CN101628946A - Method for compounding polyhexose selenide by microwave - Google Patents
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Abstract
The invention relates to a method for compounding polyhexose selenide by microwaves, comprising the following steps: 1) putting sand sagebrush polyhexose or silverweed cinquefoil root polyhexose into a reactor, and adding N, N-dimethylformamide to obtain a suspension A; 2) dropping thionyl chloride into sodium hydrogen selenite to react, and depressing and distilling reaction liquid to obtain a solid matter B; 3) solving the solid matter B by the N, N-dimethylformamide, and then, adding the liquid into the suspension A to obtain reaction liquid C under the condition of microwave radiation; 4) solving the reaction liquid C by distilled water, regulating pH which is equal to 7 by sodium hydroxide, centrifuging, loading supernatant fluid into a dialysis bag with interception molecular weight from 8000 to 14000Da, introducing tap water to dialyze, and using deionized water to dialyze; decompressing and concentrating solution in the dialysis bag, adding ethanol in the concentrated solution, standing the concentrated solution at room temperature, centrifuging, collecting lower-layer deposits, cooling, drying and obtaining silverweed cinquefoil root polyhexose selenide or sand sagebrush polyhexose selenide. The method for compounding polyhexose selenide by microwaves has short reaction time, few reaction byproducts, simple reaction process, high selenium content of products, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of selenizing polysaccharide, especially relate to the method for the synthetic selenizing polysaccharide of a kind of microwave.
Background technology
Selenium (Se) can strengthening immunity, prevent diabetes, prevent cataract, prevent cardiovascular and cerebrovascular diseases, prevent Keshan disease, Kaschin-Beck disease, sacroiliitis, detoxifcation, toxin expelling, prevent and treat effects such as hepatopathy, protection liver, is referred to as " anticancer king " in the body trace element by scientist.Contain the Selenoperoxidase of the enzyme of selenium as a class, can eliminate various superoxide and the free radicals that cause cardiovascular diseases and cancer to take place, thereby reduce the incidence of cancer, body is played antioxygenation.Therefore the height of blood selenium level has substantial connection with the health of human body.The people takes in nearly all from food the body of selenium, as the more sea-food of selenium content, animal kidney, meat, rice, cereal etc., and the less fruit of selenium content, vegetables etc.Inorganic selenium that is absorbed by body and organoselenium can change into bioactive material, and excessive absorption selenium can cause the generation of poisoning.
At present, a metabolism that focus is effective supply selenium of selenizing research significantly improves resistance of oxidation.People mainly replenish organoselenium by more edible rich selenium products.Patent ZL 02121449.2 has authorized a kind of selenium-rich water-soluble dietary fiber protective foods that contains konjac glucomanna and preparation method thereof, and the effect of the protective foods that makes existing hypoglycemic and blood fat can be cleared up intravital carcinogenic substance again; Patent CN 1223820A discloses a kind of prescription and production technique of multivitamin selenium-enriched naked oats milk powder, and the selenium content of the multivitamin fortified milk powder that makes is 11 μ g/g; Patent CN 1068254A discloses a kind of production technology of selenium-enriched eggs, and this method is to add inorganic selenium in normal diet, and the organic selenium content in the egg is 10 times of common egg; Patent ZL 00105591.7 has authorized a kind of production method of Se-rich lucid ganoderma nutritive health-care rice, and this method is to add Sodium Selenite to make health care rice in rice; Patent CN 101228953A discloses a kind of organic Se-rich lucid ganoderma healthy product and preparation method thereof, and this method is that organic Se-rich lucid ganoderma and organic Chinese caterpillar fungus mixed preparing are formed; Patent ZL 200410044942.6 has authorized a kind of production method of tea rich in selenium beer, and this method is the operation of having added one tea rich in selenium soup or its concentrated solution on original beer technology, thereby has increased the organoselenium in the beer; Patent CN 101380044A discloses a kind of rich selenium rape oil and preparation method thereof, and this method is to be raw material with the natural selenium-rich vegetable seed, and the selenium content of the rape oil that makes is 0.01-0.1mg/kg.
The selenium polysaccharide that polysaccharide and selenium organically combine is as a kind of selenium source material, compare with inorganic selenium, have characteristics such as toxicity is low, environmental pollution is little, and selenium polysaccharide has anti-oxidant significantly, strengthening immunity, biological activity such as hypoglycemic, anti-ageing, antitumor and antiviral, its activity generally is higher than polysaccharide and inorganic selenium, and is easier to absorb and utilization into body.Selenium polysaccharide not only can suppress growth of tumor, can also direct killing or kill tumor cell, and cell death inducing suppresses the propagation of tumour cell.Therefore the research to selenium polysaccharide has certain realistic meaning and important prospect.Patent CN 1560088A discloses a kind of preparation method of selenizing konjac glucomanna, adds ethanol and hydrochloric acid in a kind of Se6+ solution, obtains selenylation reaction liquid, adds konjac glucomanna, makes the selenizing konjac glucomanna, and selenium content is 125.4-197.3mg/kg; Patent ZL 200410071806.6 has authorized a kind of polysaccharide of selenic acid and preparation method thereof, and this method is that the synthetic selenous acid is reduced into selenic acid, imports then in the polysaccharide, and selenium content is 3mg-200mg/g; Patent ZL 88103347 has authorized a kind of method for making of selenocarrageenan, the selenocarrageenan of this method preparation, and selenium content lower (2500-15000ppm), and the by product Selenium hydride is poisonous; Patent CN 101024664A discloses selenium-galactose and chemosynthesis thereof, and this method obtains the pharmacologically active that monose does not have natural polysaccharide and had; Patent CN 101190951A discloses a kind of preparation method of polysaccharide selenate, and what this method adopted is inhomogeneous reaction, uses anhydrous dextran or anhydrous astragalus polysaccharides, and synthetic is the selenic acid ester, and the reaction times, selenium content was 769-2250 μ g/g about 5 hours; Patent CN1284509A discloses chitosan selenite and preparation method thereof, and this method is to use the amido of chitosan and the selenous acid reaction of adding, and the selenium content of product is 0-26%; Patent CN 101104644A discloses a kind of method for making and application thereof of polysaccharide monohydrate selenium dioxide ester, polysaccharide and selemium oxyfluoride are in pyridine, reacting by heating 0.1-100 hour, obtain polysaccharide monohydrate selenium dioxide ester, the highest selenium content can reach 45%, but this method reaction times is long, and selemium oxyfluoride also is difficult for synthetic, is not suitable for large-scale industrial production.
The selenizing technology of mentioning in the above patent exists long, shortcoming such as the products therefrom yield is low, side reaction is many of reaction times.The domestic and foreign literature patent does not report that all sodium hydroselenite and sulfur oxychloride prepare selenizing reagent, is raw material with the artemisia desertorum polysaccharide and the fern amylose of purifying, the method for synthetic selenizing fern amylose of microwave and selenizing artemisia desertorum polysaccharide.
Summary of the invention
The technical problem to be solved in the present invention provides the method for the synthetic selenizing polysaccharide of a kind of microwave; This method is with the synthetic selenizing reagent of sodium hydroselenite and sulfur oxychloride, is raw material with the artemisia desertorum polysaccharide and the fern amylose of purifying, and microwave synthesizes the selenizing polysaccharide; The reaction times of this method is short, and byproduct of reaction is few, product selenium content height.
For solving the problems of the technologies described above, the method for the synthetic selenizing polysaccharide of a kind of microwave of the present invention comprises the steps:
(1) artemisia desertorum polysaccharide or fern amylose are put into reactor, add N, dinethylformamide gets suspension liquid A;
(2) dripping thionyl chloride is reacted in the sodium hydroselenite, the reaction solution underpressure distillation, solid matter B;
(3) use N, dinethylformamide dissolves solid matter B, joins then among the suspension liquid A, reacts under the condition of microwave radiation, gets reaction liquid C;
(4) with the reaction liquid C dissolved in distilled water, regulate pH=7 with sodium hydroxide, centrifugal, be in the dialysis tubing of 8000～14000Da with pack into the molecular weight that dams of supernatant liquor, logical tap water dialysis is dialysed with deionized water again; Solution decompression in the dialysis tubing is concentrated, in concentrated solution, add ethanol, leave standstill under the room temperature, centrifugal, collect the lower sediment thing, lyophilize obtains selenizing fern amylose or artemisia desertorum polysaccharide.
Further, the concrete steps of described step (1) are as follows: the purity that takes by weighing 0.3～0.6g is put into reactor at artemisia desertorum polysaccharide more than 90% or fern amylose, adds N, and N-methylformamide 15～20ml stirs 30～45min under the room temperature, gets suspension liquid A;
Further, the concrete steps of described step (2) are as follows: take by weighing 1.5～2.0g sodium hydroselenite and add in the reactor, dripping thionyl chloride, nitrogen protection, stir by magnetic stirring apparatus, ice bath is reaction 25～45min down, at pressure 0.06～0.08MPa, 45～55 ℃ of following underpressure distillation of temperature get solid matter B; The ratio of described sodium hydroselenite and sulfur oxychloride is the 1g sodium hydroselenite: 10～15ml sulfur oxychloride;
Further, the concrete steps of described step (3) are as follows: with solid matter B with 10～15ml N, the dinethylformamide dissolving, being added drop-wise to fully among the suspension liquid A under the condition of ice bath, dripping off in 20～25min, is 50～500W at microwave power afterwards, frequency is 2450MHz, temperature be 30～60 ℃ the reaction 10min～60min, be cooled to room temperature after, reaction liquid C.
Further, the concrete steps of described step (4) are as follows: with reaction liquid C with 200～250ml dissolved in distilled water, regulating pH with the sodium hydroxide of 2～3mol/L is 7, centrifugal 8～10min under 20～25 ℃, 3500～4500 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～14000Da, tap water dialysis 18～36 hours is again with deionized water dialysis 24～48 hours; Solution in the dialysis tubing is evaporated to 1/10～1/15 of original volume under 55～65 ℃, 0.06～0.08MPa, adds ethanol in concentrated solution, described ethanol accounts for 75～90% of overall solution volume; Left standstill under the room temperature 20～24 hours, centrifugal under 20～25 ℃, 2500～4500 rev/mins condition then, collect the lower sediment thing,, obtain selenizing artemisia desertorum polysaccharide or fern amylose throw out lyophilize 24～36 hours under-60～-55 ℃, the condition of 5～20Pa.
Relatively seeing the following form of synthetic selenium polysaccharide of microwave of the present invention and inorganic method:
| Raw material | Temperature (℃) | Time (min) | Power (w) | Selenium content (μ g/g) | |
| Embodiment 1 | Artemisia desertorum polysaccharide | ??40 | ??40 | ??300 | ??22000 |
| Embodiment 2 | Artemisia desertorum polysaccharide | ??60 | ??50 | ??150 | ??32000 |
| Embodiment 3 | Artemisia desertorum polysaccharide | ??45 | ??10 | ??500 | ??18000 |
| Embodiment 4 | Fern amylose | ??30 | ??60 | ??50 | ??24000 |
| Embodiment 5 | Fern amylose | ??50 | ??30 | ??400 | ??30000 |
| Embodiment 6 | Fern amylose | ??35 | ??20 | ??200 | ??19000 |
| Comparative example 1 | Fern amylose | ??60 | ??480 | ??- | ??19000 |
| Comparative example 2 | Artemisia desertorum polysaccharide | ??65 | ??300 | ??- | ??18000 |
The invention has the beneficial effects as follows: the present invention is to be raw material with the fern amylose of purifying or artemisia desertorum polysaccharide, adopts sodium hydroselenite and sulfur oxychloride to prepare selenizing reagent, reacts with polysaccharide under microwave-assisted, obtains the selenizing polysaccharide of high selenium content.Compare with common selenizing polyoses producing method, selenium content significantly improves, microwave reaction thermo-efficiency height, and speed of reaction is fast, has solved popular response condition shortcoming consuming time, is the method for a kind of green, the synthetic selenium polysaccharide of environmental protection.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is is the XPS spectrum of artemisia desertorum polysaccharide (a) and selenizing artemisia desertorum polysaccharide (b); Artemisia desertorum polysaccharide does not have Se 3d absorption peak, and strong Se 3d absorption peak appears in the artemisia desertorum polysaccharide after the selenizing at the 62.44eV place, illustrate to form the selenizing artemisia desertorum polysaccharide.
Fig. 2 is is the x-ray photoelectron power spectrum (XPS) of fern amylose (a) and selenizing fern amylose (b); Without any absorption peak, and the fern amylose after the selenizing illustrates that at the very strong Se 3d absorption peak of 62.75eV place appearance fern amylose is by selenizing in the Se 3d of the fern amylose spectrum.
Embodiment
Embodiment 1
The present invention is the method for preparing a kind of selenizing artemisia desertorum polysaccharide under microwave-assisted fast, comprises the steps:
(1) purity that takes by weighing 0.45g is put into reactor at the fern amylose more than 90%, adds 17mlN, and dinethylformamide stirs 37min under the room temperature, gets suspension liquid A;
(2) take by weighing 1.7g and restrain in the sodium hydroselenite adding reactor, drip the 17ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 30min down, and at pressure 0.06MPa, 50 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath, dripping off in the 21min, is 300W at microwave power afterwards, and frequency is 2450MHz, temperature be 40 ℃ the reaction 40min, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 21 ℃, 3700 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 30 hours is again with deionized water dialysis 30 hours; Solution in the dialysis tubing is evaporated to 1/15 of original volume under 62 ℃, 0.08MPa, in concentrated solution, add ethanol, described ethanol accounts for 78% of overall solution volume, left standstill under the room temperature 23 hours, centrifugal under 24 ℃, 3500 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 30 hours under-57 ℃, the condition of 17Pa, obtain the selenizing artemisia desertorum polysaccharide, selenium content is 22000 μ g/g.
Referring to shown in Figure 1, Fig. 1 is is the XPS spectrum of artemisia desertorum polysaccharide (a) and selenizing artemisia desertorum polysaccharide (b); Artemisia desertorum polysaccharide does not have Se 3d absorption peak, and strong Se 3d absorption peak appears in the artemisia desertorum polysaccharide after the selenizing at the 62.44eV place, illustrate to form the selenizing artemisia desertorum polysaccharide.
Embodiment 2
The present invention is the method for preparing a kind of selenizing artemisia desertorum polysaccharide under microwave-assisted fast, comprises the steps:
(1) purity that takes by weighing 0.45g is put into reactor at the fern amylose more than 90%, adds 19mlN, and dinethylformamide stirs 45min under the room temperature, gets suspension liquid A;
(2) take by weighing 1.9g and restrain in the sodium hydroselenite adding reactor, drip the 19ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 45min down, and at pressure 0.07MPa, 55 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath, dripping off in the 25min, is 150W at microwave power afterwards, and frequency is 2450MHz, temperature be 60 ℃ the reaction 50min, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 25 ℃, 4500 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 36 hours is again with deionized water dialysis 24 hours; Solution in the dialysis tubing is evaporated to 1/12 of original volume under 57 ℃, 0.07MPa, in concentrated solution, add ethanol, described ethanol accounts for 90% of overall solution volume, left standstill under the room temperature 22 hours, centrifugal under 21 ℃, 4200 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 30 hours under-62 ℃, the condition of 15Pa, obtain the selenizing artemisia desertorum polysaccharide, selenium content is 32000 μ g/g.
Embodiment 3
The present invention is the method for preparing a kind of selenizing artemisia desertorum polysaccharide under microwave-assisted fast, comprises the steps:
(1) purity that takes by weighing 0.6g is put into reactor at the fern amylose more than 90%, adds 20ml N, and dinethylformamide stirs 42min under the room temperature, gets suspension liquid A;
(2) take by weighing 2.0g and restrain in the sodium hydroselenite adding reactor, drip the 20ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 42min down, and at pressure 0.08MPa, 52 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath, dripping off in the 23min, is 500W at microwave power afterwards, and frequency is 2450MHz, temperature be 45 ℃ the reaction 10min, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 24 ℃, 3600 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 32 hours is again with deionized water dialysis 33 hours; Solution in the dialysis tubing is evaporated to 1/14 of original volume under 63 ℃, 0.06MPa, in concentrated solution, add ethanol, described ethanol accounts for 87% of overall solution volume, left standstill under the room temperature 21 hours, centrifugal under 20 ℃, 4100 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 33 hours under-61 ℃, the condition of 5Pa, obtain the selenizing artemisia desertorum polysaccharide, selenium content is 18000 μ g/g.
Embodiment 4
The present invention is the method for preparing a kind of selenizing fern amylose under microwave-assisted fast, comprises the steps:
(1) purity that takes by weighing 0.3 gram is put into reactor at the fern amylose more than 90%, adds 15mlN, and dinethylformamide stirs 30min under the room temperature, gets suspension liquid A;
(2) take by weighing the 1.5g sodium hydroselenite and add in the reactor, drip the 15ml sulfur oxychloride,, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 25min down, and at pressure 0.07MPa, 49 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath, dripping off in the 20min, is 50W at microwave power afterwards, and frequency is 2450MHz, temperature be 30 ℃ the reaction 60min, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 23 ℃, 4000 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 20 hours is again with deionized water dialysis 40 hours; Solution in the dialysis tubing is evaporated to 1/10 of original volume under 55 ℃, 0.06MPa, in concentrated solution, add ethanol, described ethanol accounts for 85% of overall solution volume, left standstill under the room temperature 20 hours, centrifugal under 22 ℃, 4000 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 24 hours under-55 ℃, the condition of 20Pa, obtain the selenizing fern amylose, selenium content is 24000 μ g/g.
Embodiment 5
The present invention is the method for preparing a kind of selenizing fern amylose under microwave-assisted fast, comprises the steps:
(1) purity that takes by weighing 0.4g is put into reactor at the fern amylose more than 90%, adds 16ml N, and dinethylformamide stirs 35min under the room temperature, gets suspension liquid A;
(2) take by weighing 1.6g and restrain in the sodium hydroselenite adding reactor, drip the 16ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 35min down, and at pressure 0.06MPa, 47 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath, dripping off in the 24min, is 400W at microwave power afterwards, and frequency is 2450MHz, temperature be 50 ℃ the reaction 30min, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 22 ℃, 3500 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 18 hours is again with deionized water dialysis 40 hours; Solution in the dialysis tubing is evaporated to 1/13 of original volume under 60 ℃, 0.08MPa, in concentrated solution, add ethanol, described ethanol accounts for 80% of overall solution volume, left standstill under the room temperature 21 hours, centrifugal under 23 ℃, 3700 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 26 hours under-60 ℃, the condition of 10Pa, obtain the selenizing fern amylose, selenium content is 30000 μ g/g.
Referring to shown in Figure 2, Fig. 2 is is the x-ray photoelectron power spectrum (XPS) of fern amylose (a) and selenizing fern amylose (b); Without any absorption peak, and the fern amylose after the selenizing illustrates that at the very strong Se 3d absorption peak of 62.75eV place appearance fern amylose is by selenizing in the Se 3d of the fern amylose spectrum.
Embodiment 6
The present invention is the method for preparing a kind of selenizing fern amylose under microwave-assisted fast, comprises the steps:
(1) purity that takes by weighing 0.5g is put into reactor at the fern amylose more than 90%, adds 18ml N, and dinethylformamide stirs 40min under the room temperature, gets suspension liquid A;
(2) take by weighing 1.8g and restrain in the sodium hydroselenite adding reactor, drip the 18ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 40min down, and at pressure 0.08MPa, 45 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath, dripping off in the 22min, is 200W at microwave power afterwards, and frequency is 2450MHz, temperature be 35 ℃ the reaction 20min, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 20 ℃, 4300 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 24 hours is again with deionized water dialysis 36 hours; Solution in the dialysis tubing is evaporated to 1/11 of original volume under 65 ℃, 0.07MPa, in concentrated solution, add ethanol, described ethanol accounts for 75% of overall solution volume, left standstill under the room temperature 24 hours, centrifugal under 25 ℃, 4500 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 36 hours under-55 ℃, the condition of 12Pa, obtain the selenizing fern amylose, selenium content is 19000 μ g/g.
Comparative example 1
Method and conventional heating with embodiment 5 experimentize.The difference of two experiments is conventional the heating with the sodium hydroselenite in the selenous acid replacement embodiment step 2, adopts 60 ℃ of reacting by heating 480min to replace embodiment step 4, comprises the steps:
(1) purity that takes by weighing 0.3g is put into reactor at the fern amylose more than 90%, adds 15ml N, and dinethylformamide stirs 30min under the room temperature, gets suspension liquid A;
(2) take by weighing 1.5g and restrain in the sodium hydroselenite adding reactor, drip the 15ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 25min down, and at pressure 0.07MPa, 49 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, dinethylformamide dissolving is added drop-wise among the suspension liquid A under the condition of ice bath fully, drip off in the 20min, be 60 ℃ of reaction 480min in temperature afterwards, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 23 ℃, 4000 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 20 hours is again with deionized water dialysis 40 hours; Solution in the dialysis tubing is evaporated to 1/10 of original volume under 55 ℃, 0.06MPa, in concentrated solution, add ethanol, described ethanol accounts for 85% of overall solution volume, left standstill under the room temperature 20 hours, centrifugal under 22 ℃, 4000 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 24 hours under-65 ℃, the condition of 20Pa, obtain the selenizing fern amylose, selenium content is 19000 μ g/g.
Comparative example 2
Method and conventional heating with embodiment 1 experimentize.The difference of two experiments is conventional the heating with the sodium hydroselenite in the selenous acid replacement embodiment step 2, adopts 65 ℃ of reacting by heating 300min to replace embodiment step 4, comprises the steps:
(1) purity that takes by weighing 0.55g is put into reactor at the artemisia desertorum polysaccharide more than 90%, adds 19mlN, and dinethylformamide stirs 45min under the room temperature, gets suspension liquid A;
(2) take by weighing 1.9g and restrain in the sodium hydroselenite adding reactor, drip the 19ml sulfur oxychloride, nitrogen protection is stirred by magnetic stirring apparatus, and ice bath is reaction 45min down, and at pressure 0.07MPa, 55 ℃ of following underpressure distillation of temperature get solid matter B;
(3) solid matter B is used 10ml N, dinethylformamide dissolving is added drop-wise among the suspension liquid A under the condition of ice bath fully, drip off in the 25min, be 65 ℃ of reaction 300min in temperature afterwards, be cooled to room temperature after, reaction liquid C.
(4) reaction liquid C is used the 200ml dissolved in distilled water, regulating pH with the sodium hydroxide of 3.0mol/L is 7, centrifugal 10min under 25 ℃, 4500 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～12000Da, tap water dialysis 36 hours is again with deionized water dialysis 24 hours; Solution in the dialysis tubing is evaporated to 1/12 of original volume under 57 ℃, 0.07MPa, in concentrated solution, add ethanol, described ethanol accounts for 90% of overall solution volume, left standstill under the room temperature 22 hours, centrifugal under 21 ℃, 4200 rev/mins condition then, collect the lower sediment thing, with throw out lyophilize 29 hours under-62 ℃, the condition of 15Pa, obtain the selenizing artemisia desertorum polysaccharide, selenium content is 18000 μ g/g.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be qualification to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (5)
1, the method for the synthetic selenizing polysaccharide of a kind of microwave is characterized in that, comprises the steps:
(1) artemisia desertorum polysaccharide or fern amylose are put into reactor, add N, dinethylformamide gets suspension liquid A;
(2) dripping thionyl chloride is reacted in the sodium hydroselenite, the reaction solution underpressure distillation, solid matter B;
(3) use N, dinethylformamide dissolves solid matter B, joins then among the suspension liquid A, reacts under the condition of microwave radiation, gets reaction liquid C;
(4) with the reaction liquid C dissolved in distilled water, regulate pH=7 with sodium hydroxide, centrifugal, be in the dialysis tubing of 8000～14000Da with pack into the molecular weight that dams of supernatant liquor, logical tap water dialysis is dialysed with deionized water again; Solution decompression in the dialysis tubing is concentrated, in concentrated solution, add ethanol, leave standstill under the room temperature, centrifugal, collect the lower sediment thing, lyophilize obtains selenizing fern amylose or artemisia desertorum polysaccharide.
2, the method for the synthetic selenizing polysaccharide of a kind of microwave according to claim 1, it is characterized in that: the concrete steps of described step (1) are as follows: the purity that takes by weighing 0.3～0.6g is put into reactor at artemisia desertorum polysaccharide more than 90% or fern amylose, add N, dinethylformamide 15～20ml, stir 30～45min under the room temperature, get suspension liquid A;
3, the method for the synthetic selenizing polysaccharide of a kind of microwave according to claim 1, it is characterized in that: the concrete steps of described step (2) are as follows: take by weighing 1.5～2.0g sodium hydroselenite and add in the reactor, dripping thionyl chloride, nitrogen protection, stir by magnetic stirring apparatus, ice bath is reaction 25～45min down, at pressure 0.06～0.08MPa, 45～55 ℃ of following underpressure distillation of temperature get solid matter B; The ratio of described sodium hydroselenite and sulfur oxychloride is the 1g sodium hydroselenite: 10～15ml sulfur oxychloride;
4, the method for the synthetic selenizing polysaccharide of a kind of microwave according to claim 1, it is characterized in that:, the concrete steps of described step (3) are as follows: with 10～15ml N, the dinethylformamide dissolving is added drop-wise among the suspension liquid A fully under the condition of ice bath with solid matter B, drip off in 20～25min, be 50～500W at microwave power afterwards, frequency is 2450MHz, and temperature is 30～60 ℃ of reaction 10min～60min, after being cooled to room temperature, get reaction liquid C.
5, the method for the synthetic selenizing polysaccharide of a kind of microwave according to claim 1, it is characterized in that: the concrete steps of described step (4) are as follows: with reaction liquid C with 200～250ml dissolved in distilled water, regulating pH with the sodium hydroxide of 2～3mol/L is 7, centrifugal 8～10min under 20～25 ℃, 3500～4500 rev/mins condition, with pack into the molecular weight that dams of supernatant liquor is in the dialysis tubing of 8000～14000Da, tap water dialysis 18～36 hours is again with deionized water dialysis 24～48 hours; Solution in the dialysis tubing is evaporated to 1/10～1/15 of original volume under 55～65 ℃, 0.06～0.08MPa, adds ethanol in concentrated solution, described ethanol accounts for 75～90% of overall solution volume; Left standstill under the room temperature 20～24 hours, centrifugal under 20～25 ℃, 2500～4500 rev/mins condition then, collect the lower sediment thing,, obtain selenizing artemisia desertorum polysaccharide or fern amylose throw out lyophilize 24～36 hours under-60～-55 ℃, the condition of 5～20Pa.
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| CN102532339A (en) * | 2012-02-14 | 2012-07-04 | 兰州大学 | Method for selenizing pilose asiabell root polysaccharides and application of product |
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| CN107629134B (en) * | 2017-09-18 | 2019-12-31 | 西北师范大学 | Method for synthesizing selenylation artemisia desertorum polysaccharide by taking ionic liquid as solvent and catalyst |
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| CN102532339A (en) * | 2012-02-14 | 2012-07-04 | 兰州大学 | Method for selenizing pilose asiabell root polysaccharides and application of product |
| CN103356691A (en) * | 2013-07-22 | 2013-10-23 | 兰州理工大学 | Preparation method of potentilla anserina L. root crude polysaccharide with potentilla anserina L. root as raw material and use |
| CN105713104A (en) * | 2016-04-28 | 2016-06-29 | 西北师范大学 | Synthesis and application of selenized fenugreek polysaccharides |
| CN105713104B (en) * | 2016-04-28 | 2017-11-21 | 西北师范大学 | A kind of synthesis and its application of selenizing Fenugreek Polysaccharides |
| CN109384856A (en) * | 2017-08-03 | 2019-02-26 | 河北凯盛医药科技有限公司 | A kind of preparation method of fern amylose ultramicron |
| CN107573437A (en) * | 2017-10-12 | 2018-01-12 | 西北师范大学 | A kind of method of solid acid catalysis synthesis selenizing polysaccharide |
| CN107573437B (en) * | 2017-10-12 | 2019-12-27 | 西北师范大学 | Method for synthesizing selenized polysaccharide by solid acid catalysis |
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