower, and uses selenium powder and concentrated nitric acid can generate as deleterious negative products such as Selenium hydrides entail dangers to people's life on the preparation method.
Second piece of patent publication No. CN1069495, patent name are selenium polysaccharide and manufacture method thereof.This method is passed through separation and Extraction again by the fermentative preparation yeast rich in selenium, and add alkali homogenate, neutralization, concentrate, ethanol sedimentation etc. is prepared into finished product.This method prepares loaded down with trivial details, and the selenium content that obtains is also very low.
The publication number of the 3rd piece of patent is CN1288899A, and its method is to add selenite radical at Ba in polysaccharide soln
2+And H
1+Effect generate down selenium compound of polysaccharide, through adding iron(ic) chloride, NH
3-NH
4Cl solution etc. is removed selenite radical ion, the selenous acid polysaccharide that ethanol precipitation and oven dry etc. is prepared from.Selenous acid is the oxidizing reaction of selenium powder process and rare nitric acid, or tin anhydride (SeO
2) be dissolved in and generate behind the water, be deleterious compound.Selenous acid and compound thereof are reduced into tin anhydride easily through after dehydrating, and the oxidisability of selenous acid is stronger than sulfurous acid, are reduced easily to generate selenium and dissociate out when running into reducing substances such as hydrogen iodide, hydrogen sulfide, sulfurous gas.Because selenous acid and selenous acid compound thereof are extremely unstable, and human body contains the material of many oxidisability and reductibility, selenous acid and compound thereof generated can not be absorbed by the body and inorganic selenium that toxicity is bigger.
In organic sphere, the character of selenium and sulphur and similar, many polysaccharide all take place by the whole of vulcanization reaction generation is sulfated polysaccharide, as important biological materials such as chondroitin sulfate, heparin, heparitins.Sulfated polysaccharide rather than sulfurous acid polysaccharide have been selected in the evolution in several hundred million years of natural biology, exactly because the also unstable of sulfurous acid of its reason is metastable compound and organic sphere needs, with its biological function of better performance.
[summary of the invention]: the present invention seeks in order to solve the deficiencies in the prior art; a kind of synthetic method that can simplify polysaccharide of selenic acid is provided; be convenient to large-scale production; increase the content of selenium in the polysaccharide of selenic acid compound, preparation and akin stable polysaccharide of selenic acid compound---the polysaccharide of selenic acid of nature.
Polysaccharide of selenic acid provided by the invention is selenate radical to be imported to the polysaccharide of selenic acid that generates in the polysaccharide ring by oxidation-reduction method.Polysaccharide of selenic acid of the present invention mainly contains three major types: the selenic acid compound selenic acid cartilage polysaccharide of cartilage series polysaccharide, the selenic acid compound selenic acid chitosan of the saccharoidal selenic acid compound of Lalgine selenic acid Lalgine or selenic acid sodium alginate and chitosan class.
Wherein the selenic acid cartilage polysaccharide in cartilage polysaccharide-OH group place or-NH
2The group place imports the selenate radical of stable in properties and makes.Comprise: selenic acid heparin, selenic acid heparan, selenic acid chrondroitin, selenic acid hyaluronic acid.
The selenic acid chitosan be C6-OH group place in chitosan or C3-OH group place or-NH
2The group place imports the selenate radical of stable in properties and makes.
The selenic acid Lalgine be with the polymeric hydantoin alginic acid through degraded, promptly n is less than after 60, C2-OH group place in Lalgine or C3-OH group place import the selenate radical of stable in properties and make.
Above-mentioned polysaccharide of selenic acid is finished by following steps:
(1) selenic acid H
2SeO
4Preparation;
(2) contain the preparation of selenium acidifying soluble polysaccharide liquid: at first, with polysaccharide place the selenic acid that contains step preparation, and the strong OR ambient condition of strong oxidizer under, vacuum, 40 degree following low-temp reaction 10-72 hour obtain containing selenium acidifying soluble polysaccharide liquid by centrifugal or filtering method;
(3) importing of selenate radical:---can be at the hydroxyl-OH or the amino-NH of sugar ring
2Acylation reaction takes place,---or substitution reaction takes place on the group of acidylate, generate polysaccharide of selenic acid, promptly-O-SeO
3H or-NH-SeO
3H;
(4) ion in the reaction solution is removed in reaction after finishing: will go up the step molecular weight with ultra-filtration membrane and filter less than 1000 sodium ion, chlorion, the selenate radical of failing to import and unreacted selenite radical; Filtrate can recycle after concentrating;
(5) fractionation precipitation of polysaccharide of selenic acid reclaims: the polysaccharide of selenic acid through purifying after the ultrafiltration obtains 50%, 60%, 70%, 80%, 90% fractionation precipitation thing with the ethanol precipitation classification, and throw out obtains pure product polysaccharide of selenic acid after by spraying drying or lyophilize.
Selenic acid H
2SeO
4Preparation can be by tin anhydride SeO
2With water H
2The O reaction generates selenous acid H
2SeO
3, selenous acid generates selenic acid under the effect of strong oxidizer.
Can also adopt airtight electrolytic process, promptly be the anode adding tin anhydride SeO of the airtight electrolyzer of sodium-chlor at electrolytic solution
2Or selenous acid H
2SeO
3, tin anhydride SeO
2With water H
2The O reaction generates selenous acid, and selenous acid generates selenic acid at the anode generation oxidation-reduction reaction of energising.
Advantage of the present invention and effect: 1) the present invention is the chemical similarity according to occurring in nature sulphur and selenium, the sulfation of polysaccharide in simulating nature circle (as sulfated polysaccharides such as chondroitin sulfates) and making promptly imports to selenate radical by the common oxidation-reduction method of occurring in nature and generates polysaccharide of selenic acid in the polysaccharide ring; 2) increased the content of selenium in the polysaccharide of selenic acid compound; 3) character of the polysaccharide of selenic acid that obtains of the present invention is the most stable selenic acid compound of character near the structure of occurring in nature natural product, and its stability is higher than tin anhydride, selenous acid and compound thereof far away; 4) the present invention can obtain the polysaccharide of selenic acid material of any size of molecular weight as required, and the solution under water-soluble easily and any pH value, these healthcare products for medicine, the different shape of exploitation different dosage form are all very convenient, as injection, tablet, instant granular, capsule, beverage, or the like; Simultaneously, selenate radical can be according to the change of OR condition, and the importing position and the quantity of selenate radical also change, and therefore can well control the amount of the selenate radical of importing, content can reach mg more than 100, the very convenient exploitation of carrying out various pharmaceuticals and healthcare products from number mg; 5), show that this polysaccharide of selenic acid belongs to nontoxic through experimentation on animals, give Kunming white mouse long-time (60 days) this material 25g/kg that feeds, do not see any unusual; By the human blood cell cultivate show this polysaccharide of selenic acid to the protein in the blood plasma without any flocculation phenomenon (this point and chitosan are completely different, and chitosan is typical protein flocculation agent), the various cells in the blood are had no effect; But, this material is to having significant lethal effect to blood cell k562, cultivating under 1/1000 concentration can make this cell mortality reach more than 90% in 24 hours, and show significant short cancer cells and transfer the feature of dying, (referring to Fig. 4, with the contrast of selenium acidifying chitosan not, selenium acidifying chitosan and selenic acid cartilage polysaccharide all demonstrate the effect that intensive suppresses the blood cell growth activity under 1/1000 concentration and 1/10000 concentration.Fig. 5, polysaccharide of selenic acid induce blood cell k562 to transfer the result who dies: by the observation of cellular form, add polysaccharide of selenic acid (1/1000 concentration) blood cell is played significant lethal effect, when cultivating in 48 hours, make the tangible cracking of cell, cell diminishes, by 72 hours, cancer cells was all transferred and is died.); 6), the technology of preparing of polysaccharide of selenic acid, i.e. the oxidation-reduction introductory technique of selenic acid.This method is simple to operate, is convenient to produce, and simultaneously, materials such as used selenic acid, selenous acid, sulfurous gas can recycling use, is typical reproducibility recycling economy.The characteristics of this method are to utilize oxidation-reduction phenomenon common in the organic sphere to realize the selenic acidization of polysaccharide, and the polysaccharide of selenic acid stable in properties that generates, nontoxic, harmless, and the anticancer functional performance that waits is strong; In the middle of this technology of preparing, can use oxidation-reduction agent widely, as chloric acid and oxymuriate thereof, hypochlorous acid and hypochlorite thereof, hydrogen peroxide, potassium permanganate etc. can make selenous acid be oxidized to all oxygenants of selenic acid, and the concentration of oxidation-reduction agent can be any concentration; Simultaneously,, can use electrolytic process, utilize the strong oxidation-reduction of electrolyzer anode and cathode to prepare the polysaccharide of selenic acid of effect same as substituting of oxidation-reduction reaction.
[description of drawings]:
Fig. 1 is the infrared spectrogram of selenic acid chitosan not;
Fig. 2 is the infrared spectrogram of selenic acid chitosan;
Fig. 3 is the mode chart of the electrolytic preparation polysaccharide of selenic acid of chitosan;
Fig. 4 is the maximum inhibition design sketch of polysaccharide of selenic acid to blood cell k562;
Fig. 5 is that polysaccharide of selenic acid induces blood cell k562 to transfer the photo as a result of dying.
[embodiment]:
Embodiment 1:
Selenic acid cartilage polysaccharide class, i.e. selenic acid heparin, the selenic acid heparan, the selenic acid chrondroitin, the preparation of selenic acid cartilage polysaccharide such as selenic acid hyaluronic acid:
---can be directly be the raw material polysaccharide with the polysaccharide of separation and purification such as heparin, heparan, chrondroitin, hyaluronic acid; It also can be the mixture that directly prepares above material by cartilage; The polysaccharide preparation that also can utilize microbial fermentation to produce, concrete steps are as follows:
---(1) selenic acid H
2SeO
4Preparation:
Selenic acid H
2SeO
4Preparation can be by tin anhydride SeO
2With water H
2The O reaction generates selenous acid H
2SeO
3, selenous acid generates selenic acid under the strong oxidizer effect of (strong oxidizer comprises chloric acid and oxymuriate thereof, and hypochlorous acid and hypochlorite thereof, hydrogen peroxide etc. can make selenous acid be oxidized to all oxygenants of selenic acid).
Can also adopt airtight electrolytic process, promptly be the anode adding tin anhydride SeO of the airtight electrolyzer of sodium-chlor at electrolytic solution
2Or selenous acid H
2SeO
3, tin anhydride SeO
2With water H
2The O reaction generates selenous acid, and selenous acid generates selenic acid at the anode generation oxidation-reduction reaction of energising.
---(2) contain the preparation of selenium acidifying soluble polysaccharide liquid: at first, with polysaccharide place the selenic acid that contains step preparation, and the strong OR ambient condition of strong oxidizer under, vacuum, 40 degree following low-temp reaction 10-72 hour obtain containing selenium acidifying soluble polysaccharide liquid by centrifugal or filtering method;---importing of (3) selenate radical:---can be at the hydroxyl-OH or the amino-NH of sugar ring
2Acylation reaction takes place,---or substitution reaction takes place on the group of acidylate, generate polysaccharide of selenic acid, promptly-O-SeO
3H or-NH-SeO
3H;
---the ion in the reaction solution is removed in (4) reaction after finishing: will go up the step molecular weight with ultra-filtration membrane and filter less than 1000 sodium ion, chlorion, the selenate radical of failing to import and unreacted selenite radical; Filtrate can recycle after concentrating;
---the fractionation precipitation of (5) polysaccharide of selenic acid reclaims: the polysaccharide of selenic acid through purifying after the ultrafiltration obtains 50%, 60%, 70%, 80%, 90% fractionation precipitation thing with the ethanol precipitation classification, and throw out obtains pure product polysaccharide of selenic acid after by spraying drying or lyophilize.
---(6) can prepare the polysaccharide of selenic acid that molecular weight is 2,000～several ten thousand various series by membrane separation technique.
The structure of the selenic acid cartilage polysaccharide that above method makes is respectively:
The selenic acid heparin
The selenic acid heparan
Selenic acid chrondroitin (place of 2,3,4,6 or many places selenic acidization)
Selenic acid hyaluronic acid (place of 2,3,6 or many places selenic acidization)
The character of selenic acid cartilage polysaccharide is:
(1) liquid (aqueous solution) of above material (selenic acid heparin, selenic acid heparan, selenic acid chrondroitin, selenic acid hyaluronic) is transparent, and is colourless, or slightly yellow;
(2) solvability of material: water-soluble, acid is molten, and alkali is molten, and salt (sodium-chlor) is molten.Dissolved degree of separating can reach 20%-40%;
(3) according to the alcoholic acid different concns, can prepare the different dissolve with ethanol polysaccharide of selenic acid of 50%-90% respectively, the selenic acid degree of polysaccharide of selenic acid at this moment and molecular weight different can prepare different products respectively;
(4) after above (selenic acid heparin, selenic acid heparan, selenic acid chrondroitin, selenic acid hyaluronic) process spraying drying or the lyophilize, be white in color, or the beige powder;
(5) molecular weight: 2000-50000;
(6) selenic acid degree (selenium content): 3mg-200mg/g;
Embodiment 2:
The preparation of selenic acid chitosan: C6-OH group place in chitosan or C3-OH group place or-NH
2The group place imports the selenate radical of stable in properties, forms the selenic acid chitosan.The detailed process of its preparation and step are with embodiment 1, and detailed process is as follows:
(deacetylation is more than 50% to get chitosan 10g, deacetylation is high more, the import volume of selenate radical is big more), be dissolved in 5% the acetic acid solution of 200ml, treat that it dissolves fully after, the sodium hydroxide solution with 10% is neutralized to more than the pH8, make the chitosan flocks, centrifugation reclaim chitosan (above reaction is in order to make chitosan be in the superfine fiber condition, and is outstanding easily turbid in reaction solution, make the selenic acid reaction evenly and speed of response is accelerated).The chitosan that reclaims is placed the selenic acid solution with oxidizing reaction character: the content of the selenate radical of selenic acid solution is respectively 1g, 2g, 3g, 4g, 5g, 6g, 7g, 8g, 9g, 10g can obtain the different selenic acid chitosan of selenic acid degree according to the adjustment of selenate radical content; Oxidation-reduction material in the selenic acid reaction solution adopts 6% hydrogen peroxide.Above reactant and selenic acid reaction solution are put into the vacuum reaction still together, and under vacuum condition, the importing of selenate radical is finished in 45 degree reactions 24 hours, in the time of vacuum reaction, has also played the effect of vacuum concentration, and reaction has been concentrated to below the 100ml.In reaction solution, add ethanolic soln successively, make the concentration of ethanolic soln reach 50%, 60%, 70%, 80%, 90%, obtain different ethanol sedimentation things respectively.The selenic acid chitosan of post precipitation is removed materials such as unconjugated selenate radical in the reaction solution with centrifugal separation.The selenic acid chitosan of post precipitation is dissolved in the distilled water, and uses membrane separation technique, obtains molecular weight respectively at 2000Da-5000Da, 5000Da-10000Da and the selenic acid chitosan more than the 10000Da.Obtain white or off-white powder shape selenic acid chitosan after the lyophilize.
More than operation can change chitosan into chrondroitin and Sargassum polysaccharides, can obtain same selenic acid chrondroitin and selenic acid Sargassum polysaccharides.
Its structure is as follows:
The selenic acid chitosan
C6-OH or C3-OH or-NH
2The group selenic acidization
The character of selenic acid chitosan is:
(1) liquid of selenic acid chitosan (aqueous solution) is transparent, and is colourless, or slightly yellow;
(2) solvability of selenic acid chitosan: water-soluble, acid is molten, and alkali is molten, and salt (sodium-chlor) is molten.Dissolved degree of separating can reach 10%-40%;
(3) according to the alcoholic acid different concns, can prepare the different dissolve with ethanol selenic acid of 50%-90% chitosan respectively, the deacetylation difference of selenic acid degree, molecular weight and the chitosan of the selenic acid chitosan of different pure dissolubilities can prepare the product of different purposes respectively;
(4) after the aqueous solution of selenic acid chitosan process spraying drying or the lyophilize, be white in color, or the beige powder;
(5) molecular weight: 2000-50000;
(6) selenic acid degree (selenium content): 3mg-200mg/g;
(7) selenic acid chitosan and tegument glycan (not selenium acidifying chitosan) intensive stretching vibration charateristic avsorption band occurs at wavelength 865cm-1 place.
Referring to Fig. 1,2 relatively, as Fig. 1, selenium acidifying chitosan is not at wavelength 865cm
-1The stretching vibration charateristic avsorption band does not appear in the place.Fig. 2 is at wavelength 865cm
-1Intensive stretching vibration charateristic avsorption band appears in the place.
Fig. 3 is the mode chart of the electrolytic preparation polysaccharide of selenic acid of chitosan, among the figure, 1 anode, 2 vacuum valves, the penetrating film of 3 selectivity ions, 4 negative electrodes, 5,6 liquid outlets.By the oxidation-reduction reaction of electrode, make tin anhydride, selenous acid and salt thereof be oxidized to selenic acid, reaction generates polysaccharide of selenic acid under vacuum condition again.
Fig. 4: with not selenium acidifying chitosan contrast, selenium acidifying chitosan and selenic acid cartilage polysaccharide all demonstrate the effect that intensive suppresses the blood cell growth activity under 1/1000 concentration and 1/10000 concentration.
Fig. 5, polysaccharide of selenic acid induce blood cell k562 to transfer the result who dies: by the observation of cellular form, add polysaccharide of selenic acid (1/1000 concentration) blood cell is played significant lethal effect, when cultivating in 48 hours, make the tangible cracking of cell, cell diminishes, by 72 hours, cancer cells was all transferred and is died.
The preparation of selenic acid Lalgine: at first with after the polymeric hydantoin alginic acid process degraded (n is less than 60), C2-OH group place in Lalgine or C3-OH group place import the selenate radical of stable in properties, form the selenic acid Lalgine, the detailed process of preparation and step are with embodiment 1 (summary).Its structure is as follows:
The selenic acid Lalgine
The character of selenic acid Lalgine is:
(1) liquid of selenic acid Lalgine (aqueous solution) is transparent, and is colourless;
(2) solvability of selenic acid Lalgine: water-soluble, acid is molten, and alkali is molten, and salt (sodium-chlor) is molten.Dissolved degree of separating can reach 10%-20%;
(3) according to the alcoholic acid different concns, can prepare the different dissolve with ethanol selenic acid of 50%-90% Lalgine respectively, the selenic acid degree of the selenic acid Lalgine of different pure dissolubilities, molecular weight difference can prepare the product of different purposes respectively;
(4) after selenic acid marine alga aqueous acid process spraying drying or the lyophilize, be white in color, or the beige powder;
(5) molecular weight: 2000-50000;
(6) selenic acid degree (selenium content): 3mg-200mg/g;
Concrete application example of the present invention
1, polysaccharide of selenic acid capsule: adopt the polysaccharide of selenic acid of solubility to be prepared into capsule, wherein every capsules contains polysaccharide of selenic acid 0.25g, and be used for the treatment of and prevent cancer cell multiplication, enhance immunity power, the reduction serum cholesterol is obeyed 2 every day;
2, polysaccharide of selenic acid sugar coated tablet: adopt the gastric-juice-soluble polysaccharide of selenic acid to be prepared into sugar coated tablet, wherein every contains polysaccharide of selenic acid 0.25g, is suitable for middle-aged and old daily maintenences, obeys the 1-2 grain every day;
3, polysaccharide of selenic acid injection: adopt the water soluble selenium acid polysaccharide, be prepared into the polysaccharide of selenic acid sub-bottling of 0.5g earlier through lyophilize, during use with injecting behind the physiological saline solution;
4, polysaccharide of selenic acid asparate infusion: adopt the water soluble selenium acid polysaccharide, be prepared into the polysaccharide of selenic acid sub-bottling of 0.5g earlier through lyophilize, be dissolved in usefulness in the time of to infuse behind the physiological saline, each consumption 0.5g;
5, polysaccharide of selenic acid: polysaccharide of selenic acid good water solubility of the present invention, good stability, be all very stable under any pH value, and with nutritive substances such as protein, sugar, fat, Mierocrystalline cellulose, mineral substance, VITAMIN any aggregation does not take place, can be prepared into the various beverages that are fit to all kinds of consumer groups;
6, polysaccharide of selenic acid is as the nutrition and the medicinal reinforcer of various food.
Claims (10)
1, a kind of polysaccharide of selenic acid is characterized in that this polysaccharide of selenic acid is selenate radical to be imported to the polysaccharide of selenic acid that generates in the polysaccharide ring by oxidation-reduction method.
2, polysaccharide of selenic acid according to claim 1, it is characterized in that this polysaccharide of selenic acid in cartilage polysaccharide-OH group place or-NH
2The group place imports the selenate radical of stable in properties, forms the selenic acid cartilage polysaccharide.
3, polysaccharide of selenic acid according to claim 2 is characterized in that this selenic acid cartilage polysaccharide comprises: selenic acid heparin, selenic acid heparan, selenic acid chrondroitin, selenic acid hyaluronic acid, its structure are distinguished as follows: the selenic acid heparin
The selenic acid heparan
Selenic acid chrondroitin (place of 2,3,4,6 or many places selenic acidization)
Selenic acid hyaluronic acid (place of 2,3,6 or many places selenic acidization)
4, polysaccharide of selenic acid according to claim 1, it is characterized in that this polysaccharide of selenic acid be C6-OH group place in chitosan or C3-OH group place or-NH
2The group place imports the selenate radical of stable in properties, forms the selenic acid chitosan, and its structure is as follows:
The selenic acid chitosan
C6-OH or C3-OH or-NH
2The group selenic acidization
5, polysaccharide of selenic acid according to claim 1, it is characterized in that this polysaccharide of selenic acid is through degraded with the polymeric hydantoin alginic acid, be n less than after 60, C2-OH group place in Lalgine or C3-OH group place import the selenate radical of stable in properties, form the selenic acid Lalgine, its structure is as follows: the selenic acid Lalgine
6, the preparation method of the polysaccharide of selenic acid in a kind of claim 1 to 5 is characterized in that this method finishes by following steps:
(1) selenic acid H
2SeO
4Preparation;
(2) contain the preparation of selenium acidifying soluble polysaccharide liquid: at first, with polysaccharide place the selenic acid that contains step preparation, and the strong OR ambient condition of strong oxidizer under, vacuum, 40 degree following low-temp reaction 10-72 hour obtain containing selenium acidifying soluble polysaccharide liquid by centrifugal or filtering method;
(3) importing of selenate radical:---can be at the hydroxyl-OH or the amino-NH of sugar ring
2Acylation reaction takes place,---or substitution reaction takes place on the group of acidylate, generate polysaccharide of selenic acid, promptly-O-SeO
3H or-NH-SeO
3H;
(4) ion in the reaction solution is removed in reaction after finishing: will go up the step molecular weight with ultra-filtration membrane and filter less than 1000 sodium ion, chlorion, the selenate radical of failing to import and unreacted selenite radical; Filtrate can recycle after concentrating;
(5) fractionation precipitation of polysaccharide of selenic acid reclaims: the polysaccharide of selenic acid through purifying after the ultrafiltration obtains 50%, 60%, 70%, 80%, 90% fractionation precipitation thing with the ethanol precipitation classification, and throw out obtains pure product polysaccharide of selenic acid after by spraying drying or lyophilize.
7,, it is characterized in that selenic acid H according to the preparation method of claim 6 described polysaccharide of selenic acid
2SeO
4Preparation can be by tin anhydride SeO
2With water H
2The O reaction generates selenous acid H
2SeO
3, selenous acid generates selenic acid under the effect of strong oxidizer.
8,, it is characterized in that described strong oxidizer comprises the chloric acid and the oxymuriate thereof that can make selenous acid be oxidized to selenic acid, hypochlorous acid and hypochlorite thereof, and hydrogen peroxide according to the preparation method of claim 6,7 described polysaccharide of selenic acid.
9,, it is characterized in that selenic acid H according to the preparation method of claim 6 described polysaccharide of selenic acid
2SeO
4Preparation can also adopt airtight electrolytic process, be that the anode of the airtight electrolyzer of sodium-chlor adds tin anhydride SeO promptly at electrolytic solution
2Or selenous acid H
2SeO
3, tin anhydride SeO
2With water H
2The O reaction generates selenous acid, and selenous acid generates selenic acid at the anode generation oxidation-reduction reaction of energising.
10,, it is characterized in that the pure product polysaccharide of selenic acid that obtains can prepare the polysaccharide of selenic acid that molecular weight is 1,000～several ten thousand various series by membrane separation technique according to the preparation method of claim 6 described polysaccharide of selenic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936291A (en) * | 2012-11-15 | 2013-02-20 | 深圳大学 | Method for preparing selenylation poly mannuronic acid and application of selenylation poly mannuronic acid |
| CN106084080A (en) * | 2016-06-01 | 2016-11-09 | 石河子大学 | A kind of Radix Glycyrrhizae selenium polysaccharide and preparation method thereof |
-
2004
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936291A (en) * | 2012-11-15 | 2013-02-20 | 深圳大学 | Method for preparing selenylation poly mannuronic acid and application of selenylation poly mannuronic acid |
| CN102936291B (en) * | 2012-11-15 | 2014-12-31 | 深圳大学 | Method for preparing selenylation poly mannuronic acid and application of selenylation poly mannuronic acid |
| CN106084080A (en) * | 2016-06-01 | 2016-11-09 | 石河子大学 | A kind of Radix Glycyrrhizae selenium polysaccharide and preparation method thereof |
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| CN1281629C (en) | 2006-10-25 |
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