CN103601910B - A kind of preparation method of matrine molecular surface imprinting polymer material - Google Patents
A kind of preparation method of matrine molecular surface imprinting polymer material Download PDFInfo
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Abstract
The invention provides a kind of preparation method of matrine molecular surface imprinting polymer material, utilize present method can obtain high performance matrine molecular surface imprinting polymer material, it is using silica gel as matrix, and good mechanical property is suitable for industrial production; Take matrine as template molecule, glutaraldehyde as cross linker, the surface imprinted technology of novel molecular of " first graft polymerization-crosslinked trace afterwards " is adopted to prepare matrine molecular surface imprinting polymer material, a large amount of matrine imprinted cavity is distributed with in the polymer foil on its surface, special identification selection and excellent binding affinity are shown to matrine, elution property is excellent, there is good regeneration and recycle performance, this, for separation and Extraction pharmacological active substance effectively from plant tissue, has obvious reference value.
Description
Technical field
The invention belongs to the technical field of Alkaloid separation purifying and molecularly imprinted polymer, be specifically related to a kind of preparation method of matrine molecular surface engram material.
Background technology
Alkaloid is the natural organic-compound that a large class is distributed widely in various plants tissue, there is more complicated nitrogen heterocyclic structure mostly, there is important physiologically active and pharmacologically active, scientific and efficient ground extracting and developing and purifying biological alkali from plant tissue, at medicine, there is huge application potential, need to greatly develop.And matrine is a kind of alkaloid with the pharmacologically active such as antitumor, antibacterial, antiviral significantly, is mainly derived from leguminous plants kuh-seng and Herba Sophorae alopecuroidis.Matrine, as cancer therapy drug, has great Development volue.At least containing 21 kinds of alkaloids and multiple Flavonoid substances in matrine crude extract, therefore, the separation and purification of matrine is a very complicated extraction engineering.
In recent years, take molecularly imprinted polymer as the solid phase extraction techniques of solid absorption, be widely used in numerous sciemtifec and technical sphere such as extraction of the identification of material, separation, purifying, enrichment and pharmacological active substance.But the method preparing alkaloid imprinted polymer material is at present mostly traditional method, i.e. entrapping method has the shortcomings such as preparation process is numerous and diverse, product property is poor, obviously affects the efficiency of Solid-Phase Extraction.
Therefore, prepare efficient matrine molecular surface engram material, carry out separation and purification matrine for Solid-Phase Extraction and there is very important practical value.
Summary of the invention
The present invention, in order to solve the technical problem of alkaloid particularly matrine separation and purification, provides a kind of preparation method of efficient matrine molecular surface engram material.
Main thought of the present invention is: first by " surperficial Inducing Graft Polymerization " method in the graft polymerization of micron order silica particle surface the function macromole with sodium benzenesulfonate group; Then, adopt the surface imprinted technology of novel molecular of " first graft polymerization-crosslinked trace afterwards ", by the strong electrostatic interaction between function grafting macromole and matrine molecule, in conjunction with the property of glutaraldehyde, obtain high performance matrine molecular surface engram material.
Technical scheme provided by the invention is: a kind of preparation method of matrine molecular surface imprinting polymer material, comprises the following steps:
Step one, preparation function grafting particulate SAS-PGMA/SiO
2: in toluene solvant, activated silica gel and coupling agent γ-mercaptopropyl trimethoxysilane react, the obtained modified silica-gel particulate MPMS-SiO of surface containing sulfydryl
2; In DMF solvent, modified silica-gel particulate MPMS-SiO
2with monomer GMA under nitrogen atmosphere and initiator A IBN exist, make monomer GMA that surperficial Inducing Graft Polymerization occur, obtained grafting particulate PGMA/SiO
2; By grafting particulate PGMA/SiO
2join make it in DMF solvent swelling after, add and be dissolved with an aqueous solution of diamino benzene sulfonic acid sodium SAS, system pH regulator to 12, stirring at 80 DEG C makes the epoxide group of grafting macromole PGMA and SAS, between bit amino, ring-opening reaction occur, and obtains the grafting particulate SAS-PGMA/SiO of benzene sulfonic acid sodium salt functionalization after reaction terminates
2;
Step 2, function grafting particulate SAS-PGMA/SiO
2to alkaloidal saturated adsorption: by function grafting particulate SAS-PGMA/SiO
2be placed in matrine water solution, the pH value of regulation system is 6, makes the absorption of function grafting particulate to matrine reach capacity, filtering particles, vacuum-drying after constant temperature oscillation;
Step 3, prepares matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2: by saturated adsorption, the function grafting particulate of matrine is placed in matrine water solution, the pH value of regulation system is 6, add the aqueous solution being dissolved with linking agent glutaraldehyde, at 45-50 DEG C, be stirred to reaction terminate, remove template molecule matrine after washing by soaking, obtain matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2, be reduced to MIP-SASP/SiO
2.
As preferred version of the present invention, with gram for the grafting particulate PGMA/SiO of measure unit in step one
2, with milliliter be measure unit DMF solvent and to be dissolved with a usage ratio for the aqueous solution of diamino benzene sulfonic acid sodium SAS be 1.5-2.0:50:10, wherein be dissolved with in an aqueous solution of diamino benzene sulfonic acid sodium SAS, in every 10ml aqueous solution, be dissolved with diamino benzene sulfonic acid sodium SAS between 4.19-5.58g.
As preferred version of the present invention, with gram for the function grafting particulate SAS-PGMA/SiO of measure unit in step 2
2, take milliliter as the usage ratio of the matrine water solution of measure unit be 2-3:100-150, wherein the concentration of matrine water solution is 2.0g/L.
As another preferred version of the present invention, linking agent glutaraldehyde used in step 3, its concentration is 8g/L; In step 3, the concentration of matrine water solution is 2.0g/L, gram being the usage ratio being dissolved with the aqueous solution of linking agent glutaraldehyde of measure unit is for 1-1.5:10-15 for the saturated adsorption function grafting particulate of matrine of measure unit, with milliliter.
Beneficial effect of the present invention is as follows:
(1) using silica gel as matrix, good mechanical property, is suitable for industrial production;
(2) take matrine as template molecule, glutaraldehyde as cross linker, the surface imprinted new technology of novel molecular of " first graft polymerization-crosslinked trace afterwards " is adopted to prepare matrine molecular surface imprinting polymer material, a large amount of matrine imprinted cavity is distributed with in the polymer foil on its surface, special identification selection and excellent binding affinity are shown to matrine, elution property is excellent, there is good regeneration and recycle performance, this, for separation and Extraction pharmacological active substance effectively from plant tissue, has obvious reference value.
Accompanying drawing explanation
Fig. 1 is function grafting particulate SAS-PGMA/SiO
2preparation process;
Fig. 2 is matrine molecular surface imprinting polymer material MIP-SASP/SiO
2preparation process;
Fig. 3 is grafting particulate PGMA/SiO
2with function grafting particulate SAS-PGMA/SiO
2infrared spectrogram;
Fig. 4 is function grafting particulate SAS-PGMA/SiO
2to three kinds of alkaloidal isothermal adsorption line charts;
Fig. 5 is matrine molecular surface imprinting polymer material MIP-SASP/SiO
2to three kinds of alkaloidal isothermals in conjunction with line chart;
Fig. 6 is function grafting particulate SAS-PGMA/SiO
2to three kinds of alkaloidal dynamic adsorption graphic representations;
Fig. 7 is matrine molecular surface imprinting polymer material MIP-SASP/SiO
2to three kinds of alkaloidal dynamic bind graphic representations.
Embodiment
The preparation method of a kind of matrine molecular surface imprinting polymer material alleged by the present invention is described in further detail below in conjunction with accompanying drawing specific embodiment, the technician in described field is after having read this specific embodiment, can technical solutions according to the invention be realized, also can embody advantage of the present invention and positively effect simultaneously.
Embodiment 1:
The preparation method of a kind of matrine molecular surface imprinting polymer material of the present invention, concrete steps are as follows: step one, preparation function grafting particulate SAS-PGMA/SiO
2:
1. in the four-hole bottle that electric mixer, condensing reflux pipe and thermometer are housed, add 2.5g activated silica gel, coupling agent γ-the mercaptopropyl trimethoxysilane (KH-590) of 125ml toluene solvant and 2.5mL, 12h is reacted at 110 DEG C, after terminating reaction, suction filtration, product particles first uses toluene wash, use ethanol repetitive scrubbing again, vacuum-drying, i.e. the obtained modified silica-gel particulate MPMS-SiO of surface containing sulfydryl
2;
2., in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed, the modified granular MPMS-SiO of 1.2g is added
2, then adding DMF and the 9.9-10.0mL monomer GMA of 70mL, logical nitrogen 30min, with the air in eliminating system, rises to 55 DEG C by the temperature of system, then adds 0.0867g initiator A IBN, and constant temperature carries out graft polymerization reaction under stirring; After reaction terminates, suction filtration, isolates product particles, then in Soxhlet extractor, use acetone extraction 20-24h, and to remove the homopolymer that physics is adsorbed on microparticle surfaces, then vacuum-drying is to constant weight, obtains grafting particulate PGMA/SiO
2;
3., in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed, 1.5g grafting particulate PGMA/SiO is added
2, add 50mL solvent DMF make it swelling after, add the aqueous solution that 10ml is dissolved with diamino benzene sulfonic acid sodium SAS between 4.19g, system pH regulator to 12,80 DEG C, under agitation condition, carry out ring-opening reaction; After reaction terminates, suction filtration, with distilled water and ethanol repetitive scrubbing, vacuum-drying, to constant weight, obtains the grafting particulate SAS-PGMA/SiO of benzene sulfonic acid sodium salt functionalization
2 .
Step 2, function grafting particulate SAS-PGMA/SiO
2to alkaloidal saturated adsorption:
Take 2g function grafting particulate SAS-PGMA/SiO
2, be placed in the matrine water solution that 100mL concentration is 2.0g/L, the pH value of regulation system, makes pH=6, and solution is placed in constant temperature oscillator, constant temperature oscillation 4-6h, the absorption of function grafting particulate to matrine is reached capacity, filtering particles, vacuum-drying.
Step 3, prepares matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2:
Take the function grafting particulate of 1g saturated adsorption matrine, be placed in the aqueous solution that concentration is 2.0g/L matrine, the pH value of regulation system, makes pH=6, add the aqueous solution that 10mL is dissolved with linking agent glutaraldehyde (concentration is 8g/L), stirring reaction 24h at 45 DEG C; After reaction terminates, under agitation use rare NaOH(pH=11) solution washing by soaking repeatedly, removing template molecule matrine, vacuum-drying, obtains matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2, be reduced to MIP-SASP/SiO
2.
Embodiment 2:
Step one, preparation function grafting particulate SAS-PGMA/SiO
2:
1. in the four-hole bottle that electric mixer, condensing reflux pipe and thermometer are housed, add 3.0g activated silica gel, coupling agent γ-the mercaptopropyl trimethoxysilane (KH-590) of 130ml toluene solvant and 3.0mL, 12h is reacted at 110 DEG C, after terminating reaction, suction filtration, product particles first uses toluene wash, use ethanol repetitive scrubbing again, vacuum-drying, i.e. the obtained modified silica-gel particulate MPMS-SiO of surface containing sulfydryl
2;
2., in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed, the modified granular MPMS-SiO of 1.5g is added
2, then adding DMF and the 10.0mL monomer GMA of 70mL, logical nitrogen 30min, with the air in eliminating system, rises to 55 DEG C by the temperature of system, then adds 0.0874g initiator A IBN, and constant temperature carries out graft polymerization reaction under stirring; After reaction terminates, suction filtration, isolates product particles, then in Soxhlet extractor, use acetone extraction 20-24h, and to remove the homopolymer that physics is adsorbed on microparticle surfaces, then vacuum-drying is to constant weight, obtains grafting particulate PGMA/SiO
2;
3., in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed, 2.0g grafting particulate PGMA/SiO is added
2, add 50mL solvent DMF make it swelling after, add the aqueous solution that 10ml is dissolved with diamino benzene sulfonic acid sodium SAS between 5.58g, system pH regulator to 12,80 DEG C, under agitation condition, carry out ring-opening reaction; After reaction terminates, suction filtration, with distilled water and ethanol repetitive scrubbing, vacuum-drying, to constant weight, obtains the grafting particulate SAS-PGMA/SiO of benzene sulfonic acid sodium salt functionalization
2 ;
Step 2, function grafting particulate SAS-PGMA/SiO
2to alkaloidal saturated adsorption:
Take 3g function grafting particulate SAS-PGMA/SiO
2, be placed in the matrine water solution that 150mL concentration is 2.0g/L, the pH value of regulation system, makes pH=6, and solution is placed in constant temperature oscillator, constant temperature oscillation 4-6h, the absorption of function grafting particulate to matrine is reached capacity, filtering particles, vacuum-drying;
Step 3, prepares matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2:
Take the function grafting particulate of 1.5g saturated adsorption matrine, be placed in the aqueous solution that concentration is 2.0g/L matrine, the pH value of regulation system, makes pH=6, add the aqueous solution that 15mL is dissolved with linking agent glutaraldehyde (concentration is 8g/L), stirring reaction 24h at 50 DEG C; After reaction terminates, under agitation use rare NaOH(pH=11) solution washing by soaking repeatedly, removing template molecule matrine, vacuum-drying, obtains matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2, be reduced to MIP-SASP/SiO
2.
Fig. 1 and Fig. 2 respectively illustrates function grafting particulate SAS-PGMA/SiO
2with matrine molecular surface imprinting polymer material MIP-SASP/SiO
2preparation process.
Fig. 3 shows grafting particulate PGMA/SiO
2with function grafting particulate SAS-PGMA/SiO
2infrared spectrogram, at grafting particulate PGMA/SiO
2infrared spectrum in, in 908cm
-1place and 1740cm
-1place has occurred that the epoxide group of grafting macromole PGMA and ester carbonyl group eigen vibration absorb; And at SAS-PGMA/SiO
2infrared spectrum in, at 1600cm
-1and 1486cm
-1having there is the framework characteristic vibration absorption peak of phenyl ring in place, the more important thing is 908cm
-1the charateristic avsorption band of place's epoxide group disappears, and at 660cm
-1there is amino charateristic avsorption band in place, and at 3440cm
-1there is the vibration absorption peak of hydroxyl in place, this is all the result of epoxide group ring-opening reaction.In addition, at 1010cm
-1there is sulfonic characteristic absorbance in place.The change of above-mentioned spectrum peak data fully shows, SAS there occurs ring-opening reaction with the epoxide group of grafting macromole PGMA, sodium benzenesulfonate group is bonded in grafting macromolecule side chain side chain, defines function grafting particulate SAS-PGMA/SiO
2.
Selective oxidation matrine and Tocosamine, as two kinds of contrasts, investigate matrine molecular surface engram material MIP-SASP/SiO
2molecular recognition properties.Oxymatyine is a kind of oxidised form of matrine, its chemical structure and matrine quite similar, just more than matrine Sauerstoffatoms in molecular structure; Tocosamine is also a kind of important alkaloid, its chemical structure also with matrine by certain similarity; The more important thing is that Oxymatyine and sparteine and matrine are all be present in the leguminous plantss such as kuh-seng, three kinds of alkaloids all have very high pharmaceutical use.
Effect proves experiment one:
Adopt stationary method, using function grafting particulate SAS-PGMA/SiO
2with matrine molecular surface imprinting polymer material MIP-SASP/SiO
2, respectively adsorption isotherm experiment has been carried out to the matrine in water medium, Oxymatyine and Tocosamine.Detailed process is: under room temperature, the matrine solution of 20mL concentration series change, and adds the matrine molecular surface imprinting polymer material MIP-SASP/SiO that the quality accurately taken is about 0.1g respectively
2, constant temperature oscillation 4h in bath constant temperature oscillator, makes combination reach balance, standing separation, measures the equilibrium concentration of matrine in supernatant liquor, calculates the junction at equilibrium resultant of matrine
q e (mg/g), isothermal joint line is drawn; Adopt same method, by matrine molecular surface imprinting polymer material MIP-SASP/SiO
2add respectively in Oxymatrine alkaline solution and Tocosamine solution, determine this two kinds of alkaloidal equilibrium concentrations, their isothermal joint line of drawing him; And the drafting function grafting particulate SAS-PGMA/SiO that uses the same method
2to three kinds of alkaloidal sorption isotherms.Fig. 4 shows SAS-PGMA/SiO
2to the sorption isotherm of three kinds of materials, Fig. 5 shows MIP-SASP/SiO
2to the isothermal joint line of three kinds of materials.Fig. 4 shows, function grafting particulate SAS-PGMA/SiO
2all have high loading capacity (loading capacity is at 31-39mg/g) to three kinds of biological alkalescence, obviously, absorption does not have selectivity.But, but clearly illustrate in Fig. 5, matrine molecular surface imprinting polymer material MIP-SASP/SiO
2significantly decline to the binding capacity of Tocosamine and Oxymatyine, the former maximal absorptive capacity drops to 5mg/g by 31mg/g, and the maximal absorptive capacity of the latter then drops to 20mg/g by 37mg/g.Obviously, matrine molecular surface imprinting polymer material MIP-SASP/SiO
2to the basic nonrecognition of Tocosamine be not combined, the bonding properties of Oxymatyine is also greatly reduced.But for matrine, not only maintain originally high binding capacity, but also increase (most high adsorption capacity rises to 45mg/g by 38mg/g).Above-mentioned experimental fact fully shows that, MIP-SASP/SiO
2the special identification selection have matrine and binding affinity highly.Matrine molecular surface imprinting polymer material MIP-SASP/SiO
2in the polymer foil on surface, be distributed with the trace hole of a large amount of matrine molecule, these holes in size, space structure and action site etc. with template molecule matrine molecule be matched, therefore to matrine, there is special recognition capability, produce very strong keying action, cause very high binding capacity; And for Tocosamine, matrine trace hole is all be with it unmatched in size, space structure and action site etc., imprinted cavity is difficult to hold sparteine molecule and enters wherein, therefore imprinted material MIP-SASP/SiO
2to the basic nonrecognition of sparteine be not combined, cause very low binding capacity; For Oxymatyine, although its chemical structure is quite similar with matrine, molecular structure changes after all to some extent, and its molecular volume is also slightly larger than matrine, cause the mismatch of matrine imprinted cavity and Oxymatrine base molecule certain degree, therefore binding capacity greatly declines.
Effect proves experiment two:
Adopt dynamic method, using function grafting particulate SAS-PGMA/SiO
2with matrine molecular surface imprinting polymer material MIP-SASP/SiO
2, respectively dynamic adsorption isotherm experiment has been carried out to the Tocosamine in water medium, matrine and Oxymatyine.Detailed process is: under room temperature, is the matrine molecular surface imprinting polymer material MIP-SASP/SiO loading 2.0g in the Glass tubing of 10mm at internal diameter
2, make the bed volume of packed column be 2mL; Be that the matrine solution of 1g/L is with 4BVh by concentration
-1flow velocity in a counter-current fashion by packed column, with the interval collection effluent liquid of 2BV, measure kuh-seng paper mill wastewater in effluent liquid, draw dynamic bind curve; Adopt same method, make Oxymatyine and Tocosamine solution respectively upstream by matrine molecular surface imprinting polymer material MIP-SASP/SiO
2packed column, measure the alkaloidal concentration of two contrasts in effluent liquid, draw their dynamic bind curve; And the drafting function grafting particulate SAS-PGMA/SiO that uses the same method
2to three kinds of alkaloidal dynamic adsorption curves.Fig. 6 shows SAS-PGMA/SiO
2to three kinds of alkaloidal dynamic adsorption curves, Fig. 7 shows MIP-SASP/SiO
2to three kinds of alkaloidal dynamic bind curves.As can be seen from Figure 6, when three kinds of alkaloid solution flow velocity respectively adverse current pass through SAS-PGMA/SiO
2during packed column, leakage volume is respectively 12BV(Tocosamine), 16BV(matrine) and 17BV(Oxymatyine), be more or less the same, show that this packed column is close to three kinds of alkaloidal absorption properties, substantially without identification selection.As seen from Figure 7, when three kinds of alkaloid solution adverse currents pass through MIP-SASP/SiO
2during packed column, the leakage volume of two kinds of contrast materials significantly declines, 2BV is down to by Tocosamine, 6BV is down to by Oxymatyine, fully demonstrate that matrine imprinted material packed column is not selected substantially for two kinds of contrast alkaloids, nonrecognition and not combining, its reason be still these holes in size, space structure and action site etc. with the mismatch of combined thing.And when matrine solution adverse current passes through MIP-SASP/SiO
2during packed column, leakage volume still keeps higher numerical value, and also increases to some extent, increases to 19BV by 16BV, shows matrine molecular surface imprinting polymer material packed column and has special identification selection to matrine.As calculated, leakage binding capacity and the saturated binding capacity of Tocosamine are only 2mg/g and 8mg/g, and the leakage adsorptive capacity of matrine and saturated extent of adsorption are then up to 36mg/g and 48mg/g.
Effect proves experiment three:
Employing competitive adsorption is tested, the Binary Mixtures of preparation matrine/Tocosamine and matrine/Oxymatyine, uses matrine molecular surface imprinting polymer material MIP-SASP/SiO
2, carried out competitive adsorption experiment.Detailed process is: compound concentration is matrine/Oxymatyine and matrine/Tocosamine two kinds of Binary Mixtures of 1g/L, get 20mL mixed solution, add the matrine molecular surface imprinting polymer material MIP-SASP/SiO of the about 0.1g of precise respectively
2, vibrate 4h in constant temperature oscillator, makes absorption reach balance, standing separation, measures the equilibrium concentration of each material in supernatant liquor, calculates the partition ratio of three kinds of materials.Table 1 and table 2 list the partition ratio of each material
k dand the selectivity coefficient of material
k.
The partition ratio of table 1 matrine/Tocosamine system and selectivity coefficient data
The partition ratio of table 2 matrine/Oxymatrine alkali systems and selectivity coefficient data
The data of table 1 and table 2 show: relative to Tocosamine and Oxymatyine two kinds contrast alkaloid, function grafting particulate SAS-PGMA/SiO
2(non-imprinted material) is respectively 1.3 and 0.9 to the selectivity coefficient of matrine, all close to 1, this means SAS-PGMA/SiO
2very close to the adsorptive power of kind of the material of two in Binary Mixtures, lack selectivity.But, relative to Tocosamine, matrine molecular surface imprinting polymer material MIP-SASP/SiO
2to the selectivity coefficient of matrine up to 10.7, show very high identification selection; Even if relative to molecular structure and the quite similar Oxymatyine of matrine, matrine imprinted material MIP-SASP/SiO
2still 5.6 are reached to the selectivity coefficient of matrine, also demonstrates higher identification selection.Competitive experimental data clearly reveals further, matrine molecular surface imprinting polymer material MIP-SASP/SiO
2have single-minded in conjunction with selectivity to template molecule matrine.
Effect proves experiment four:
Adopt elution experiments, with rare NaOH aqueous solution for elutriant, carry out elution experiments, be bonded to matrine molecular surface imprinting polymer material MIP-SASP/SiO
2the matrine molecule on surface, owing to being distributed in the polymer foil of silica particle surface, be thus easy to desorption occurs, in 20 bed volumes, desorption efficiency can reach 99.3%, i.e. matrine molecular surface imprinting polymer material MIP-SASP/SiO
2there is excellent regeneration and recycle performance.
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the amendment not having creative contribution as required after reading this specification sheets, as long as but be all subject to the protection of patent law in right of the present invention.
Claims (5)
1. a preparation method for matrine molecular surface imprinting polymer material, is characterized in that comprising the following steps:
Step one, preparation function grafting particulate SAS-PGMA/SiO
2: in toluene solvant, activated silica gel and coupling agent γ-mercaptopropyl trimethoxysilane react, the obtained modified silica-gel particulate MPMS-SiO of surface containing sulfydryl
2; In DMF solvent, modified silica-gel particulate MPMS-SiO
2with monomer GMA under nitrogen atmosphere and initiator A IBN exist, make monomer GMA that surperficial Inducing Graft Polymerization occur, obtained grafting particulate PGMA/SiO
2; By grafting particulate PGMA/SiO
2join make it in DMF solvent swelling after, add and be dissolved with an aqueous solution of diamino benzene sulfonic acid sodium SAS, system pH regulator to 12, stirring at 80 DEG C makes the epoxide group of grafting macromole PGMA and SAS, between bit amino, ring-opening reaction occur, and obtains the grafting particulate SAS-PGMA/SiO of benzene sulfonic acid sodium salt functionalization after reaction terminates
2 ;
Step 2, function grafting particulate SAS-PGMA/SiO
2to alkaloidal saturated adsorption: by function grafting particulate SAS-PGMA/SiO
2be placed in matrine water solution, the pH value of regulation system is 6, makes the absorption of function grafting particulate to matrine reach capacity, filtering particles, vacuum-drying after constant temperature oscillation;
Step 3, prepares matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2: by saturated adsorption, the function grafting particulate of matrine is placed in matrine water solution, the pH value of regulation system is 6, add the aqueous solution being dissolved with linking agent glutaraldehyde, at 45-50 DEG C, be stirred to reaction terminate, remove template molecule matrine after washing by soaking, obtain matrine molecular surface imprinting polymer material MIP-SAS-PGMA/SiO
2, be reduced to MIP-SASP/SiO
2.
2. the preparation method of a kind of matrine molecular surface imprinting polymer material according to claim 1, is characterized in that: with gram for the grafting particulate PGMA/SiO of measure unit in step one
2, with milliliter be measure unit DMF solvent and to be dissolved with a usage ratio for the aqueous solution of diamino benzene sulfonic acid sodium SAS be 1.5-2.0:50:10, wherein be dissolved with in an aqueous solution of diamino benzene sulfonic acid sodium SAS, in every 10ml aqueous solution, be dissolved with diamino benzene sulfonic acid sodium SAS between 4.19-5.58g.
3. the preparation method of a kind of matrine molecular surface imprinting polymer material according to claim 1, is characterized in that: with gram for the function grafting particulate SAS-PGMA/SiO of measure unit in step 2
2, take milliliter as the usage ratio of the matrine water solution of measure unit be 2-3:100-150, wherein the concentration of matrine water solution is 2.0g/L.
4. the preparation method of a kind of matrine molecular surface imprinting polymer material according to claim 1, is characterized in that: the working concentration of the glutaraldehyde of linking agent described in step 3 is 8g/L.
5. the preparation method of a kind of matrine molecular surface imprinting polymer material according to claim 1 or 4, it is characterized in that: in step 3, the concentration of matrine water solution is 2.0g/L, gram being the usage ratio being dissolved with the aqueous solution of linking agent glutaraldehyde of measure unit is for 1-1.5:10-15 for the saturated adsorption function grafting particulate of matrine of measure unit, with milliliter.
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| CN107649101B (en) * | 2017-09-29 | 2019-09-10 | 湖南大学 | Mercapto-functionalized titania molecule trace composite material and its aqueous phase preparation method and application |
| CN112791712B (en) * | 2021-01-05 | 2022-05-10 | 南开大学 | Adsorbent for removing protein-bound uremic toxin through blood perfusion and preparation method thereof |
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| CN101775152A (en) * | 2010-02-25 | 2010-07-14 | 中北大学 | Preparation method of surface imprinted material for matrine substance separation and purification |
| CN103289030A (en) * | 2013-05-22 | 2013-09-11 | 中北大学 | Novel method for efficiently grafting glycidyl methacrylate (GMA) on surface of silica gel |
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| CN103289030A (en) * | 2013-05-22 | 2013-09-11 | 中北大学 | Novel method for efficiently grafting glycidyl methacrylate (GMA) on surface of silica gel |
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