CN1164619C - Process for preparing microspheres of molecular blot polymer in water medium - Google Patents
Process for preparing microspheres of molecular blot polymer in water medium Download PDFInfo
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- CN1164619C CN1164619C CNB021214840A CN02121484A CN1164619C CN 1164619 C CN1164619 C CN 1164619C CN B021214840 A CNB021214840 A CN B021214840A CN 02121484 A CN02121484 A CN 02121484A CN 1164619 C CN1164619 C CN 1164619C
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Abstract
The present invention discloses a method for preparing a molecularly imprinted polymer microsphere in a water medium. By using the method, the particle diameter of a molecularly imprinted polymer microsphere can be adjusted according to requirements. The present invention has the advantages of good molecular recognition performance, simpleness, easy application and low cost and is realized by the following technical schemes: (1) hydroxyethyl cellulose is put in water and is stirred until the hydroxyethyl cellulose is completely dissolved; (2) a functional monomer and a mould plate molecule are put in water; (3) trimethylolpropane trimethacrylate, an initiating agent and a diluting agent are mixed and stirred; (4) the three solutions are mixed, a nitrogen gas is introduced into a mixed solution, and the mixed solution is sealed; the mixed solution is stirred for 6 to 10 hours at constant speed of 300 to 400 rpm and at a constant temperature of 65 to 80 DEG C; (5) a polymer obtained by reaction is cleaned and is eluted by a dilute acid solution until mould plate molecules are removed; (6) the polymers of the mould plate molecules are removed by water until neutrality appears. By airing at normal temperature, the molecularly imprinted polymer microsphere is obtained. The present invention is used for the field of biological materials.
Description
Technical field
The present invention relates to a kind of preparation method of polymkeric substance, more particularly, relate to a kind of preparation method who template molecule is had the polymkeric substance of singleness identity.
Background technology
Usually, molecularly imprinted polymer adopts mass polymerization to make, and product is block, can use behind grinding, the particle that obtains required size that sieves.Yet grinding can cause the part conjugated group to be destroyed, thereby makes the molecular recognition and selection degradation of molecularly imprinted polymer MIPs, and adopts the out-of-shape of this method gained particulate, imitates also lower as the post of chromatographic stationary phase time.In addition, grind the sieve process and can only obtain the part useful products, cause huge waste, thereby cause producing and the use cost increase.
On the other hand, nearly all trace process is all carried out in non-aqueous system, and seldom adopts water miscible material as template.Because water molecules damages the keying action between microsphere and the functional group especially hydrogen bond easily, if the condition of trace is selected the improper failure that just probably causes trace.Yet the trace in the organic solvent is not simulated the aqueous environments in the practical application as a rule again, can not satisfy the diversified demand of actual environment for use.
2002 the 20th volumes of " chromatogram " magazine the 2nd phase " the seed swelling suspension polymerization prepares a molecular blotting polymer microsphere " literary composition discloses a kind of preparation method of molecular blotting polymer microsphere, it adopts following step: (1) adds vinylbenzene, Potassium Persulphate in the entry, stir, feed nitrogen, be heated to 70 ℃, constant temperature 18 hours feeds nitrogen again in the emulsion that makes, obtain kind of a ball emulsion; (2) will plant the ball emulsion joins by swelling in pore-creating agent, initiator, the prepared solution of dispersion agent; (3) tyrosine, methacrylic acid MAA are mixed the back with TRIM and stir, and said mixture is distributed to the tax category with dispersion agent; (4) join swelling in kind of the ball according to above-mentioned dispersion liquid; (5) above-mentioned swelling solution is joined in the airtight reactor, feed nitrogen, and add the reductive agent emulsion, stir, initiated polymerization, reaction was at room temperature carried out 24 hours; (6) suspension filtered that reaction is obtained obtains polymer microballoon.(7) polymer microballoon is distributed in the water, under whipped state, boils, filter back water flushing, then microballoon is put into toluene and soak after-filtration with boiling water; (8) gains are cleaned with organic solvent, dry under the normal temperature, promptly make molecular blotting polymer microsphere.
Though the molecularly imprinted polymer that adopts aforesaid method to make has recognition performance preferably in aqueous medium, complicated process of preparation, preparation cycle is long, is unfavorable for the penetration and promotion of product.
Summary of the invention
The objective of the invention is to overcome weak point of the prior art; provide a kind of simple, save time, easily capable, with low cost and the preparation method of the molecular blotting polymer microsphere of good molecular recognition performance arranged in aqueous medium; make product have the advantage that shape is regular, specific surface big, particle diameter can be adjusted as required; further widening the use range of trace environment and molecular imprinting, and promote this technology by theory to the transformation of using.
The present invention is achieved through the following technical solutions:
(1) prepare material according to following prescription: the mol ratio of template molecule, function monomer and trimethylolpropane trimethacrylate is 1～3: 2～9: 71; Described function monomer is single function monomer or bi-functional monomer, and the mol ratio of two kinds of components is 1: 1 in the described bi-functional monomer; The volume ratio of thinner and trimethylolpropane trimethacrylate is 1: 1.3～4; The cumulative volume of thinner and trimethylolpropane trimethacrylate and the volume ratio of water are 1: 5.7～6.8; The mass percent that Natvosol accounts for trimethylolpropane trimethacrylate is 0.83～1%; (2) Natvosol is placed water, be stirred to its whole dissolvings, and solution is heated to 65～80 ℃; (3) function monomer and template molecule are placed water; (4), stir with trimethylolpropane trimethacrylate, initiator and mixing diluents; (5) above-mentioned three kinds of solution are mixed, airtight behind the feeding nitrogen, stirred 6～10 hours in the constant speed of 65～80 ℃ of constant temperature with 300～400 rev/mins; (6) polymkeric substance that reaction is obtained cleans with organic solvent earlier, uses the dilute acid soln wash-out again, to removing template molecule; (7) the polymkeric substance water that will remove template molecule cleans to neutral, dries at normal temperatures, promptly makes molecular blotting polymer microsphere.
Beneficial effect of the present invention:
(1) the suspension preparation method that the present invention developed is that dispersion medium, water soluble molecules are template molecule with water, the molecular recognition material of gained has good molecular recognition performance in aqueous environments, for the trace in the aqueous medium and identification problem provide a kind of feasible solution.
(2) molecularly imprinted polymer for preparing of the present invention need not to grind, sieves and can directly use, and by the adjusting to dispersant dosage the size of microballoon can be controlled for spherical, thereby has guaranteed accessibility and high efficiency that this product uses.
(3) compare with the existing method that in aqueous medium, prepares molecularly imprinted polymer MIPMs, the present invention has that preparation technology is simple, preparation cycle is short, cost is low, easily realize and the advantage of excellent product performance, thereby more helps molecularly imprinted polymer MIPMs popularizing on using.
Embodiment
The invention will be further described below in conjunction with embodiment.
Reagent of the present invention and material requirements:
Trimethylolpropane trimethacrylate TRIM, chemical pure;
Cimitidine Type A/AB Cimetidine, different rich fourth, tyrosine, L-phenylalanine L-Phenylalaine are biochemical reagents, analytical pure;
Natvosol HEC, benzoyl peroxide BPO and Diisopropyl azodicarboxylate AIBN are chemical pure;
Toluene, acetonitrile, tetracol phenixin, 2-acrylamide-2-methyl propane sulfonic acid AMPS, methacrylic acid MAA, 2-vinyl pyridine 2-VP, acrylamide and other compounds and solvent are analytical pure.
Embodiment 1.
0.2 gram Natvosol HEC, 150 ml waters are placed reactor, and stirring makes it dissolving and is heated to 65 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in 20 ml waters, also add in the reactor.Toluene with 20 milliliters of trimethylolpropane trimethacrylate TRIM, 0.2 gram, Diisopropyl azodicarboxylate AIBN and 10 milliliters mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, stirs at 65 ℃ of constant temperature, with the 365rpm constant speed and finishes in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100 milliliters of acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 255 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 2.
0.22 gram Natvosol HEC, 150 ml waters are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in 20 ml waters, also add in the reactor.Toluene with 20 milliliters of trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10 milliliters mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 3 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100 milliliters of acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 161 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 3.
0.23 gram Natvosol HEC, 150 ml waters are placed reactor, and stirring makes it dissolving and is heated to 70 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in 20 ml waters, also add in the reactor.Toluene with 20 milliliters of trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10 milliliters mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, 70 ℃ of constant temperature, 365rpm constant speed stir end in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100 milliliters of acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 108 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 4.
0.24 gram Natvosol HEC, 150 ml waters are placed reactor, stir, make it dissolving and be heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in 20 ml waters, also add in the reactor.Toluene with 20 milliliters of trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10 milliliters mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100 milliliters of acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 5
0.24 gram Natvosol HEC, 100ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in the 70ml water, also add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 6.
0.24 gram Natvosol HEC, 125ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in the 45ml water, also add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 7.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 65 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in the 20ml water, also add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 65 ℃ of constant temperature, 365rpm constant speed stir and finished in 10 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 8.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 80 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in the 20ml water, also add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 6 minutes to feed nitrogen, and 80 ℃ of constant temperature, 365rpm constant speed stir and finished in 6 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 9.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in the 20ml water, also add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 300rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 10.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS and 0.107 gram tyrosine are dissolved in the 20ml water, also add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 400rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 50 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 11.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.107 gram tyrosine, 0.6 gram 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 12.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.107 gram tyrosine, 0.35 gram acrylamide and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the tyrosine trace MIPMs that median size is 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 13.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.With 0.492 gram methacrylic acid, 0.107 gram tyrosine, 0.6 gram 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 14.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.With 0.492 gram methacrylic acid, 0.107 gram tyrosine, 0.35 gram acrylamide and 20ml water is mixed and add in the reactor.The toluene that 20ml TRIM, 0.2 is restrained Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, adds in the reactor after Diisopropyl azodicarboxylate AIBN dissolving, and feeding nitrogen is airtight after 5 minutes, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 15.
0.24 gram Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276 gram 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.107 gram tyrosine, 0.6 gram 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Tetracol phenixin with 20ml trimethylolpropane trimethacrylate TRIM, 0.2 gram Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 16.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.144g Cimitidine Type A/AB, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml ethanol earlier; Use the HCl aqueous solution wash-out of 1mol/l again, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects Cimitidine Type A/AB concentration under 206nm, and the concentration of Cimitidine Type A/AB is lower than 1 * 10 in elutriant
-4Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the Cimitidine Type A/AB trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 17.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.144g Cimitidine Type A/AB, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Tetracol phenixin with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml ethanol earlier; Use the HCl aqueous solution wash-out of 1mol/l again, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects Cimitidine Type A/AB concentration under 206nm, and the concentration of Cimitidine Type A/AB is lower than 1 * 10 in elutriant
-4Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the Cimitidine Type A/AB trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 18.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.144g Cimitidine Type A/AB and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 8 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml ethanol earlier; Use the HCl aqueous solution wash-out of 1mol/l again, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects Cimitidine Type A/AB concentration under 206nm, and the concentration of Cimitidine Type A/AB is lower than 1 * 10 in elutriant
-4Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the Cimitidine Type A/AB trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 19.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.144g Cimitidine Type A/AB, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Acetonitrile with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml ethanol earlier; Use the HCl aqueous solution wash-out of 1mol/l again, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects Cimitidine Type A/AB concentration under 206nm, and the concentration of Cimitidine Type A/AB is lower than 1 * 10 in elutriant
-4Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the Cimitidine Type A/AB trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 20.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.144g Cimitidine Type A/AB and 20ml water is mixed and add in the reactor.Acetonitrile with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml ethanol earlier; Use the HCl aqueous solution wash-out of 1mol/l again, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects Cimitidine Type A/AB concentration under 206nm, and the concentration of Cimitidine Type A/AB is lower than 1 * 10 in elutriant
-1Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the Cimitidine Type A/AB trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 21.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.107g tyrosine, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Then 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 5ml toluene are mixed, stir, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 5 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 22.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.276g 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.107g tyrosine, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Then 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 15ml toluene are mixed, stir, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, it is airtight after 6 minutes to feed nitrogen, and 75 ℃ of constant temperature, 365rpm constant speed stir and finished in 8 hours.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be acetate and the methanol mixed eluant solution of 1: 3 1mol/l again with mol ratio, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 65 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 23.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 80 ℃.1.276g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.187g tyrosine, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.4g benzoyl peroxide BPO and 10ml mixes, stirs then, having served as Oxybenzene formyl dissolving back adds in the reactor, airtight behind the feeding nitrogen 5min, 80 ℃ of constant temperature, 365rpm constant speed stir 8h and finish.
The polymkeric substance of above-mentioned reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 24.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 85 ℃.1.276g 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.187g tyrosine, 0.6g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.4g benzoyl peroxide BPO and 10ml mixes, stirs then, having served as Oxybenzene formyl dissolving back adds in the reactor, airtight behind the feeding nitrogen 5min, 85 ℃ of constant temperature, 365rpm constant speed stir 6h and finish.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 25.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.0.425g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.187g tyrosine, 0.2g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, airtight behind the feeding nitrogen 5min, 75 ℃ of constant temperature, 365rpm constant speed stir 8h and finish.The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 26.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.0.851g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.187g tyrosine, 0.4g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, airtight behind the feeding nitrogen 5min, 75 ℃ of constant temperature, 365rpm constant speed stir 8h and finish.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration concentration of tyrosine in elutriant and is lower than 1 * 10 under 276nm
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 27.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.914g 2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.187g tyrosine, 0.9g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, airtight behind the feeding nitrogen 5min, 75 ℃ of constant temperature, 365rpm constant speed stir 8h and finish.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 28.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.914g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.374g tyrosine, 0.9g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, airtight behind the feeding nitrogen 5min, 75 ℃ of constant temperature, 365rpm constant speed stir 8h and finish.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration concentration of tyrosine in elutriant and is lower than l * 10 under 276nm
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Embodiment 29.
0.24g Natvosol HEC, 150ml water are placed reactor, and stirring makes it dissolving and is heated to 75 ℃.1.914g2-acrylamide-2-methyl propane sulfonic acid AMPS, 0.561g tyrosine, 0.9g 2-vinyl pyridine and 20ml water is mixed and add in the reactor.Toluene with 20ml trimethylolpropane trimethacrylate TRIM, 0.2g Diisopropyl azodicarboxylate AIBN and 10ml mixes, stirs then, after Diisopropyl azodicarboxylate AIBN dissolving, add in the reactor, airtight behind the feeding nitrogen 5min, 75 ℃ of constant temperature, 365rpm constant speed stir 8h and finish.
The polymkeric substance of reaction gained is cleaned twice with 100ml acetone earlier; Be 1 with mol ratio again: the acetate of 31mol/l and methanol mixed eluant solution, the 756MC UV-VIS ultraviolet spectrophotometer of producing with the Shanghai second analytical instrument factory detects tyrosine concentration under 276nm, and the concentration of tyrosine is lower than 1 * 10 in elutriant
-2Mmol/l; Clean repeatedly to neutrality with deionized water, the polymkeric substance behind the wash-out is dried at normal temperatures promptly get the molecularly imprinted polymer MIPMs that median size is the tyrosine trace of 60 μ m at last, its molecular recognition performance sees Table 1.
Table 1 is the molecular recognition performance table of different embodiment products therefroms, and wherein separation factor is defined as the ratio of template molecule and the partition ratio of competition substrate in MIPs surface and solution.It is an important parameter of weighing MIPs Molecular Selection performance, show that MIPs has the certain selectivity energy when separation factor is about 1 the time, and the selection specificity of the big more MIPs of separation factor is also good more; Separation factor is than the ratio of the separation factor that is defined as MIPs and its corresponding blank polymkeric substance, and it has mainly embodied MIPs and the difference of blank polymkeric substance on the Molecular Selection absorption property, is the main foundation of weighing the trace effect.
The molecular recognition performance table of the different embodiment products therefroms of table 1
MIPMs template molecule competition substrate separation factor is separated because of median size
---son is than (μ m)
Embodiment 1 tyrosine L-phenylalanine 1.43 1.36 255
Embodiment 2 tyrosine L-phenylalanines 1.45 1.37 161
Embodiment 3 tyrosine L-phenylalanines 1.45 1.38 108
Embodiment 4 tyrosine L-phenylalanines 1.44 1.37 60
Embodiment 5 tyrosine L-phenylalanines 1.44 1.37 60
Embodiment 6 tyrosine L-phenylalanines 1.44 1.37 60
Embodiment 7 tyrosine L-phenylalanines 1.45 1.37 60
Embodiment 8 tyrosine L-phenylalanines 1.42 1.36 60
Embodiment 9 tyrosine L-phenylalanines 1.45 1.38 60
Embodiment 10 tyrosine L-phenylalanines 1.45 1.39 50
Embodiment 11 tyrosine L-phenylalanines 1.83 1.79 60
Embodiment 12 tyrosine L-phenylalanines 1.76 1.64 60
Embodiment 13 tyrosine L-phenylalanines 1.77 1.70 60
Embodiment 14 tyrosine L-phenylalanines 1.65 1.57 60
Embodiment 15 tyrosine L-phenylalanines 1.67 1.61 60
The different rich fourth 2.14 1.89 60 of embodiment 16 Cimitidine Type A/ABs
The different rich fourth 1.92 1.67 60 of embodiment 17 Cimitidine Type A/ABs
The different rich fourth 1.63 1.46 60 of embodiment 18 Cimitidine Type A/ABs
The different rich fourth 1.82 1.59 60 of embodiment 19 Cimitidine Type A/ABs
The different rich fourth 1.69 1.51 60 of embodiment 20 Cimitidine Type A/ABs
Embodiment 21 tyrosine L-phenylalanines 1.71 1.62 60
Embodiment 22 tyrosine L-phenylalanines 1.76 1.70 65
Embodiment 23 tyrosine L-phenylalanines 1.83 1.78 65
Embodiment 24 tyrosine L-phenylalanines 1.81 1.77 65
Embodiment 25 tyrosine L-phenylalanines 1.53 1.47 65
Embodiment 26 tyrosine L-phenylalanines 1.61 1.56 65
Embodiment 27 tyrosine L-phenylalanines 1.89 1.83 65
Embodiment 28 tyrosine L-phenylalanines 2.11 2.02 65
Embodiment 29 tyrosine L-phenylalanines 2.12 2.04 65
Claims (4)
1. method that in aqueous medium, prepares molecular blotting polymer microsphere, it is characterized in that it may further comprise the steps: (1) prepares material according to following prescription: the mol ratio of template molecule, function monomer and trimethylolpropane trimethacrylate is 1～3: 2～9: 71; Described function monomer is single function monomer or bi-functional monomer; The mol ratio of two kinds of components is 1: 1 in the described bi-functional monomer; The volume ratio of thinner and trimethylolpropane trimethacrylate is 1: 1.3～4; The cumulative volume of thinner and trimethylolpropane trimethacrylate and the volume ratio of water are 1: 5.7～6.8; The mass percent that Natvosol accounts for trimethylolpropane trimethacrylate is 0.83～1%; (2) Natvosol is placed water, be stirred to its whole dissolvings, and solution is heated to 65～80 ℃; (3) function monomer and template molecule are placed water; (4), stir with trimethylolpropane trimethacrylate, initiator and mixing diluents; (5) above-mentioned three kinds of solution are mixed, airtight behind the feeding nitrogen, stirred 6～10 hours in the constant speed of 65～80 ℃ of constant temperature with 300～400rpm; (6) polymkeric substance that above-mentioned reaction is obtained cleans with organic solvent earlier, uses the dilute acid soln wash-out again, to removing template molecule; (7) the polymkeric substance water that will remove template molecule cleans to neutral, dries at normal temperatures, promptly makes molecular blotting polymer microsphere; Described single function monomer is 2-acrylamide-2-methyl propane sulfonic acid or methacrylic acid; Described bi-functional monomer is any in the mixture of the mixture of mixture, methacrylic acid and acrylamide of 2-acrylamide-2-methyl propane sulfonic acid and acrylamide and 2-vinyl pyridine and 2-acrylamide-2-methyl propane sulfonic acid; Described template molecule is tyrosine or Cimitidine Type A/AB.
2. the method for preparing molecular blotting polymer microsphere in aqueous medium according to claim 1 is characterized in that, described thinner is any in toluene, tetracol phenixin and the acetonitrile.
3. the method for preparing molecular blotting polymer microsphere in aqueous medium according to claim 1 is characterized in that, described Heating temperature is 75 ℃.
4. the method for preparing molecular blotting polymer microsphere in aqueous medium according to claim 1 is characterized in that, the time of described feeding nitrogen is 3～8 minutes.
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| CN101817908B (en) * | 2010-02-04 | 2011-11-30 | 南京医科大学 | Preparation method of molecular imprinting polymer of PSD-95/nNOS uncoupler |
| CN102070753B (en) * | 2010-12-16 | 2013-10-16 | 公安部物证鉴定中心 | Brodifacoum (anticoagulation raticide) molecularly imprinted polymer and use thereof of as solid phase extraction agent |
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| CN105693960B (en) * | 2016-03-03 | 2018-07-17 | 华南师范大学 | A kind of preparation method of glutamic acid molecular imprinted polymer on surface silica gel microball |
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