CN107573437B - Method for synthesizing selenized polysaccharide by solid acid catalysis - Google Patents
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Abstract
The invention discloses a method for synthesizing selenized polysaccharide by solid acid catalysis, which belongs to the technical field of biological macromolecules, wherein artemisia sphaerocephala polysaccharide is used as a raw material, ZnO which is a solid acid is used as a catalyst to catalyze and synthesize the selenized artemisia sphaerocephala polysaccharide, the selenized artemisia sphaerocephala polysaccharide is synthesized under mild conditions, and the selenium content in the selenized artemisia sphaerocephala polysaccharide reaches 15012 ~ 21745 mu g/g.
Description
Technical Field
The invention belongs to the technical field of biological macromolecules, and relates to a method for efficiently synthesizing selenized polysaccharide under the catalysis condition of solid acid (ZnO).
Background
Selenium (Se), as a necessary trace element of life, plays an extremely important role in improving immunity of organisms, resisting cancer, resisting oxidation, treating keshan disease and the like, and is known as 'vital fire' and 'king of cancer'. Selenium exists in nature in two forms, inorganic selenium and organic selenium. Inorganic selenium has the advantages of high selenium content, low price and the like, but has accumulative toxic and side effects and mutagenic effect. Compared with inorganic selenium, the organic selenium has obvious advantages in the aspects of application safety, biological activity, immune reaction activation and the like. Common organic selenium mainly comprises selenium-containing amino acid, selenoprotein and selenium polysaccharide. Selenium polysaccharide plays a very important role in the selection of selenium supplement, and has become a research hotspot in the field of biomacromolecules.
The method for preparing selenium polysaccharide mainly comprises biological conversion and chemical synthesis of selenium polysaccharide, generally, biological conversion comprises selenium-rich culture and extraction of selenium polysaccharide from natural products, for example, patent CN101525646B discloses a cultivation method for extracting selenium-rich from Pholiota adiposa hyphae and an extraction process of Pholiota adiposa polysaccharide, wherein the content of selenium polysaccharide obtained by hot water leaching is 2120ppm, patent CN106749719A discloses a preparation method of selenium polysaccharide from selenium-rich Grifola frondosa, wherein the content and bioactivity of selenium polysaccharide obtained by hot water leaching are lower, so that research and application of selenium polysaccharide are limited, at present, the selenium polysaccharide is prepared by adopting a chemical synthesis method, which belongs to esterification reaction, the catalyst is a key factor influencing difficult degree and high yield of reaction, and is a toxic reaction method for preparing selenium polysaccharide, such as a method for catalyzing sodium selenite with acetic acid, selenium polysaccharide, wherein the chemical synthesis reaction of selenium polysaccharide belongs to esterification reaction, the reaction is a toxic reaction method for influencing the reaction, such as high difficulty and low yield, wherein the toxic reaction method for preparing selenium polysaccharide is carried out under the conditions of 3520 g, the same as a toxic reaction for catalyzing sodium selenious acid sodium selenite with selenite, selenium acetate, selenium polysaccharide prepared by a selenylation reaction, a selenylation reaction method for preparing selenium polysaccharide, a selenylation reaction method for example, a selenylation polysaccharide prepared by adopting a selenylation reaction method for preparing selenium chloride medium for 3570, a selenylation reaction method for preparing selenium chloride medium, a toxic reaction method for preparing selenium polysaccharide, a toxic reaction method for a selenylation reaction method for preparing selenium polysaccharide, a toxic reaction for a selenylation reaction method for a toxic reaction for preparing polysaccharide, a toxic reaction for a selenylation reaction for a toxic reaction for a selenylation reaction for preparing selenium-containing no more than a selenylation reaction for a selenylation reaction, a selenylation reaction for a selenylation reaction, a selenylation reaction for a selenylation reaction, a selenylation reaction for a selenylation.
The solid acid catalyst is used as a heterogeneous catalyst in the esterification reaction, overcomes the defects that the traditional liquid acid catalyst is not easy to separate, corrodes equipment, uses toxic solvents and the like, and is a green and environment-friendly catalyst. Patent CN104841419A discloses a MoO3/ZnO/TiO2Method for preparing solid acid, exemplified by esterification of ethanol and acetic acid, MoO3/ZnO/TiO2The conversion rate of the esterification reaction of the catalyst reaches 90 percent; zhang Yongli et al composite solid super acidic SO4 2-/Fe2O3 /ZnO/ZrO2The catalyst is used for esterification reaction of isoamyl alcohol and glacial acetic acid to synthesize isoamyl acetate, and the esterification rate can reach 85.1 percent (applied to chemical engineering, 2012, 8, 1380-1383) after the reaction is carried out at 120 ℃ for 50 min; patent CN102259008B discloses a solid super strong catalyst S2O8 2-The preparation method of ZrO is applied to synthesizing butyl acetate and butyl oleate, the highest acetic acid conversion rate can reach 99.5%, and the highest oleic acid conversion rate can reach 98.8%.
Disclosure of Invention
In view of the above, the present invention aims at providing a method for catalytically synthesizing selenium polysaccharide by using artemisia sphaerocephala polysaccharide as a raw material and using solid acid ZnO as a catalyst. Through search, domestic and foreign documents and patents do not relate to a method for synthesizing selenylation artemisia sphaerocephala polysaccharide by taking solid acid (ZnO) as a catalyst.
The purpose of the invention can be realized by the following technical scheme:
a method for synthesizing selenized polysaccharide under the catalysis of solid acid comprises the following steps:
1. preparing a artemisia sphaerocephala polysaccharide formamide solution:
stirring Artemisia sphaerocephala Krasch polysaccharide at ~ 90 deg.C and 400 ~ 600rpm for 3 ~ 6h, and dissolving in anhydrous formamide to obtain formamide solution of Artemisia sphaerocephala Krasch polysaccharide.
Wherein the weight average molecular weight of Artemisia sphaerocephala Krasch polysaccharide is 6.963 × 104 Da, the total sugar content is 89.7%, and the mass-volume ratio of the artemisia sphaerocephala polysaccharide to the formamide is 3 ~ 5 mg/mL.
2. Preparation of solid acid catalyst ZnO
Reacting NH3•H2O was added dropwise to ZnCl under continuous stirring at a rate of 60 ~ 80 drops/min2Adding the solution to pH7.0, stirring at 800 ~ 1200rpm for 2 ~ 3h, standing at room temperature for 2 ~ 4h, vacuum filtering, and washing the filter cake with deionized water until no Cl is detected-And drying the filter cake after decompression and suction filtration again, fully grinding, sieving by a 100-mesh sieve, and roasting at 400 ~ 550 and 550 ℃ for 2 ~ 4h to obtain the powdery ZnO solid acid catalyst, wherein the particle size of the catalyst is less than 150 mu m.
Wherein NH3•H2The mass fraction of O is10 ~ 25 percent, ZnCl2Has a concentration of 0.8 ~ 1.2.2 mol/L, NH3•H2O and ZnCl2The molar ratio of (1) to (2), the vacuum of 0.06 ~ 0.08.08 MPa, the drying temperature of 90 ~ 110 ℃ and the drying time of 9 ~ 12 h.
3. Synthesis of selenylation artemisia sphaerocephala polysaccharide
Adding selenious acid and ZnO into formamide rapidly at 60 deg.C of ~ 80 deg.C and N2Reacting for 1 ~ 2h under protection, adding formamide solution of Artemisia sphaerocephala polysaccharide into the above mixture under air isolation at 40 ~ 60 drops/min, and heating at 60 deg.C ~ 80 deg.C and N2Protecting, stirring at 600 ~ rpm for 2 ~ h, filtering with 0.45 μm organic microporous membrane under reduced pressure after reaction, repeatedly washing the filtrate with acetone, detecting the supernatant with ascorbic acid to make it not appear red, placing the washed precipitate into dialysis bag, with cut-off molecular weight of 8000 ~ 14000Da, dialyzing with running water for 24 ~ h, dialyzing with deionized water for 12 ~ h, concentrating the content of dialysis bag at 55 ~ deg.C and 0.06 ~.08 MPa to original value1/25 ~ 1/35, adding acetone into the concentrated solution, wherein the acetone content accounts for 75 ~ 85% of the total volume, performing vacuum filtration under 0.06 ~ 0.08.08 MPa, and freeze-drying the obtained filter cake at-70 ~ -55 deg.C under 3 ~ 10Pa for 24 ~ 60h to obtain selenized artemisia sphaerocephala polysaccharide.
The mass ratio of the selenious acid to the ZnO is 10:1 ~ 20: 20, the mass-volume ratio of the selenious acid to the formamide is 35 ~ 50 mg/mL, and the molar ratio of the artemisia sphaerocephala polysaccharide to the selenious acid is 1: 3.
Test and characterization of selenylation artemisia sphaerocephala polysaccharide
The invention adopts a fluorescence photometry, Fourier transform infrared spectroscopy analysis, X-ray photoelectron spectroscopy (XPS) and molecular weight measurement to analyze the structural characteristics of the prepared selenated artemisia sphaerocephala polysaccharide, and the description is as follows:
1. and (3) determination of selenium content: measuring the selenium content of the sample by fluorescence photometry
Weighing dried selenized Artemisia sphaerocephala Krasch polysaccharide sample to be tested, and adding mixed acid (HNO)3:H2SO4:HClO4=1:1: 4), standing overnight, digesting for 2 ~ 3 hours at 135 ℃, diluting the digestion solution with distilled water to constant volume, taking 8mL, adding 0.2 mol/L EDTA-2Na solution and 4 ~ 6mL of 0.5 mol/L hydroxylamine hydrochloride respectively, standing for 10 ~ 15min after uniform oscillation, adding 4 ~ 6mL of 0.1% 2, 3-diaminonaphthalene solution in a dark place, boiling in a water bath for 5 ~ 8min, taking out, cooling to room temperature, adding 6mL of cyclohexane, fully oscillating and extracting, taking a cyclohexane layer, measuring a fluorescence value (excitation wavelength 376 nm and emission wavelength 520 nm) in a fluorescence spectrophotometer, and calculating the selenium content by using a working curve method.
2. Analysis of infrared spectrogram
The fully dried sample was tableted with KBr and analyzed by Thermo Nicolet is10 Infrared Spectroscopy at 400 ~ 4000 cm-1Scanning within the range, the scanning times are 16 times, and the resolution is 4 cm-1。
FIG. 1 is an infrared spectrum of Artemisia sphaerocephala polysaccharide and selenated Artemisia sphaerocephala polysaccharide prepared by the invention. The infrared spectrum of the artemisia sphaerocephala polysaccharide in the figure shows that the artemisia sphaerocephala polysaccharide has the characteristic peaks of the polysaccharide: 3400 cm-1The left and right extremely wide and strong absorption peaks are O-H stretching vibration of polysaccharide hydroxyl, and are 2930cm-1Is represented by C-telescopic vibration of H-bond. Compared with the infrared spectrum of the artemisia sphaerocephala selengensis polysaccharide, the artemisia sphaerocephala selengensis polysaccharide has characteristic absorption peaks of the polysaccharide and is 1080cm-1At a sum of 708 cm-1New absorption peaks appear at the positions, namely stretching vibration of Se = O and bending vibration of C-O-Se respectively, which indicates that part-OH in the artemisia sphaerocephala polysaccharide structure is replaced by selenious acid groups to generate a selenization reaction.
3. X-ray photoelectron spectroscopy (X-ray photoelectron spectrometry)
XPS (PHI-5702, USA) selects MgKa line as excitation source, the passing energy is 29.35eV, and the pressure of sample chamber is 2.67X 10-7Pa, voltage 15KV, power 200W, and binding energy test accuracy of 0.3 eV.
FIG. 2 is XPS spectra of Artemisia sphaerocephala Krasch polysaccharide and Artemisia sphaerocephala Krasch polysaccharide selenide. As can be seen from fig. 2: the artemisia selengensis polysaccharide Se 3d spectrum has no peak, while the artemisia selengensis polysaccharide Se 3d combination energy peak in 58.7eV, and Se has valence state of Se4+The selenylation reaction of the artemisia sphaerocephala polysaccharide is shown, and the selenium in the selenylation artemisia sphaerocephala polysaccharide appears in the form of selenite.
4. Determination of molecular weight
The absolute molecular weight of the sample is determined by using a size exclusion chromatography-light scattering combined instrument. The multi-angle laser light scattering instrument (MALLS; DAWN EOS, Wyatt Technology Co., USA) wavelength was 690 nm. Chromatographic column (Ultrahydrogel)TMcolumn, Waters, USA) specification 7.8 mm by 300 mm.
The sample is prepared into the required concentration by ultrapure water, the dissolved sample is filtered by a 0.22 mu m microporous filter membrane to remove the undissolved sample, the sample feeding amount is 50 mu L, the flow rate is 0.5 mL/min, the temperature of a chromatographic column is 30 ℃, and the ultrapure water is used as a mobile phase. Measuring the molecular weight of the selenylated artemisia sphaerocephala polysaccharide at 6.687 x 104 Da~4.017×104 Da range.
The invention has the advantages and beneficial effects that:
1. according to the invention, the artemisia sphaerocephala polysaccharide is used as a raw material, the selenious acid is catalyzed by the solid acid to synthesize the selenylated artemisia sphaerocephala polysaccharide, the solid acid does not corrode equipment, a toxic selenium-containing intermediate is not required to be used, no pollutant is discharged, the time required by the reaction is effectively shortened, and the synthetic reaction can be carried out under mild conditions;
2. the selenium content of the selenized artemisia sphaerocephala polysaccharide prepared by the method can be adjusted and optimized through reaction conditions, so that the selenium content in the synthesized selenized artemisia sphaerocephala polysaccharide is improved, and the selenium content in the selenized artemisia sphaerocephala polysaccharide reaches 15012 ~ 21745 mu g/g;
3. compared with the prior art, the invention does not need special equipment, is simple and controllable, has low cost and is suitable for popularization and application.
Drawings
FIG. 1 is an infrared spectrum of Artemisia sphaerocephala Krasch polysaccharide and its selenized Artemisia sphaerocephala Krasch polysaccharide.
FIG. 2 is X-ray photoelectron spectroscopy (XPS) chart of Artemisia sphaerocephala Krasch polysaccharide and Artemisia sphaerocephala Krasch polysaccharide selenide.
Detailed Description
The preparation method for synthesizing selenylation artemisia sphaerocephala polysaccharide by catalyzing solid acid ZnO in the invention is further explained by the following specific examples:
example 1
(1) Preparing a artemisia sphaerocephala polysaccharide formamide solution: 300mg of artemisia sphaerocephala polysaccharide is stirred and reacted for 3 hours at 80 ℃ and the rotating speed of 500rpm to dissolve the artemisia sphaerocephala polysaccharide in 60mL of formamide, so that formamide solution of the artemisia sphaerocephala polysaccharide is obtained. Wherein the weight average molecular weight of Artemisia sphaerocephala Krasch polysaccharide is 6.903 × 104Da, total sugar content 89.7%.
(2) Preparation of solid acid catalyst ZnO: mixing NH with the mass fraction of 10%3•H2O is added dropwise at a rate of 70 drops/min to 60mL of 1.2 mol/L ZnCl with continuous stirring2Stirring the solution for 3h at the rotation speed of 800rpm until the pH value of the solution is 7.0 serving as a titration end point, standing the solution for 4h at room temperature, performing vacuum filtration at 0.07 MPa, and continuously washing the obtained filter cake with deionized water until no Cl is detected-And reducing the pressure to 0.07 MPa again, drying the filter cake after suction filtration at 100 ℃ for 10h, fully grinding and sieving the solid to 100 meshes after the solid is cooled to room temperature, and roasting the solid at 500 ℃ for 4h to obtain powdery solid acid catalyst ZnO, wherein the particle size of the catalyst is less than 150 mu m. .
(3) Selenylation artemisia sphaerocephala (Schw.) wolfAnd (3) sugar synthesis: 0.645g selenious acid and 0.033g ZnO were quickly added to 15mL anhydrous formamide over N2Stirring at 70 ℃ and 700 rpm for 1h under protection. Adding 60mL of formamide solution of Artemisia sphaerocephala polysaccharide obtained in (1) into the mixed solution at a speed of 50 drops/min under the condition of air isolation, and adding N at 70 deg.C2Stirring and reacting for 4 hours under the protection condition, quickly filtering by using an organic microporous filter membrane with the diameter of 0.45 mu m under reduced pressure after the reaction is finished, repeatedly washing the obtained filtrate by using acetone, detecting the supernatant by using ascorbic acid to ensure that the supernatant does not show red, filling the washed precipitate into a dialysis bag, dialyzing the dialysis bag by using running water for 36 hours, dialyzing the dialysis bag by using deionized water for 24 hours, concentrating the content in the dialysis bag under the reduced pressure of 55 ℃ and 0.07 MPa to 1/35 with the original volume, adding acetone into the concentrated solution, wherein the content of the acetone accounts for 75 percent of the total volume, then carrying out suction filtration under the reduced pressure of 0.07 MPa, freezing and drying the obtained filter cake at-65 ℃ and 10Pa for 48 hours to obtain the selenylation artemisia sphaerocephala polysaccharide, wherein the weight average artemisia sphaerocephala powder is dark red amorphous powder, the content of selenium is 16090 mu g/g, and the molecular weight is 6.6874 Da。
Example 2
(1) Preparing a artemisia sphaerocephala polysaccharide formamide solution: stirring 200mg of artemisia sphaerocephala polysaccharide at 60 ℃ and rotating at 400rpm for reacting for 4h to dissolve the artemisia sphaerocephala polysaccharide in 50ml of formamide to obtain formamide solution of the artemisia sphaerocephala polysaccharide.
(2) Preparation of solid acid catalyst ZnO: mixing NH with the mass fraction of 25%3•H2O was added dropwise at a rate of 80 drops/min to 60mL of 0.8 mol/LZnCl while stirring2Stirring the solution for 2.5h at 900rpm until pH7.0 is the titration end point, standing the solution for 3h at room temperature, performing vacuum filtration under 0.06 MPa, and continuously washing the obtained filter cake with deionized water until no Cl is detected-And reducing the pressure to 0.06 MPa again, drying the filter cake after suction filtration at 90 ℃ for 12h, fully grinding and sieving the solid to 100 meshes after the solid is cooled to room temperature, and roasting the solid at 400 ℃ for 3h to obtain powdery solid acid catalyst ZnO, wherein the particle size of the catalyst is less than 150 mu m.
(3) Synthesis of selenylation artemisia sphaerocephala polysaccharide: 0.430g selenious acid and 0.029g ZnO were quickly added to 18mL anhydrous formamide in N2Stirring at 80 ℃ and 600rpm for 2h under protection. Dripping 50mL formamide solution of Artemisia sphaerocephala polysaccharide obtained in (1) into the above mixed solution at 40 drops/min under air isolation, and heating at 80 deg.C and N2Stirring and reacting for 2h under the protection condition, quickly filtering with an organic microporous filter membrane of 0.45 mu m under reduced pressure after the reaction is finished, repeatedly washing the obtained filtrate with acetone, detecting the supernatant with ascorbic acid to make the supernatant not to appear red, filling the washed precipitate into a dialysis bag, dialyzing with running water for 24h and deionized water for 36h, concentrating the content in the dialysis bag under reduced pressure at 60 ℃ and 0.06 MPa to 1/25 of the original volume, adding acetone (the content of the acetone accounts for 80 percent of the total volume) into the concentrated solution, filtering under reduced pressure at 0.06 MPa, freeze-drying the obtained filter cake at-70 ℃ and 7 Pa for 60h to obtain selenylation artemisia sphaerocephala polysaccharide, wherein the selenylation artemisia sphaerocephala polysaccharide is dark red amorphous powder, the content of selenium is 21745 mu g/g, and the molecular weight is 4.984 multiplied by 104Da。
Example 3
(1) Preparing a artemisia sphaerocephala polysaccharide formamide solution: 210mg of artemisia sphaerocephala polysaccharide is stirred and reacted for 6 hours at the temperature of 90 ℃ and the rotating speed of 600rpm to dissolve the artemisia sphaerocephala polysaccharide in 70ml of formamide, so that formamide solution of the artemisia sphaerocephala polysaccharide is obtained.
(2) Preparation of solid acid catalyst ZnO: mixing 15% of NH3•H2O is added dropwise into 60mL of 1mol/L ZnCl under continuous stirring at the speed of 60 drops/min2Stirring the solution for 2h at the rotation speed of 1200rpm until the pH value of the solution is 7.0 serving as a titration end point, standing the solution for 2h at room temperature, performing vacuum filtration at 0.08MPa, and continuously washing the obtained filter cake with deionized water until no Cl is detected-And reducing the pressure to 0.08MPa again, drying the filter cake after suction filtration at 110 ℃ for 9h, fully grinding and sieving the solid to 100 meshes after the solid is cooled to room temperature, and roasting the solid at 550 ℃ for 2h to obtain powdery solid acid catalyst ZnO, wherein the particle size of the catalyst is less than 150 mu m.
(3) Synthesis of selenylation artemisia sphaerocephala polysaccharide: 0.452g selenious acid and 0.045g ZnO were quickly added to 20mL anhydrous formamide, at 80 deg.C and N2Stirring for 1.5h under protection. 70ml of formamide solution of artemisia sphaerocephala polysaccharide obtained in the step (1) is addedAdding dropwise into the above mixed solution at a speed of 60 drops/min under air-tight condition, and adding N2Stirring for 3h at the rotation speed of 800rpm at 60 ℃ under protection, quickly filtering the solution with an organic microporous filter membrane of 0.45 mu m under reduced pressure after the reaction is finished, repeatedly washing the obtained filtrate with acetone, detecting the supernatant with ascorbic acid to ensure that the supernatant does not show red color, filling the washed precipitate into a dialysis bag, carrying out dialysis with a cut-off molecular weight of 8000 ~ 14000Da on the dialysis bag, carrying out dialysis with running water for 72h, carrying out dialysis with deionized water for 12h, carrying out reduced pressure concentration on the content in the dialysis bag at 65 ℃ and 0.08MPa to 1/30 of the original volume, adding acetone into the concentrated solution, wherein the acetone content accounts for 85 percent of the total volume, carrying out reduced pressure suction filtration at 0.08MPa, and carrying out freeze drying on the obtained filter cake at-60 ℃ and 7 Pa for 72h to obtain the selenylation artemisia polysaccharide, wherein the selenylation artemisia anomala is dark red amorphous powder, the selenium4Da。
Comparative example 1
(1) Preparing a artemisia sphaerocephala polysaccharide formamide solution: 300mg of artemisia sphaerocephala polysaccharide is stirred and reacted for 6 hours at the temperature of 90 ℃ and the rotating speed of 600rpm to dissolve the artemisia sphaerocephala polysaccharide in 70ml of formamide, so that formamide solution of the artemisia sphaerocephala polysaccharide is obtained.
(2) Synthesis of selenylation artemisia sphaerocephala polysaccharide: 0.429g selenious acid was quickly added to 20mL anhydrous formamide, at 80 ℃ and N2Stirring for 1.5h under protection. Dripping 70mL of formamide solution of artemisia sphaerocephala polysaccharide obtained in the step (1) into the solution at the speed of 60 drops/min under the condition of air isolation, and carrying out N2Protecting, stirring at 60 ℃ and 800rpm for 3h, repeatedly washing with acetone after the reaction is finished, detecting the supernatant with ascorbic acid to be not red, filling the washed precipitate into a dialysis bag (the cut-off molecular weight is 8000 ~ 14000 Da), dialyzing with running water for 72h, dialyzing with deionized water for 12h, concentrating the content in the dialysis bag at 65 ℃ and 0.08MPa under reduced pressure to 1/30 of the original volume, adding acetone (the acetone content accounts for 85 percent of the total volume) into the concentrated solution, filtering under reduced pressure at 0.08MPa, freeze-drying the obtained filter cake at-60 ℃ for 60h to obtain selenized artemisia sphaerocephala polysaccharide, wherein the selenium content of the selenized artemisia sphaeroa polysaccharide is 5040 mu g/g, and the weight-average molecular weight is 4.461 multiplied by 10, and the filter cake is freeze-dried at-60 ℃ for 60h to4Da。
The difference between the parameters of the comparative example 1 and the parameters of the examples 1 to 3 is that the selenium content of the selenylation artemisia sphaerocephala polysaccharide obtained in the comparative example 1 is 5040 mu g/g without adopting a catalyst, while the selenium content of the selenylation artemisia sphaerocephala polysaccharide obtained in the examples 1 to 3 is 15012 ~ 21745 by adopting solid acid ZnO as a catalyst, the selenous acid is used as a medium-strong acid, weak esterification reaction can be carried out without the catalyst, and the selenylation artemisia sphaerocephala polysaccharide can also be obtained, but the selenium content of the obtained selenylation polysaccharide is lower.
Claims (7)
1. A method for synthesizing selenized polysaccharide by solid acid catalysis comprises the following process steps:
a. preparing formamide solution of Artemisia sphaerocephala Krasch polysaccharide, dissolving Artemisia sphaerocephala Krasch polysaccharide in anhydrous formamide at 60 deg.C of ~ 90 deg.C and 400 ~ 600rpm under stirring for 3 ~ 6h to obtain formamide solution of Artemisia sphaerocephala Krasch polysaccharide;
b. preparation of solid acid ZnO: reacting NH3•H2O was added dropwise to ZnCl under continuous stirring at a rate of 60 ~ 80 drops/min2Adding the solution to pH7.0, stirring at 800 ~ 1200rpm for 2 ~ 3h, standing at room temperature for 2 ~ 4h, vacuum filtering, and washing the filter cake with deionized water until no Cl is detected-Drying the filter cake obtained after decompression and suction filtration at 90 ~ 110 ℃ for 9 ~ 12h, fully grinding, sieving with a 100-mesh sieve, and roasting at 400 ~ 550 ℃ for 2 ~ 4h to obtain a powdery ZnO solid acid catalyst, wherein the particle size of the catalyst is less than 150 mu m;
c. and (c) synthesizing selenylated artemisia selengensis polysaccharide, namely rapidly adding selenious acid and ZnO obtained in the step (b) into a proper amount of formamide, and carrying out reaction at the temperature of 60 ℃ of ~ 80 ℃ and at the temperature of N2Stirring under protection for 1 ~ 2h, adding dropwise formamide solution of Artemisia sphaerocephala polysaccharide obtained in step a into the above mixture at 40 ~ 60 drops/min under air-proof condition with dropping funnel, and stirring at 60 deg.C ~ 80 deg.C and N2Stirring to react for 2 ~ 4h under the protection condition, and quickly using the mixture after the reaction is finishedFiltering with 0.45 μm organic microporous membrane under reduced pressure, repeatedly washing the filtrate with acetone, detecting the supernatant with ascorbic acid to show no red color, loading the washed precipitate into dialysis bag, dialyzing with flowing water for 24 ~ h, dialyzing with deionized water for 12 ~ 36h, concentrating the content in the dialysis bag under reduced pressure to 1/25 ~ 1/35 of original volume, adding acetone into the concentrated solution, wherein the acetone content accounts for 75 ~% of the total volume, vacuum filtering under 0.06 ~.08 MPa, freeze drying the obtained filter cake at-70 ~ -65 deg.C and 3 ~ Pa for 48 ~ h to obtain selenylated Artemisia sphaerocephala polysaccharide.
2. The method for the solid acid catalyzed synthesis of selenized polysaccharide of claim 1, wherein: in the step (a), the weight average molecular weight of the artemisia sphaerocephala polysaccharide is 6.903 multiplied by 104Da, total sugar content 89.7%.
3. The method for synthesizing selenized polysaccharide through solid acid catalysis as claimed in claim 1, wherein in step (a), the mass-to-volume ratio of artemisia sphaerocephala polysaccharide to formamide is 3 ~ 5 mg/mL.
4. The method for the solid acid catalyzed synthesis of selenized polysaccharide of claim 1, wherein: in the step (b), the step (c),
NH3•H2the mass fraction of O was 10 ~ 25%.
5. The method for the solid acid catalyzed synthesis of selenized polysaccharide of claim 1, wherein: in step (b), ZnCl2Has a concentration of 0.8 ~ 1.2.2 mol/L, NH3•H2O and ZnCl2In a molar ratio of 2: 1.
6. The method for the solid acid catalyzed synthesis of selenized polysaccharide of claim 1, wherein: in the step (c), the molar ratio of the artemisia sphaerocephala polysaccharide to the selenious acid is 1: 3.
7. The method for synthesizing selenized polysaccharide through solid acid catalysis in claim 1, wherein the mass ratio of the selenious acid to the solid acid ZnO in the step (c) is 10:1 ~ 20: 1.
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| CN106589157A (en) * | 2016-12-21 | 2017-04-26 | 福建农林大学 | Selenium modification method for improving immunological competence of radix pseudostellariae polysaccharides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101624425A (en) * | 2009-08-05 | 2010-01-13 | 西北师范大学 | Method for preparing seleno-polysaccharide by organic method |
| CN101628946A (en) * | 2009-08-07 | 2010-01-20 | 西北师范大学 | Method for compounding polyhexose selenide by microwave |
| CN105713104A (en) * | 2016-04-28 | 2016-06-29 | 西北师范大学 | Synthesis and application of selenized fenugreek polysaccharides |
| CN106589157A (en) * | 2016-12-21 | 2017-04-26 | 福建农林大学 | Selenium modification method for improving immunological competence of radix pseudostellariae polysaccharides |
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