CN101560267A - Preparation method of polysaccharide selenite - Google Patents
Preparation method of polysaccharide selenite Download PDFInfo
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- CN101560267A CN101560267A CNA2009101435777A CN200910143577A CN101560267A CN 101560267 A CN101560267 A CN 101560267A CN A2009101435777 A CNA2009101435777 A CN A2009101435777A CN 200910143577 A CN200910143577 A CN 200910143577A CN 101560267 A CN101560267 A CN 101560267A
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Abstract
The invention discloses a preparation method of polysaccharide selenite, which comprises the following steps: polysaccharide is mixed with saltpeter solution and stirred at room temperature to cause the polysaccharide to swell; sodium selenite and stannic chloride are added into the obtained polysaccharide saltpeter solution and react in water bath at temperature of 60-80 DEG C for six to fourteen hours in a stirring manner, and then cooled to room temperature; and suction filtration treatment and primary centrifuging treatment are conducted under the pressure of 0.07-0.08MPa; primary supernatant obtained is put into a dialysis bag, dialyzed with running water and distilled water in sequence and then depressurized and concentrated to 1/40 to 1/20 of the original volume; the obtained concentrated solution is deposited in alcohol and goes through secondary centrifuging treatment to obtain subsided deposit; and the subsided deposit is freeze dried to obtain the polysaccharide selenite. The preparation method has the advantages of controllable reaction conditions and high repeatability.
Description
Technical field
The present invention relates to selenizing polysaccharide technical field, particularly, relate to a kind of preparation method of polysaccharide monohydrate selenium dioxide ester.
Background technology
Polysaccharide is isolating protein and the outer important biomacromolecule of another class of nucleic acid in the organism, have immunologic injuries such as anti-infective, treatment and prevention of tumour, viral hepatitis, Rheumatoid and acquired immune deficiency syndrome (AIDS) or immunodeficiency disease and many-sided function and biological activity such as anti-oxidant, be subjected to people's generally attention in recent years.In recent years, the existing big progress of the molecular modification of relevant polysaccharide research.In the molecular modification of polysaccharide, utilize hydroxyl, carboxyl and amino groups on the saccharide residue, the utilization chemical process is modified, and might improve the activity of polysaccharide.Here, the chemical process of the molecular modification of polysaccharide comprises sulfation, carboxymethylation, selenic acidization and Phosphation etc.
In addition, selenium is essential trace element in the humans and animals vital movement process, and human body lacks selenium can cause fatal scarce selenium syndromes, as Keshan disease, and more than 40 kind of diseases such as Kaschin-Beck disease and cataract, all relevant with the selenium content of human body.Recent studies also shows, the generation that selenium can the immune stimulatory sphaeroprotein has anti-oxidant and antitumous effect.But, take in the excessive middle toxicity syndrome such as cataract, alopecia and piptonychia that also can cause of selenium.Can mend selenium by picked-up inorganic selenium and biological activity selenium by conventional benefit selenium form.Sodium Selenite also is a kind of medicine of mending selenium, but Sodium Selenite is a kind of inorganic salt simultaneously, and dosage is wayward, and effectively absorptivity is poor.
In application number is 00114699.8 patent application, a kind of chitosan selenite and preparation method thereof is provided, this chitosan selenite is that the content that reacts selenium in the products therefrom is 0～26% with chitosan and selenous acid reaction gained; Adopt the chitosan and selenous acid reaction of different molecular weight, can prepare the chitosan selenite of different molecular weight, the reaction products therefrom according to its molecular weight size and bonded selenous acid how much, and have different water-soluble.This chitosan selenite toxicity is low, easily be absorbed, and can be used as selenium-replenishing preparation, is used for fields such as medicine, healthcare products, makeup and agricultural.
In addition, in application number is 200610045482.8 patent application, a kind of method for making and application thereof of polysaccharide monohydrate selenium dioxide ester are provided, this polysaccharide monohydrate selenium dioxide ester is made by polysaccharide or polysaccharide compound and selenizing reagent react, wherein, selenizing reagent can be zirconyl oxyhalides selenium or the compound that contains oxyhalogen selenium structure, and the molar ratio of oh group is 1: 0.1～20 in selenizing reagent and the polysaccharide; The polysaccharide monohydrate selenium dioxide ester that makes can be used for the preparation of cancer therapy drug and anti-oxidation medicine.Here, the selenium content of polysaccharide monohydrate selenium dioxide ester is higher.
Lily polysaccharide and cynomorium songaricum polysaccharide are the natural polysaccharide superpolymer of a class, and wherein, lily derives from lanzhou lily (Lilium davidii var.unicolor Salisb.) dry meat scale leaf, and is sweet in flavor and cold in property, has the effect of nourishing YIN and clearing away lung-heat and clearing away the heart fire and tranquillizing.Modern medicine study shows, effects such as that lanzhou lily has is anticancer, antifatigue, hypoxia tolerance and cough-relieving contain chemical ingredientss such as saponin(e, alkaloid, polysaccharide, phosphatide, protein, amino acid, VITAMIN, starch and a large amount of trace elements in the Chinese medicine lanzhou lily.At present, the lanzhou lily STUDY ON POLYSACHAROSE still is in the starting stage, but because of its good prospects for application, causes increasing concern in recent years gradually.
At application number is in the patent application of ZL200610041681.1, a kind of preparation method of antifatigue lanzhou lily polysaccharide is provided, with natural lanzhou lily bulb is raw material, handle through extraction, deproteinated, separation and column chromatography, prepare new natural lanzhou lily polysaccharide with antifatigue effect; This natural lanzhou lily polysaccharide has the advantage that antifatigue is effective and have no side effect.
In addition, at application number is in the patent application of ZL200810097243.6, a kind of preparation method of lily polysaccharide of strengthening immunity is provided, and is raw material with natural lanzhou lily bulb, prepares a kind of natural polysaccharide of strengthening immunity through steps such as extraction, purifying, separation, deproteinated; This natural lanzhou lily polysaccharide is compared with other enhancing immunity product, and it is simple to have production technique, easy to use, and characteristic is with the obvious advantage, the resource reserve abundance.
Cynomorium songaricum has another name called Herba Cynomorii, is the kind of important help establishing-Yang in traditional mongolian medicine, and the neutral monose of active total polysaccharides is formed and is semi-lactosi, glucose, pectinose, rhamnosyl, seminose and ribose etc. in the cynomorium songaricum; Belonging to the parasitic draft of perennial meat, is the dry meat stem of Cynomoriaceae plant cynomorium songaricum (Cynomorium songaricum Rupr.); The sweet temperature of property, the function that has kidney-replenishing, benefiting essence-blood and relax bowel; Clinically be used for osteopyrexia and fever, the leg knee flaccidity is unable and the dry constipation of intestines etc.The diabetic mice experiment shows, when using all left and right sides of cynomorium songaricum polysaccharide 3, the blood glucose value of diabetic mice obviously reduces, hepatic glycogen content significantly raises, every blood parameters gpt, glutamic-oxal(o)acetic transaminase, blood urea nitrogen and creatinine all obviously reduce, and illustrates that cynomorium songaricum polysaccharide can improve the hepatic and renal function of diabetic mice, make the active raising of each organ SOD of liver, kidney and the heart, MDA content reduces, thereby shows that cynomorium songaricum polysaccharide can improve diabetic mice liver and kidney resistance of oxidation.
In application number is 200510055385.2 patent application, a kind of compound cynomorium drip pill and preparation method thereof is provided, this compound cynomorium drip pill is a raw material with three extracts of distinguishing the flavor of the Chinese medicine active ingredients that contain cynomorium songaricum, wolfberry fruit and shizandra berry, is prepared from pharmaceutically acceptable matrix; This compound cynomorium drip pill has invigorating the liver and kidney, benefiting essence-blood, strengthening the bones and muscles effect, the pharmaceutical composition that is used for treatment for diseases such as the dry constipation of the soft intestines of waist knee impotence, this compound cynomorium drip pill have that bioavailability height, medicament contg height, drug effect are fast, easy administration and cheap advantage.
In the preparation of above-mentioned polysaccharide and selenous acid, the selenium content of polysaccharide monohydrate selenium dioxide ester is limited; And, because the complicacy of polysaccharide structures, preparation method's difference of different its monohydrate selenium dioxide esters of polysaccharide, therefore, the method for setting up a kind of suitable selenous acid esterification at certain specific polysaccharide is very necessary.In the prior art, do not see as yet with lanzhou lily polysaccharide or cynomorium songaricum polysaccharide and be raw material, prepare the method for polysaccharide monohydrate selenium dioxide ester.
Summary of the invention
The objective of the invention is at the problems referred to above, propose a kind of preparation method of polysaccharide monohydrate selenium dioxide ester, to realize the advantage of selenium content height and good drug efficacy.
For achieving the above object, the invention provides a kind of preparation method of polysaccharide monohydrate selenium dioxide ester, comprise step: a, press polysaccharide: the proportion relation of nitric acid=1g: 100ml, with described polysaccharide and corresponding salpeter solution mixing, at room temperature stir, make described polysaccharide swelling, obtain the polysaccharide salpeter solution; B, in described polysaccharide salpeter solution, add Sodium Selenite and tin chloride, be 60～80 ℃ stirred in water bath in temperature, after the esterification 6～14 hours, be cooled to room temperature, when pressure is 0.07～0.08Mpa, carry out suction filtration and handle and a centrifugal treating, obtain supernatant liquor one time; C, a described supernatant liquor is packed in the dialysis tubing, carry out successively being evaporated to 1/40～1/20 of original volume after flowing water dialysis treatment and distill water dialysis handle, obtain concentrated solution; D, described concentrated solution carried out alcohol precipitation is handled and secondary centrifuging is handled, obtain precipitation; Again described precipitation is carried out lyophilize and handle, obtain described polysaccharide monohydrate selenium dioxide ester.
Wherein, described polysaccharide is lanzhou lily polysaccharide or cynomorium songaricum polysaccharide.
Further, in step a, the volumetric concentration of described salpeter solution is 0.3～0.8%.
Further, in step b, between a described suction filtration processing and a described centrifugal treating, further comprising the steps of: use anhydrous sodium carbonate, the pH value of described suction filtration being handled gained filtrate transfers to 5～6.
Further, in step b, the weight ratio of described Sodium Selenite and described tin chloride is 1: 1.675～3.35, and described tin chloride is a catalyzer.
Further, in step c, when the redness of liquid disappeared when add xitix, described dialysis tubing in described dialysis tubing in, described distill water dialysis was finished dealing with.
Further, in step c, the time of described flowing water dialysis treatment is 36～48 hours; The temperature that described concentrating under reduced pressure is handled is that 50～60 ℃, pressure conditions are 0.07～0.08Mpa; The molecular weight cut-off of described dialysis tubing is 8000～12000 dalton.
Further, in steps d, described alcohol precipitation is handled and is specifically comprised: add ethanol in described concentrated solution, at room temperature left standstill 20～30 hours; Wherein, described alcoholic acid volume accounts for 75～80% of described concentrated solution and described total ethanol volume.
Further, in step b and d, the described temperature of once handling with secondary centrifuging is that 15～20 ℃, rotating speed are 4000～4500 rev/mins, and the temperature that described lyophilize is handled is that-60 ℃～-50 ℃, time are 36～48 hours.
The preparation method of the polysaccharide monohydrate selenium dioxide ester of various embodiments of the present invention, with lanzhou lily polysaccharide or cynomorium songaricum polysaccharide is major ingredient, with nitric acid and Sodium Selenite is auxiliary material, with the tin chloride is catalyzer, press polysaccharide: nitric acid=1g: the proportion relation of 100ml, with lanzhou lily polysaccharide or cynomorium songaricum polysaccharide and corresponding salpeter solution mixing, at room temperature stir and spend the night, make lanzhou lily polysaccharide or cynomorium songaricum polysaccharide swelling; In the polysaccharide salpeter solution that obtains, add Sodium Selenite and tin chloride, be 60～80 ℃ stirred in water bath in temperature, esterification was cooled to room temperature after 6～14 hours, carries out suction filtration and handle and a centrifugal treating when pressure is 0.07～0.08Mpa; A supernatant liquor that obtains is packed in the dialysis tubing, carry out successively being evaporated to 1/40～1/20 of original volume after flowing water dialysis treatment and distill water dialysis handle; The concentrated solution that obtains is carried out alcohol precipitation processing and secondary centrifuging processing, obtain precipitation; Again this precipitation is carried out lyophilize and handle, can make lanzhou lily polysaccharide or cynomorium songaricum polysaccharide monohydrate selenium dioxide ester, this lanzhou lily polysaccharide or cynomorium songaricum polysaccharide have the high and good advantage of the property of medicine of selenium content.
In a word, the present invention with the extract that contains natural phant lanzhou lily or cynomorium songaricum, be that lanzhou lily polysaccharide or cynomorium songaricum polysaccharide are raw material, first under the katalysis of nitric acid-tin chloride, utilization utilizes Sodium Selenite that lanzhou lily polysaccharide or cynomorium songaricum polysaccharide are carried out molecular modification, synthesized lanzhou lily polysaccharide monohydrate selenium dioxide ester or cynomorium songaricum polysaccharide monohydrate selenium dioxide ester, this reaction conditions is controlled, and repeatability is high, solvability is good, and market outlook are good; In addition, introduce selenite radical in molecular structure, wherein selenium is positive tetravalence, selenium is the valence state that mediates, and both can oxidizedly also can be reduced, as seen, utilize preparation method of the present invention, the polysaccharide monohydrate selenium dioxide ester that makes has the potential biological activity in human body.
Other features and advantages of the present invention will be set forth in the following description, and, partly from specification sheets, become apparent, perhaps understand by implementing the present invention.Purpose of the present invention and other advantages can realize and obtain by specifically noted structure in the specification sheets of being write, claims and accompanying drawing.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Accompanying drawing is used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used from explanation the present invention with embodiments of the invention one, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the ultraviolet spectrogram of lanzhou lily polysaccharide and monohydrate selenium dioxide ester thereof among the preparation method of the polysaccharide monohydrate selenium dioxide ester according to the present invention;
Fig. 2 is the ultraviolet spectrogram of cynomorium songaricum polysaccharide and monohydrate selenium dioxide ester thereof among the preparation method of the polysaccharide monohydrate selenium dioxide ester according to the present invention;
Fig. 3 is the infrared spectrogram of lanzhou lily polysaccharide and monohydrate selenium dioxide ester thereof among the preparation method of the polysaccharide monohydrate selenium dioxide ester according to the present invention;
Fig. 4 is the infrared spectrogram of cynomorium songaricum polysaccharide and monohydrate selenium dioxide ester thereof among the preparation method of the polysaccharide monohydrate selenium dioxide ester according to the present invention.
In conjunction with the accompanying drawings, Reference numeral is as follows in the embodiment of the invention:
A1-lanzhou lily polysaccharide; B1-lanzhou lily polysaccharide monohydrate selenium dioxide ester; The A2-cynomorium songaricum polysaccharide; B2-cynomorium songaricum polysaccharide monohydrate selenium dioxide ester.
Embodiment
Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in qualification the present invention.
Basic thought of the present invention is: with lanzhou lily polysaccharide or cynomorium songaricum polysaccharide, promptly the extract that contains lanzhou lily or cynomorium songaricum Chinese medicine active ingredient is a raw material, in volumetric concentration is 0.3～0.8% salpeter solution, stir and spend the night, make its swelling, obtain the salpeter solution of lanzhou lily polysaccharide or cynomorium songaricum polysaccharide, place under the room temperature condition standby; With the salpeter solution of the lanzhou lily polysaccharide that obtains or cynomorium songaricum polysaccharide, with the mixture of Sodium Selenite and tin chloride, in 60～80 ℃ the aqueous solution, stir 6～14 hours after, be cooled to room temperature, filter, and adopt anhydrous sodium carbonate, the pH value of filtrate that filtration is obtained adjusts to 5～6, carries out centrifugal treating again; The supernatant liquor that centrifugal treating obtains is dialysed, precipitate with ethanol, at room temperature static after, carry out secondary centrifuging and handle, the sinking precipitation that secondary centrifuging obtains is carried out lyophilize, obtain the lanzhou lily polysaccharide monohydrate selenium dioxide ester or the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester of purifying.
In Fig. 1-Fig. 4, A1 represents the lanzhou lily polysaccharide, and B1 represents the lanzhou lily polysaccharide monohydrate selenium dioxide ester; A2 represents cynomorium songaricum polysaccharide, and B2 represents the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester.
By Fig. 1 and Fig. 2 contrast as can be known, among Fig. 1 among lanzhou lily polysaccharide monohydrate selenium dioxide ester B1 and Fig. 2 cynomorium songaricum polysaccharide monohydrate selenium dioxide ester B2 at λ=334nm place absorption peak is arranged, identical substantially with selenium in the documents and materials of the absorption peak of λ=335nm; In Fig. 3,3400cm
-1About-the OH absorption peak, 2928cm
-1About C-H stretching vibration peak and 1400-1200cm
-1C-H angle vibration peak all be the charateristic avsorption band of the compound of carbohydrate, by Fig. 3 and Fig. 4 contrast as can be known, the lanzhou lily polysaccharide monohydrate selenium dioxide ester has also increased 870.05cm except polysaccharide parent charateristic avsorption band
-1The absorption peak at place is the stretching vibration of Se=O in the monohydrate selenium dioxide ester, and this is the charateristic avsorption band of monohydrate selenium dioxide ester; Simultaneously, the lanzhou lily polysaccharide monohydrate selenium dioxide ester is at 2928cm
-1Near hydroxyl absorption peak decreases, and shows that part of hydroxyl is esterified, and visible polysaccharide has formed monohydrate selenium dioxide ester; In Fig. 4, by the infrared spectra comparative analysis of cynomorium songaricum polysaccharide and cynomorium songaricum polysaccharide monohydrate selenium dioxide ester, the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester has also increased 871.65cm except polysaccharide parent charateristic avsorption band keeps as can be seen
-1The absorption at place is the stretching vibration of Se=O in the monohydrate selenium dioxide ester, and this is the charateristic avsorption band of monohydrate selenium dioxide ester, proves absolutely that by UV spectrum and infrared spectra cynomorium songaricum polysaccharide has formed the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester.
Embodiment one
According to the embodiment of the invention, provide a kind of preparation method of polysaccharide monohydrate selenium dioxide ester.In the present embodiment, this polysaccharide is the lanzhou lily polysaccharide, and the preparation method of this lanzhou lily polysaccharide monohydrate selenium dioxide ester comprises:
Step 1: swelling treatment: it is in 0.3% salpeter solution that 1.0g lanzhou lily polysaccharide is added the 100ml volumetric concentration, at room temperature stirs and spends the night, and makes its abundant swelling, obtains lanzhou lily polysaccharide salpeter solution, places at room temperature standby;
Step 2: esterification: in the lanzhou lily polysaccharide salpeter solution that step 1 obtains, add the mixture 2.145g of Sodium Selenite and tin chloride, 60 ℃ stirred in water bath reactions after 6 hours, be cooled to room temperature, suction filtration under 0.07Mpa;
After using anhydrous sodium carbonate, the pH value of the filtrate behind the suction filtration being transferred to 5, carry out centrifugal treating one time, obtain supernatant liquor one time; Here, the mass ratio of Sodium Selenite and tin chloride is 1: 1.675;
Step 3: purifying: the supernatant liquor that step 2 is obtained, the interception of packing into is in 8000～12000 daltonian dialysis tubings, the flowing water dialysis is after 36 hours, carry out distill water dialysis, when redness disappeared when the liquid in dialysis tubing added xitix, stop distill water dialysis, and under 50 ℃, 0.07Mpa, the liquid in the dialysis tubing is evaporated to 1/20 of original volume;
Step 4: adding ethanol in the concentrated solution that step 3 obtains, make the alcoholic acid volume account for 75% of concentrated solution and total ethanol volume, at room temperature leave standstill and carried out alcohol precipitation in 20 hours, is that 15 ℃, 4000 rev/mins rotating speed carries out secondary centrifuging and handles with temperature afterwards;
Secondary centrifuging is handled the sinking obtain be deposited under-50 ℃, the condition of 1Pa lyophilize 36 hours, obtain the lanzhou lily polysaccharide monohydrate selenium dioxide ester of purifying.
To step 4, can make the lanzhou lily polysaccharide monohydrate selenium dioxide ester through above-mentioned steps 1, detect through ICP-AES and know that the selenium content in this lanzhou lily polysaccharide monohydrate selenium dioxide ester is 2508mg/kg.
In the present embodiment, flowing water dialysis refers to use tap water to dialyse, and water is mobile, needs constantly more renew water in other words in dialysis procedure; Distill water dialysis refers to use distilled water to dialyse.
Embodiment two
In the present embodiment, the preparation method of lanzhou lily polysaccharide monohydrate selenium dioxide ester comprises:
Step 1: swelling treatment: it is in 0.8% salpeter solution that 1.0g lanzhou lily polysaccharide is added the 100ml volumetric concentration, at room temperature stirs and spends the night, and makes its abundant swelling, obtains lanzhou lily polysaccharide salpeter solution, places at room temperature standby;
Step 2: esterification: in the lanzhou lily polysaccharide salpeter solution that step 1 obtains, add the mixture 2.748g of Sodium Selenite and tin chloride, 70 ℃ stirred in water bath reactions after 10 hours, be cooled to room temperature, suction filtration under 0.075Mpa;
After using anhydrous sodium carbonate, the pH value of the filtrate behind the suction filtration being transferred to 5.5, carry out centrifugal treating one time, obtain supernatant liquor one time; Here, the mass ratio of Sodium Selenite and tin chloride is 1: 2.146;
Step 3: purifying: the supernatant liquor that step 2 is obtained, the interception of packing into is in 8000～12000 daltonian dialysis tubings, the flowing water dialysis is after 44 hours, carry out distill water dialysis, when redness disappeared when the liquid in dialysis tubing added xitix, stop distill water dialysis, and under 55 ℃, 0.075Mpa, the liquid in the dialysis tubing is evaporated to 1/30 of original volume;
Step 4: adding ethanol in the concentrated solution that step 3 obtains, make the alcoholic acid volume account for 77.5% of concentrated solution and total ethanol volume, at room temperature leave standstill and carried out alcohol precipitation in 25 hours, is 18 ℃ with temperature afterwards, and 4200 rev/mins rotating speed carries out secondary centrifuging to be handled;
Secondary centrifuging is handled the sinking obtain be deposited under-55 ℃, the condition of 3Pa lyophilize 40 hours, obtain the lanzhou lily polysaccharide monohydrate selenium dioxide ester of purifying.
To step 4, can make the lanzhou lily polysaccharide monohydrate selenium dioxide ester through above-mentioned steps 1, detect through ICP-AES and know that the selenium content in this lanzhou lily polysaccharide monohydrate selenium dioxide ester is 5617mg/kg.
Embodiment three
In the present embodiment, the preparation method of lanzhou lily polysaccharide monohydrate selenium dioxide ester comprises:
Step 1: swelling treatment: it is in 0.5% salpeter solution that 1.0g lanzhou lily polysaccharide is added the 100ml volumetric concentration, at room temperature stirs and spends the night, and makes its abundant swelling, obtains lanzhou lily polysaccharide salpeter solution, places at room temperature standby;
Step 2: esterification: in the lanzhou lily polysaccharide salpeter solution that step 1 obtains, add the mixture 3.350g of Sodium Selenite and tin chloride, 80 ℃ stirred in water bath reactions after 14 hours, be cooled to room temperature, suction filtration under 0.08Mpa;
After using anhydrous sodium carbonate, the pH value of the filtrate behind the suction filtration being transferred to 6, carry out centrifugal treating one time, obtain supernatant liquor one time; Here, the mass ratio of Sodium Selenite and tin chloride is 1: 2.616;
Step 3: purifying: the supernatant liquor that step 2 is obtained, the interception of packing into is in 8000～12000 daltonian dialysis tubings, the flowing water dialysis is after 48 hours, carry out distill water dialysis, when redness disappeared when the liquid in dialysis tubing added xitix, stop distill water dialysis, and under 60 ℃, 0.08Mpa, the liquid in the dialysis tubing is evaporated to 1/40 of original volume;
Step 4: adding ethanol in the concentrated solution that step 3 obtains, make the alcoholic acid volume account for 80% of concentrated solution and total ethanol volume, at room temperature leave standstill and carried out alcohol precipitation in 30 hours, is 20 ℃ with temperature afterwards, and 4500 rev/mins rotating speed carries out secondary centrifuging to be handled;
Secondary centrifuging is handled the sinking obtain be deposited under-60 ℃, the condition of 5Pa lyophilize 48 hours, obtain the lanzhou lily polysaccharide monohydrate selenium dioxide ester of purifying.
To step 4, can make the lanzhou lily polysaccharide monohydrate selenium dioxide ester through above-mentioned steps 1, detect through ICP-AES and know that the selenium content in this lanzhou lily polysaccharide monohydrate selenium dioxide ester is 9431mg/kg.
Embodiment 4
In the present embodiment, provide a kind of preparation method of polysaccharide monohydrate selenium dioxide ester, this polysaccharide is a cynomorium songaricum polysaccharide, and the preparation method of this cynomorium songaricum polysaccharide comprises:
Step 1: swelling treatment: it is in 0.8% salpeter solution that the 1.0g cynomorium songaricum polysaccharide is added the 100ml volumetric concentration, at room temperature stirs and spends the night, and makes its abundant swelling, obtains the cynomorium songaricum polysaccharide salpeter solution, places at room temperature standby;
Step 2: esterification: in the cynomorium songaricum polysaccharide salpeter solution that step 1 obtains, add the mixture 2.145g of Sodium Selenite and tin chloride, 60 ℃ stirred in water bath reactions after 14 hours, be cooled to room temperature, suction filtration under 0.07Mpa;
After using anhydrous sodium carbonate, the pH value of the filtrate behind the suction filtration being transferred to 5, carry out centrifugal treating one time, obtain supernatant liquor one time; Here, the mass ratio of Sodium Selenite and tin chloride is 1: 1.675;
Step 3: purifying: the supernatant liquor that step 2 is obtained, the interception of packing into is in 8000～12000 daltonian dialysis tubings, the flowing water dialysis is after 36 hours, carry out distill water dialysis, when redness disappeared when the liquid in dialysis tubing added xitix, stop distill water dialysis, and under 50 ℃, 0.07Mpa, the liquid in the dialysis tubing is evaporated to 1/20 of original volume;
Step 4: adding ethanol in the concentrated solution that step 3 obtains, make the alcoholic acid volume account for 75% of concentrated solution and total ethanol volume, at room temperature leave standstill and carried out alcohol precipitation in 20 hours, is 15 ℃ with temperature afterwards, and 4000 rev/mins rotating speed carries out secondary centrifuging to be handled;
Secondary centrifuging is handled the sinking obtain be deposited under-50 ℃, the condition of 2Pa lyophilize 36 hours, obtain the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester of purifying.
To step 4, can make the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester through above-mentioned steps 1, detect through ICP-AES and know that the selenium content in this cynomorium songaricum polysaccharide monohydrate selenium dioxide ester is 2678mg/kg.
Embodiment 5
In the present embodiment, the preparation method of cynomorium songaricum polysaccharide monohydrate selenium dioxide ester comprises:
Step 1: swelling treatment: it is in 0.5% salpeter solution that the 1.0g cynomorium songaricum polysaccharide is added the 100ml volumetric concentration, at room temperature stirs and spends the night, and makes its abundant swelling, obtains the cynomorium songaricum polysaccharide salpeter solution, places at room temperature standby;
Step 2: esterification: in the cynomorium songaricum polysaccharide salpeter solution that step 1 obtains, add the mixture 2.748g of Sodium Selenite and tin chloride, 70 ℃ stirred in water bath reactions after 10 hours, be cooled to room temperature, suction filtration under 0.075Mpa;
After using anhydrous sodium carbonate, the pH value of the filtrate behind the suction filtration being transferred to 5.5, carry out centrifugal treating one time, obtain supernatant liquor one time; Here, the mass ratio of Sodium Selenite and tin chloride is 1: 2.146;
Step 3: purifying: the supernatant liquor that step 2 is obtained, the interception of packing into is in 8000～12000 daltonian dialysis tubings, the flowing water dialysis is after 44 hours, carry out distill water dialysis, when redness disappeared when the liquid in dialysis tubing added xitix, stop distill water dialysis, and under 55 ℃, 0.075Mpa, the liquid in the dialysis tubing is evaporated to 1/30 of original volume;
Step 4: adding ethanol in the concentrated solution that step 3 obtains, make the alcoholic acid volume account for 77.5% of concentrated solution and total ethanol volume, at room temperature leave standstill and carried out alcohol precipitation in 25 hours, is 18 ℃ with temperature afterwards, and 4200 rev/mins rotating speed carries out secondary centrifuging to be handled;
Secondary centrifuging is handled the sinking obtain be deposited under-55 ℃, the condition of 4Pa lyophilize 40 hours, obtain the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester of purifying.
To step 4, can make the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester through above-mentioned steps 1, detect through ICP-AES and know that the selenium content in this cynomorium songaricum polysaccharide monohydrate selenium dioxide ester is 3761mg/kg.
Embodiment 6
In the present embodiment, the preparation method of cynomorium songaricum polysaccharide monohydrate selenium dioxide ester comprises:
Step 1: swelling treatment: it is in 0.3% salpeter solution that the 1.0g cynomorium songaricum polysaccharide is added the 100ml volumetric concentration, at room temperature stirs and spends the night, and makes its abundant swelling, obtains the cynomorium songaricum polysaccharide salpeter solution, places at room temperature standby;
Step 2: esterification: in the cynomorium songaricum polysaccharide salpeter solution that step 1 obtains, add the mixture 3.350g of Sodium Selenite and tin chloride, 60 ℃ stirred in water bath reactions after 6 hours, be cooled to room temperature, suction filtration under 0.08Mpa;
After using anhydrous sodium carbonate, the pH value of the filtrate behind the suction filtration being transferred to 6, carry out centrifugal treating one time, obtain supernatant liquor one time; Here, the mass ratio of Sodium Selenite and tin chloride is 1: 2.616;
Step 3: purifying: the supernatant liquor that step 2 is obtained, the interception of packing into is in 8000～12000 daltonian dialysis tubings, the flowing water dialysis is after 48 hours, carry out distill water dialysis, when redness disappeared when the liquid in dialysis tubing added xitix, stop distill water dialysis, and under 60 ℃, 0.08Mpa, the liquid in the dialysis tubing is evaporated to 1/40 of original volume;
Step 4: adding ethanol in the concentrated solution that step 3 obtains, make the alcoholic acid volume account for 75% of concentrated solution and total ethanol volume, at room temperature leave standstill and carried out alcohol precipitation in 20 hours, is 20 ℃ with temperature afterwards, and 4500 rev/mins rotating speed carries out secondary centrifuging to be handled;
Secondary centrifuging is handled the sinking obtain be deposited under-60 ℃, the condition of 5Pa lyophilize 48 hours, obtain the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester of purifying.
To step 4, can make the cynomorium songaricum polysaccharide monohydrate selenium dioxide ester through above-mentioned steps 1, detect through ICP-AES and know that the selenium content in this cynomorium songaricum polysaccharide monohydrate selenium dioxide ester is 7859mg/kg.
The various embodiments described above of the present invention are raw material with lanzhou lily polysaccharide or cynomorium songaricum polysaccharide, utilize nitric acid-tin chloride method, prepare the natural plant polyose monohydrate selenium dioxide ester efficiently, fast; Concrete, with natural plant polyose lanzhou lily or cynomorium songaricum polysaccharide is raw material, under the katalysis of nitric acid～tin chloride, utilize Sodium Selenite that lanzhou lily polysaccharide or cynomorium songaricum polysaccharide are carried out molecular modification first, synthesized lanzhou lily polysaccharide monohydrate selenium dioxide ester or cynomorium songaricum polysaccharide monohydrate selenium dioxide ester.Reaction conditions is controlled, and repeatability is high, and solvability is good, and market outlook are good; Introduce selenite radical in molecular structure, wherein selenium is positive tetravalence, and selenium is the valence state that mediates, and both can oxidizedly also can be reduced, and therefore polysaccharide monohydrate selenium dioxide ester of the present invention has the potential biological activity in human body.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a polysaccharide monohydrate selenium dioxide ester is characterized in that, comprises the steps:
A, press polysaccharide weight: the proportion relation of nitric acid volume=1g: 100ml, described polysaccharide and corresponding salpeter solution are mixed, at room temperature stir, make described polysaccharide swelling, obtain the polysaccharide salpeter solution;
B, in described polysaccharide salpeter solution, add Sodium Selenite and tin chloride, be 60～80 ℃ stirred in water bath in temperature, after the esterification 6～14 hours, be cooled to room temperature, when pressure is 0.07～0.08Mpa, carry out suction filtration and handle and a centrifugal treating, obtain supernatant liquor one time;
C, a described supernatant liquor is packed in the dialysis tubing, carry out successively being evaporated to 1/40～1/20 of original volume after flowing water dialysis treatment and distill water dialysis handle, obtain concentrated solution;
D, described concentrated solution carried out alcohol precipitation is handled and secondary centrifuging is handled, obtain precipitation; Again described precipitation is carried out lyophilize and handle, obtain described polysaccharide monohydrate selenium dioxide ester.
2. the preparation method of polysaccharide monohydrate selenium dioxide ester according to claim 1 is characterized in that, described polysaccharide is the lanzhou lily polysaccharide.
3. the preparation method of polysaccharide monohydrate selenium dioxide ester according to claim 1 is characterized in that, described polysaccharide is a cynomorium songaricum polysaccharide.
4. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that in step a, the volumetric concentration of described salpeter solution is 0.3～0.8%.
5. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that, in step b, between a described suction filtration processing and a described centrifugal treating, further comprising the steps of: use anhydrous sodium carbonate, the pH value of described suction filtration being handled gained filtrate transfers to 5～6.
6. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that in step b, the weight ratio of described Sodium Selenite and described tin chloride is 1: 1.675～3.35.
7. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that in step c, when the redness of liquid disappeared when add xitix, described dialysis tubing in described dialysis tubing in, described distill water dialysis was finished dealing with.
8. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that in step c, the time of described flowing water dialysis treatment is 36～48 hours;
The temperature that described concentrating under reduced pressure is handled is that 50～60 ℃, pressure conditions are 0.07～0.08Mpa;
The molecular weight cut-off of described dialysis tubing is 8000～12000 dalton.
9. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that in steps d, described alcohol precipitation is handled and specifically comprised:
In described concentrated solution, add ethanol, at room temperature left standstill 20～30 hours; Wherein, described alcoholic acid volume accounts for 75～80% of described concentrated solution and described total ethanol volume.
10. according to the preparation method of each described polysaccharide monohydrate selenium dioxide ester among the claim 1-3, it is characterized in that, in step b and d, the described temperature of once handling with secondary centrifuging is that 15～20 ℃, rotating speed are 4000～4500 rev/mins, and the temperature that described lyophilize is handled is that-60 ℃～-50 ℃, pressure are that 1-5Pa, time are 36～48 hours.
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