CN103980443B - A kind of half covalent method prepares the method for wetting ability bisphenol A molecular engram polymer - Google Patents
A kind of half covalent method prepares the method for wetting ability bisphenol A molecular engram polymer Download PDFInfo
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Abstract
Adopting half covalent method to prepare a method for wetting ability bisphenol A molecular engram polymer, it relates to a kind of method preparing wetting ability bisphenol A molecular engram polymer. It is an object of the invention to be solved existing bisphenol A molecular engram polymer and the problem that product rate is low, site utilization ratio is low is existed for the poor selectivity of dihydroxyphenyl propane in water and adsorption efficiency is low and prepared by body half covalency polymerization molecularly imprinted polymer. The inventive method: one, silica gel activating; Two, silica gel connects double bond; Three, beta-cyclodextrin activation and modification; Four, it is polymerized. The present invention is mainly for the preparation of wetting ability bisphenol A molecular engram polymer.
Description
Technical field
The present invention relates to a kind of method preparing wetting ability bisphenol A molecular engram polymer.
Background technology
Dihydroxyphenyl propane (BPA) is most popular a kind of industrial raw material in the world, and meanwhile, as typical environment endocrine disrupter, dihydroxyphenyl propane can play the effect of the synthesis of interference human body inner estrogen. But in actual environmental sample, content of bisphenol A is few, complicated component, therefore before dihydroxyphenyl propane detects, it is necessary to sample is carried out pre-treatment. Molecularly imprinted polymer is because of its good special adsorption selection ability, and its long service life in addition, the advantage of the aspect such as practical, can be widely used in the field such as Solid-Phase Extraction and sensor. Therefore, molecular imprinting has very important significance in the separation and Extraction speed improving BPA in actual sample.
Molecular imprinting is for the preparation of the high molecular polymer that there is three-dimensional cavity, the hole shape of this polymkeric substance and the configuration of target molecule are identical, have in hole can and template molecule react the functional group of (such as covalent reaction or non-covalent reaction), therefore target molecule can be had special Selective adsorption by this polymkeric substance. Prepare molecularly imprinted polymer with half covalent method in recent years and become focus, because namely it combine the advantage that configuration is clear and special Selective adsorption is good of covalent method, combine again the advantage that the object release rate of non-covalence method is fast, in fact the method is by molecular self-assembling and pre-assembled combines, first template molecule and function monomer are combined by the mode of covalent linkage, by chemical process wash-out, be combined in the way of non covalent bond with function monomer residue wherein when template enters in trace chamber again. Bisphenol A molecular engram polymer prepared by tradition half covalent method, operates loaded down with trivial details, and Specific adsorption selectivity is low, and adsorption efficiency is poor, and recognition site utilization ratio is low.
At present, most molecularly imprinted polymer is because of synthetic materials and the character of self, comprise in practical application in preparation process and being all limited in organic solvent, there is situation according to dihydroxyphenyl propane in actual environment, the main problem that bisphenol A molecular engram polymer faces from now on is the bisphenol A molecular engram polymer that preparation can be applicable to water-based system. That has reported is roughly divided into two kinds, and one is be function monomer taking cyclodextrin because cyclodextrin can the performance of coated any small molecules, the molecularly imprinted polymer Specific adsorption selectivity that therefore prepared by the method is low; Another kind is grafting hydrophilic group, and grafting hydrophilic group can take too much binding site and cavity, and the molecularly imprinted polymer adsorption efficiency that therefore prepared by the method is low.
Summary of the invention
It is an object of the invention to be solved existing wetting ability bisphenol A molecular engram polymer and the problem that product rate is low, site utilization ratio is low is existed for the poor selectivity of dihydroxyphenyl propane and adsorption efficiency is low and prepared by body half covalent method molecularly imprinted polymer, thus provide a kind of half covalent method to prepare the method for wetting ability bisphenol A molecular engram polymer.
Half covalent method prepares a method for wetting ability bisphenol A molecular engram polymer, specifically completes according to the following steps:
One, silica gel activating: silica gel is scattered in the hydrochloric acid that massfraction is 1%��10%, 12h��24h is left standstill when temperature is 15 DEG C��25 DEG C, obtain solid reaction product, distilled water is utilized solid reaction product to be washed till filtrate in, till neutrality, obtaining neutral solid, the solid of neutrality is put into retort furnace, from room temperature to 350 DEG C��450 DEG C, and when temperature is 350 DEG C��450 DEG C roasting 10h��24h, be naturally down to room temperature, obtain activated silica gel; The quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 1%��10% is 1g:(5mL��10mL);
Two, silica gel connects double bond: add activated silica gel and vinyltrimethoxy silane that step one obtains in dry toluene, stirring at room temperature 12h��24h under nitrogen protection, the solid toluene wash obtained 6 times��8 times, finally dry 24h with vacuum drying oven when temperature is 60 DEG C��100 DEG C, obtain grafting silica gel; The quality of the activated silica gel described in step 2 is (1g��4g): 15mL with the ratio of the volume of dry toluene; The volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is (3��14): 4;
Three, beta-cyclodextrin activation and modification: beta-cyclodextrin and sodium hydroxide are added anhydrous N, in N '-dimethyl methane amide, 1h��3h is stirred at temperature is 15 DEG C��25 DEG C, filtrate is got in filtration, chlorallylene is dropwise added in filtrate, the condition lower magnetic force being 60 DEG C��90 DEG C in temperature stirs 8h��12h, naturally 1 DEG C��5 DEG C natural crystallize outs it are down to, filter residue is got in filtration, with methanol wash filter residue 6 times��8 times, obtain the beta-cyclodextrin processed, it is dry 8h��12h under the vacuum condition of 90 DEG C��110 DEG C in temperature by the beta-cyclodextrin processed, beta-cyclodextrin after being modified, the quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (1g��5g): 10mL, the quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (2g��5g): 100mL, the quality of the beta-cyclodextrin described in step 3 and the volume ratio of chlorallylene are (1g��5g): (1mL��3mL),
Four, it is polymerized: willBeta-cyclodextrin after grafting silica gel that methacrylic chloride, step 2 obtain and the modification that step 3 obtains joins in the round-bottomed flask that toluene is housed, 8h��12h is stirred when temperature is 15 DEG C��25 DEG C, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate again, mechanical stirring 18h��30h when being 55 DEG C��80 DEG C under nitrogen protection with temperature after ultrasonic disperse is even, obtains polymeric reaction product; Methyl alcohol is adopted polymeric reaction product to be carried out supersound washing 6 times��8 times, the sodium hydrate methanol solution that the solid obtained take concentration as 0.01mol/L��0.1mol/L carries out surname extraction for solvent, surname extraction 3d��5d, the extract obtained first adopts methanol wash, adopt distilled water wash again, finally adopting methanol wash again, the product after washing is vacuum-drying 24h��48h when temperature is 60 DEG C, obtains wetting ability bisphenol A molecular engram polymer; The quality of the grafting silica gel described in step 4 and the volume ratio of toluene are (2g��5g): 20mL; Described in step 4Quality and the volume ratio of toluene be (3g��7g): 400mL; The quality of the methacrylic chloride described in step 4 and the volume ratio of toluene are (1g��4g): 200mL; The quality of the beta-cyclodextrin after the modification described in step 4 and the volume ratio of toluene are (2g��5g): 20mL; The volume ratio of the Ethylene glycol dimethacrylate described in step 4 and toluene is (5��9): 20; The quality of the Diisopropyl azodicarboxylate described in step 4 and the volume ratio of toluene are (0.7g��1g): 200mL.
Described in step 4No. CAS be 2444-90-8.
Advantage of the present invention:
One, the wetting ability bisphenol A molecular engram polymer that prepared by the present invention uses firstAs template molecule, the advantage of this template molecule is the Na contained in template+O-Oh group in group specific activity dihydroxyphenyl propane is active high, easy and methacrylic chloride occurs reaction to generate stable covalency ligand complex, thus making molecularly imprinted polymer have hole profile clearly, the use of this template molecule simultaneously also thoroughly solves the problem that in practical application, the seepage of dihydroxyphenyl propane causes detected result inaccurate;
Two, the wetting ability bisphenol A molecular engram polymer that prepared by the present invention, use the close ester inner chamber of beta-cyclodextrin and the chlorine base of methacrylic chloride jointly to provide recognition site, overcome the shortcoming that existing dihydroxyphenyl propane imprinted material special adsorption selection ability is low and adsorption efficiency is low; The hydrophilic exocoel of beta-cyclodextrin, as hydrophilic radical, makes the molecularly imprinted polymer of preparation can be applicable to the absorption of dihydroxyphenyl propane in aqueous phase;
Three, the bisphenol A molecular engram polymer that prepared by the present invention uses surface molecule print technology, the bisphenol A molecular engram polymer prepared compared with conventional art thoroughly solve embedded dark, site utilization ratio is too low, the problem of particulate matter setting, and product rate height, adsorption rate height;
Four, the bisphenol A molecular engram polymer that prepared by the present invention adopts the method for half covalency, prepares profile clear, and each intermolecular combination is firm, and in holey crosslinking structure, this structure makes molecularly imprinted polymer have higher resolving power and adsorption rate;
Dihydroxyphenyl propane is had obvious Selective recognition ability by the wetting ability bisphenol A molecular engram polymer that five, prepared by the present invention, and the wetting ability bisphenol A molecular engram polymer prepared of the present invention can be good be applied in planar water dihydroxyphenyl propane, adsorption efficiency can reach more than 80%.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the activated silica gel that test one step one obtains;
Fig. 2 is the scanning electron microscope (SEM) photograph of the grafting silica gel that test one step 2 obtains;
Fig. 3 is the scanning electron microscope (SEM) photograph of the wetting ability bisphenol A molecular engram polymer of test one preparation;
Fig. 4 is the red spectrogram of Fourier, in figure, A represents the red spectrogram of Fourier of the activated silica gel that test one step one obtains, in figure, B represents the red spectrogram of Fourier of the grafting silica gel that test one step 2 obtains, and in figure, C represents the red spectrogram of Fourier of the wetting ability bisphenol A molecular engram polymer of test one preparation;
Fig. 5 is wetting ability bisphenol A molecular engram polymer ultrasonic disperse photo figure after 10min in water of test one preparation;
Fig. 6 tests a wetting ability bisphenol A molecular engram polymer prepared from dripping in water, the contact angle figure in 30 seconds;
Fig. 7 is curve of adsorption kinetics figure, and in figure, curve 1 represents the curve of adsorption kinetics of the wetting ability bisphenol A molecular engram polymer of test one preparation, and curve 2 represents the curve of adsorption kinetics of the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane;
Fig. 8 is adsorption selectivity column diagram, and A is capable represents dihydroxyphenyl propane, and B is capable represents phenol, and C is capable represents nonyl phenol, and 1 row represent the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane that test two obtains, and 2 row represent the wetting ability bisphenol A molecular engram polymer of test one preparation.
Embodiment
Embodiment one: present embodiment is a kind of method that half covalent method prepares wetting ability bisphenol A molecular engram polymer, specifically completes according to the following steps:
One, silica gel activating: silica gel is scattered in the hydrochloric acid that massfraction is 1%��10%, 12h��24h is left standstill when temperature is 15 DEG C��25 DEG C, obtain solid reaction product, distilled water is utilized solid reaction product to be washed till filtrate in, till neutrality, obtaining neutral solid, the solid of neutrality is put into retort furnace, from room temperature to 350 DEG C��450 DEG C, and when temperature is 350 DEG C��450 DEG C roasting 10h��24h, be naturally down to room temperature, obtain activated silica gel; The quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 1%��10% is 1g:(5mL��10mL);
Two, silica gel connects double bond: add activated silica gel and vinyltrimethoxy silane that step one obtains in dry toluene, stirring at room temperature 12h��24h under nitrogen protection, the solid toluene wash obtained 6 times��8 times, finally dry 24h with vacuum drying oven when temperature is 60 DEG C��100 DEG C, obtain grafting silica gel; The quality of the activated silica gel described in step 2 is (1g��4g): 15mL with the ratio of the volume of dry toluene; The volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is (3��14): 4;
Three, beta-cyclodextrin activation and modification: beta-cyclodextrin and sodium hydroxide are added anhydrous N, in N '-dimethyl methane amide, 1h��3h is stirred at temperature is 15 DEG C��25 DEG C, filtrate is got in filtration, chlorallylene is dropwise added in filtrate, the condition lower magnetic force being 60 DEG C��90 DEG C in temperature stirs 8h��12h, naturally 1 DEG C��5 DEG C natural crystallize outs it are down to, filter residue is got in filtration, with methanol wash filter residue 6 times��8 times, obtain the beta-cyclodextrin processed, it is dry 8h��12h under the vacuum condition of 90 DEG C��110 DEG C in temperature by the beta-cyclodextrin processed, beta-cyclodextrin after being modified, the quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (1g��5g): 10mL, the quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (2g��5g): 100mL, the quality of the beta-cyclodextrin described in step 3 and the volume ratio of chlorallylene are (1g��5g): (1mL��3mL),
Four, it is polymerized: willBeta-cyclodextrin after grafting silica gel that methacrylic chloride, step 2 obtain and the modification that step 3 obtains joins in the round-bottomed flask that toluene is housed, 8h��12h is stirred when temperature is 15 DEG C��25 DEG C, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate again, mechanical stirring 18h��30h when being 55 DEG C��80 DEG C under nitrogen protection with temperature after ultrasonic disperse is even, obtains polymeric reaction product; Methyl alcohol is adopted polymeric reaction product to be carried out supersound washing 6 times��8 times, the sodium hydrate methanol solution that the solid obtained take concentration as 0.01mol/L��0.1mol/L carries out surname extraction for solvent, surname extraction 3d��5d, the extract obtained first adopts methanol wash, adopt distilled water wash again, finally adopting methanol wash again, the product after washing is vacuum-drying 24h��48h when temperature is 60 DEG C, obtains wetting ability bisphenol A molecular engram polymer; The quality of the grafting silica gel described in step 4 and the volume ratio of toluene are (2g��5g): 20mL; Described in step 4Quality and the volume ratio of toluene be (3g��7g): 400mL; The quality of the methacrylic chloride described in step 4 and the volume ratio of toluene are (1g��4g): 200mL; The quality of the beta-cyclodextrin after the modification described in step 4 and the volume ratio of toluene are (2g��5g): 20mL; The volume ratio of the Ethylene glycol dimethacrylate described in step 4 and toluene is (5��9): 20; The quality of the Diisopropyl azodicarboxylate described in step 4 and the volume ratio of toluene are (0.7g��1g): 200mL.
The advantage of present embodiment:
One, the wetting ability bisphenol A molecular engram polymer that prepared by present embodiment uses firstAs template molecule, the advantage of this template molecule is the Na contained in template+O-Oh group in group specific activity dihydroxyphenyl propane is active high, easy and methacrylic chloride occurs reaction to generate stable covalency ligand complex, thus making molecularly imprinted polymer have hole profile clearly, the use of this template molecule simultaneously also thoroughly solves the problem that in practical application, the seepage of dihydroxyphenyl propane causes detected result inaccurate;
Two, the wetting ability bisphenol A molecular engram polymer that prepared by present embodiment, use the close ester inner chamber of beta-cyclodextrin and the chlorine base of methacrylic chloride jointly to provide recognition site, overcome the shortcoming that existing dihydroxyphenyl propane imprinted material special adsorption selection ability is low and adsorption efficiency is low; The hydrophilic exocoel of beta-cyclodextrin, as hydrophilic radical, makes the molecularly imprinted polymer of preparation can be applicable to the absorption of dihydroxyphenyl propane in aqueous phase;
Three, the wetting ability bisphenol A molecular engram polymer that prepared by present embodiment uses surface molecule print technology, the bisphenol A molecular engram polymer that relatively prepared by conventional art thoroughly solves and embedded deeply, and site utilization ratio is too low, the problem of particulate matter setting, and product rate height, adsorption rate height;
Four, the wetting ability bisphenol A molecular engram polymer that prepared by present embodiment adopts the method for half covalency, prepare profile clear, each intermolecular combination is firm, and in holey crosslinking structure, this structure makes this molecularly imprinted polymer have higher resolving power and adsorption rate;
Dihydroxyphenyl propane is had obvious Selective recognition ability by the wetting ability bisphenol A molecular engram polymer that five, prepared by present embodiment, and the wetting ability bisphenol A molecular engram polymer prepared of present embodiment can be good be applied in planar water dihydroxyphenyl propane, clearance can reach more than 80%.
Embodiment two: the difference of present embodiment and embodiment one is: to be particle diameter the be amorphous silica gel of 20 ��m��100 ��m of the silica gel described in step one or particle diameter are 20 ��m��100 ��m spherical silica gels. Other are identical with embodiment one.
Embodiment three: the difference of one of present embodiment and embodiment one or two is: the quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 1%��10% is 1g:(5.3mL��9.4mL). Other are identical with embodiment one or two.
Embodiment four: the difference of one of present embodiment and embodiment one to three is: the quality of the activated silica gel described in step 2 and the volume ratio of toluene are (2g��3g): 15mL. Other are identical with embodiment one to three.
Embodiment five: the difference of one of present embodiment and embodiment one to four is: the volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is (5��8): 4. Other are identical with embodiment one to four.
Embodiment six: the difference of one of present embodiment and embodiment one to five is: the quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (1g��2g): 5mL. Other are identical with embodiment one to five.
Embodiment seven: the difference of one of present embodiment and embodiment one to six is: the quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (3g��4g): 100mL. Other are identical with embodiment one to six.
Embodiment eight: the difference of one of present embodiment and embodiment one to seven is: the quality of the beta-cyclodextrin described in step 3 and the volume ratio of methyl alcohol are (1g��2g): 15mL. Other are identical with embodiment one to seven.
Embodiment nine: the difference of one of present embodiment and embodiment one to eight is: the quality of the grafting silica gel described in step 4 and the volume ratio of toluene are (3g��4g): 20mL. Other are identical with embodiment one to eight.
Embodiment ten: the difference of one of present embodiment and embodiment one to nine is: beta-cyclodextrin and the volume ratio of toluene after the modification described in step 4 are (3g��4g): 20mL. Other are identical with embodiment one to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: this test is a kind of method that half covalent method prepares wetting ability bisphenol A molecular engram polymer, specifically completes according to the following steps:
One, silica gel activating: the spherical silica gel that particle diameter is 50 ��m is scattered in the hydrochloric acid that massfraction is 10%, 24h is left standstill when temperature is 20 DEG C, obtain solid reaction product, distilled water is utilized solid reaction product to be washed till filtrate in, till neutrality, obtaining neutral solid, the solid of neutrality is put into retort furnace, from room temperature to 400 DEG C, and when temperature is 400 DEG C roasting 24h, be naturally down to room temperature, obtain activated silica gel; The quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 10% is 1g:10mL;
Two, silica gel connects double bond: add activated silica gel and vinyltrimethoxy silane that step one obtains in dry toluene, stirring at room temperature 24h under nitrogen protection, the solid toluene wash obtained 8 times, finally dries 24h with vacuum drying oven when temperature is 80 DEG C, obtains grafting silica gel; The quality of the activated silica gel described in step 2 is 3g:10mL with the ratio of the volume of dry toluene; The volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is 3:1;
Three, beta-cyclodextrin activation and modification: beta-cyclodextrin and sodium hydroxide are added anhydrous N, in N '-dimethyl methane amide, 1h is stirred at temperature is 20 DEG C, filtrate is got in filtration, chlorallylene is dropwise added in filtrate, the condition lower magnetic force being 80 DEG C in temperature stirs 12h, naturally 5 DEG C of natural crystallize outs it are down to, filter residue is got in filtration, with methanol wash filter residue 8 times, obtain the beta-cyclodextrin processed, it is dry 12h under the vacuum condition of 110 DEG C in temperature by the beta-cyclodextrin processed, the beta-cyclodextrin after being modified; The quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is 3g:10mL; The quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is 3g:100mL; The quality of the beta-cyclodextrin described in step 3 and the volume ratio of chlorallylene are 3g:2mL;
Four, wetting ability bisphenol A molecular engram polymer is prepared: willBeta-cyclodextrin after grafting silica gel that methacrylic chloride, step 2 obtain and the modification that step 3 obtains joins in the round-bottomed flask that toluene is housed, 12h is stirred when temperature is 20 DEG C, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate again, mechanical stirring 24h when being 60 DEG C with temperature under nitrogen protection after ultrasonic disperse is even, obtains polymeric reaction product; Adopt methyl alcohol that polymeric reaction product is carried out supersound washing 8 times, the sodium hydrate methanol solution that the solid obtained take concentration as 0.05mol/L carries out surname extraction for solvent, surname extraction 4d, the extract obtained first adopts methanol wash, adopt distilled water wash again, finally adopting methanol wash again, the product after washing is vacuum-drying 48h at 60 DEG C, obtains wetting ability bisphenol A molecular engram polymer; The quality of the grafting silica gel described in step 4 and the volume ratio of toluene are 3g:20mL; Described in step 4Quality and the volume ratio of toluene be 1g:80mL; The quality of the methacrylic chloride described in step 4 and the volume ratio of toluene are 3g:200mL; The quality of the beta-cyclodextrin after the modification described in step 4 and the volume ratio of toluene are 3g:20mL; The volume ratio of the Ethylene glycol dimethacrylate described in step 4 and toluene is 7:20; The quality of the Diisopropyl azodicarboxylate described in step 4 and the volume ratio of toluene are 0.7g:200mL.
Fig. 1 is 500 times of scanning electron microscope (SEM) photographs of the activated silica gel that test one step one obtains, and the silica gel that this test uses as shown in Figure 1 is spherical silica gel, and there is a small amount of impurity on surface.
Fig. 2 is 500 times of scanning electron microscope (SEM) photographs of the grafting silica gel that test one step 2 obtains, grafting silica gel surface relative smooth as shown in Figure 2, this is owing to silane coupling agent generates caused by rete in silica gel surface reaction, in simultaneous reactions process, silica gel surface impurity reduces to some extent under vigorous stirring, and this proves that silane coupling agent is successfully grafted on silica gel on the surface.
Fig. 3 is 40000 times of scanning electron microscope (SEM) photographs of the wetting ability bisphenol A molecular engram polymer of test one preparation, as shown in Figure 3, the spherical silica gel network that is made up of imprinted polymer microballoon of surface and hole structure and make its surface irregularity uneven, this illustrates that imprinted polymer has successfully been grafted to above silica gel.
Fig. 4 is the red spectrogram of Fourier, in figure, curve A is the red spectrogram of Fourier of the activated silica gel that test one step one obtains, curve B is the red spectrogram of Fourier of the grafting silica gel that test one step 2 obtains, and curve C represents the red spectrogram of Fourier of the wetting ability bisphenol A molecular engram polymer of test one preparation; From figure, curve A can draw, 3433.47cm-1For SiO2��H2In O planar water with the absorption vibration peak of-OH, 1634.61cm-1Place, 1096.67cm-1Place, 956.74cm-1, 801.75cm-1And 477.49cm-1It is respectively in silica gel H-O-H flexural vibration peak, the vibration absorption peak of Si-O-Si, Si-OH and Si-O. By in the infrared spectrum of correlation curve A and B, 956.74cm-1The vibration absorption peak of the Si-OH at place weakens, and this phenomenon is owing to, in grafting process, silica gel surface there occurs what hydrolysis-condensation reaction caused, meanwhile, and 3433.47cm-1Place weakens at peak to some extent, also illustrate that the success of silica gel surface grafting. In infrared spectrum curve C, add 2929.27cm-1, 1737.68cm-1, 1465.33cm-1, 1096.67cm-1Peak everywhere, this represents C-H stretching vibration peak in peak everywhere respectively, C=O double bond stretching vibration peak, and-OH absorbs vibration peak and C-O and C-C vibration peak. This is due to the methacryloyl unit in function monomer; ethylene glycol dimethacrylate unit in Ethylene glycol dimethacrylate and the C=O in ��-CD and-OH; meanwhile, in infrared spectrogram, the peak of phenyl ring does not occur, this pattern of descriptive parts molecule is by successful wash-out. By analyzing above and can draw, the bisphenol A molecular engram polymer of silica gel surface hydrophilicity is successfully prepared.
Fig. 5 is wetting ability bisphenol A molecular engram polymer ultrasonic disperse photo figure after 10min in water of test one preparation, can find out that wetting ability bisphenol A molecular engram polymer is dispersed in water uniformly, the good hydrophilic property of wetting ability bisphenol A molecular engram polymer prepared by this test is described.
Fig. 6 is that the wetting ability bisphenol A molecular engram polymer testing a preparation is from dripping in water, contact angle figure in 30 seconds, as can be seen from the figure the wetting ability bisphenol A molecular engram polymer of this test preparation drops to 7.5 �� from 84.81 �� along with time contact angle, contact angle is less than 90 ��, wetting ability bisphenol A molecular engram polymer good hydrophilic property prepared by this test is described, linearly fabulous, this is because the wetting ability of wetting ability bisphenol A molecular engram polymer is better, water droplet drops on imprinted material can drawout rapidly, in the document that contrast has been delivered, contact angle data are provable, the wetting ability bisphenol A molecular engram polymer wetting ability of this test preparation is extremely good.
Test two: prepare the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane: this test is a kind of method that half covalent method prepares the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane, specifically completes according to the following steps:
One, silica gel activating: the spherical silica gel that particle diameter is 50 ��m is scattered in the hydrochloric acid that massfraction is 10%, 24h is left standstill when temperature is 20 DEG C, obtain solid reaction product, distilled water is utilized solid reaction product to be washed till filtrate in, till neutrality, obtaining neutral solid, the solid of neutrality is put into retort furnace, from room temperature to 400 DEG C, and when temperature is 400 DEG C roasting 24h, be naturally down to room temperature, obtain activated silica gel; The quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 10% is 1g:10mL;
Two, silica gel connects double bond: add activated silica gel and vinyltrimethoxy silane that step one obtains in dry toluene, stirring at room temperature 24h under nitrogen protection, the solid toluene wash obtained 8 times, finally dries 24h with vacuum drying oven when temperature is 80 DEG C, obtains grafting silica gel; The quality of the activated silica gel described in step 2 is 3g:10mL with the ratio of the volume of dry toluene; The volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is 3:1;
Three, beta-cyclodextrin activation and modification: beta-cyclodextrin and sodium hydroxide are added anhydrous N, in N '-dimethyl methane amide, 1h is stirred at temperature is 20 DEG C, filtrate is got in filtration, chlorallylene is dropwise added in filtrate, the condition lower magnetic force being 80 DEG C in temperature stirs 12h, naturally 5 DEG C of natural crystallize outs it are down to, filter residue is got in filtration, with methanol wash filter residue 8 times, obtain the beta-cyclodextrin processed, it is dry 12h under the vacuum condition of 110 DEG C in temperature by the beta-cyclodextrin processed, the beta-cyclodextrin after being modified; The quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is 3g:10mL; The quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is 3g:100mL; The quality of the beta-cyclodextrin described in step 3 and the volume ratio of chlorallylene are 3g:2mL;
Four, it is polymerized: the beta-cyclodextrin after the modification that grafting silica gel methacrylic chloride, step 2 obtained and step 3 obtain joins in the round-bottomed flask that toluene is housed, 12h is stirred when temperature is 20 DEG C, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate again, mechanical stirring 24h when being 60 DEG C with temperature under nitrogen protection after ultrasonic disperse is even, obtains polymeric reaction product; Adopt methyl alcohol that polymeric reaction product is carried out supersound washing 8 times, the sodium hydrate methanol solution that the solid obtained take concentration as 0.05mol/L carries out surname extraction for solvent, surname extraction 4d, the extract obtained first adopts methanol wash, adopt distilled water wash again, finally adopting methanol wash again, the product after washing is vacuum-drying 48h at 60 DEG C, obtains wetting ability bisphenol A molecular engram polymer; The quality of the grafting silica gel described in step 4 and the volume ratio of toluene are 3g:20mL; The quality of the methacrylic chloride described in step 4 and the volume ratio of toluene are 3g:200mL; The quality of the beta-cyclodextrin after the modification described in step 4 and the volume ratio of toluene are 3g:20mL; The volume ratio of the Ethylene glycol dimethacrylate described in step 4 and toluene is 7:20; The quality of the Diisopropyl azodicarboxylate described in step 4 and the volume ratio of toluene are 0.7g:200mL.
Test three: adsorptive power detects:
The every part of quality taking 11 parts respectively is the wetting ability bisphenol A molecular engram polymer of test one preparation of 20mg, then join in the dihydroxyphenyl propane acetonitrile solution that the concentration that every part of 11 parts is 10mL is 0.5mmol/L respectively, shake in case at constant temperature and shake 2 respectively, 5, 10, 15, 20, 30, 40, 60, 80, 120, 150min, supernatant liquor carries out after centrifugal ultraviolet spectrophotometer survey detect, three times measure average and by formula: Q=V (Co-Ct)/M is to calculate adsorptive capacity, wherein Co is the starting point concentration (mg/L) of BPA in solution, Ct is the concentration (mg/L) of the BPA in solution when absorption reaches balance, V is liquor capacity (L), M is the quality (g) of wetting ability bisphenol A molecular engram polymer.
The every part of quality taking 11 parts respectively is the non-molecularly imprinted polymers of wetting ability dihydroxyphenyl propane of test two preparation of 20mg, join in the dihydroxyphenyl propane acetonitrile solution that the concentration that every part of 11 parts is 10mL is 0.5mmol/L respectively, shake in case at constant temperature and shake 2 respectively, 5, 10, 15, 20, 30, 40, 60, 80, 120, 150min, supernatant liquor carries out after centrifugal ultraviolet spectrophotometer survey detect, three times measure average and by formula: Q=V (Co-Ct)/M is to calculate adsorptive capacity, wherein Co is the starting point concentration (mg/L) of BPA in solution, Ct is the concentration (mg/L) of the BPA in solution when absorption reaches balance, V is liquor capacity (L), M is the quality (g) of the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane.
Fig. 7 is curve of adsorption kinetics figure, and in figure, curve 1 represents the curve of adsorption kinetics of the wetting ability bisphenol A molecular engram polymer of test one preparation, and curve 2 represents the curve of adsorption kinetics of the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane of test two preparation, as seen in Figure 7, when the concussion time is 0��15min, the adsorptive capacity of dihydroxyphenyl propane is increased by wetting ability bisphenol A molecular engram polymer and the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane along with the increase of time, to arriving adsorption equilibrium during 15min, now dihydroxyphenyl propane is had the adsorptive capacity of 8.3mg/g by wetting ability bisphenol A molecular engram polymer, and dihydroxyphenyl propane is only had 2.3mg/g adsorptive capacity by the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane, therefore dihydroxyphenyl propane is had Specific adsorption selectivity by wetting ability bisphenol A molecular engram polymer, the adsorptive power of wetting ability bisphenol A molecular engram polymer is far above the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane, from figure, we also can find out, it is that these two imprinted polymers of about 15min reach adsorption equilibrium in the concussion time, therefore we reach a conclusion, time of equilibrium adsorption and molecular imprinting surface cross-linked network shape looks have direct relation, good surface topography is conducive to the rate of mass transfer accelerated between recognition site and template molecule, namely surface topography is more good, and adsorption equilibrium required time is more short, otherwise more long.
Test three: have selected 2 kinds of phenolic comp ' ds pollution phenol similar to dihydroxyphenyl propane molecular structure and nonyl phenol for competing molecule.
The wetting ability bisphenol A molecular engram polymer taking 20mg test one preparation add three are equipped with dihydroxyphenyl propane acetonitrile solution that 10mL concentration is 0.05mmol/L, 10mL concentration is 0.05mmol/L phenol acetonitrile solution respectively and 10mL concentration be 0.05mmol/L the plastic centrifuge tube of nonyl phenol acetonitrile solution in, room temperature concussion 12h, centrifugal, ultraviolet, survey supernatant, the adsorption efficiency of wetting ability bisphenol A molecular engram polymer can be calculated. The calculation formula of adsorption efficiency E (%) can represent: E=(Co-Cp)/Co, and wherein Co is the starting point concentration (mg/L) of dihydroxyphenyl propane in solution; Cp is the concentration (mg/L) of the dihydroxyphenyl propane in solution when absorption reaches balance.
The non-molecularly imprinted polymers of wetting ability dihydroxyphenyl propane taking 20mg test two preparation add three are equipped with dihydroxyphenyl propane acetonitrile solution that 10mL concentration is 0.05mmol/L, 10mL concentration is 0.05mmol/L phenol acetonitrile solution respectively and 10mL concentration be 0.05mmol/L the plastic centrifuge tube of nonyl phenol acetonitrile solution in, room temperature concussion 12h, centrifugal, ultraviolet, survey supernatant, the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane can be calculated to the adsorption efficiency of three kinds of molecules. The calculation formula of adsorption efficiency E (%) can represent: E=(Co-Cp)/Co, and wherein Co is the starting point concentration (mg/L) of dihydroxyphenyl propane in solution; Cp is the concentration (mg/L) of the dihydroxyphenyl propane in solution when absorption reaches balance.
Fig. 8 is adsorption selectivity column diagram, A is capable represents dihydroxyphenyl propane, B is capable represents phenol, C is capable represents nonyl phenol, 1 row represent the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane that test two obtains, 2 row represent the wetting ability bisphenol A molecular engram polymer of test one preparation, as can be seen from Figure 8, the clearance of competition molecule phenol and nonyl phenol is respectively 26.15% and 21.73% by the wetting ability bisphenol A molecular engram polymer of test one preparation, to template molecule clearance then up to 83.14%, this illustrates that template molecule is had obvious Selective recognition ability by the wetting ability bisphenol A molecular engram polymer of test one preparation. and the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane is very low and close to the clearance of three kinds of materials, being respectively 32.64%, 24.17%, 18.53%, this illustrates that dihydroxyphenyl propane is not had Selective recognition ability by the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane. this is because after wetting ability bisphenol A molecular engram polymer eluted template molecule dihydroxyphenyl propane, imprinted polymer has the hole mated mutually with dihydroxyphenyl propane molecular configuration formed, the recognition site to dihydroxyphenyl propane adsorption selection is there is in this hole, in adsorption process, absorption is played an important role by recognition site. but the non-molecularly imprinted polymer of wetting ability dihydroxyphenyl propane does not have hole and recognition site, therefore dihydroxyphenyl propane molecule can not be carried out effective selective recognition.
Claims (10)
1. one and half covalent methods prepare the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that the method that half covalent method prepares wetting ability bisphenol A molecular engram polymer completes according to the following steps:
One, silica gel activating: silica gel is scattered in the hydrochloric acid that massfraction is 1%��10%, 12h��24h is left standstill when temperature is 15 DEG C��25 DEG C, obtain solid reaction product, distilled water is utilized solid reaction product to be washed till filtrate in, till neutrality, obtaining neutral solid, the solid of neutrality is put into retort furnace, from room temperature to 350 DEG C��450 DEG C, and when temperature is 350 DEG C��450 DEG C roasting 10h��24h, be naturally down to room temperature, obtain activated silica gel; The quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 1%��10% is 1g:(5mL��10mL);
Two, silica gel connects double bond: add activated silica gel and vinyltrimethoxy silane that step one obtains in dry toluene, stirring at room temperature 12h��24h under nitrogen protection, the solid toluene wash obtained 6 times��8 times, finally dry 24h with vacuum drying oven when temperature is 60 DEG C��100 DEG C, obtain grafting silica gel; The quality of the activated silica gel described in step 2 is (1g��4g): 15mL with the ratio of the volume of dry toluene; The volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is (3��14): 4;
Three, beta-cyclodextrin activation and modification: beta-cyclodextrin and sodium hydroxide are added anhydrous N, in N '-dimethyl methane amide, 1h��3h is stirred at temperature is 15 DEG C��25 DEG C, filtrate is got in filtration, chlorallylene is dropwise added in filtrate, the condition lower magnetic force being 60 DEG C��90 DEG C in temperature stirs 8h��12h, naturally 1 DEG C��5 DEG C natural crystallize outs it are down to, filter residue is got in filtration, with methanol wash filter residue 6 times��8 times, obtain the beta-cyclodextrin processed, it is dry 8h��12h under the vacuum condition of 90 DEG C��110 DEG C in temperature by the beta-cyclodextrin processed, beta-cyclodextrin after being modified, the quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (1g��5g): 10mL, the quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (2g��5g): 100mL, the quality of the beta-cyclodextrin described in step 3 and the volume ratio of chlorallylene are (1g��5g): (1mL��3mL),
Four, it is polymerized: willBeta-cyclodextrin after grafting silica gel that methacrylic chloride, step 2 obtain and the modification that step 3 obtains joins in the round-bottomed flask that toluene is housed, 8h��12h is stirred when temperature is 15 DEG C��25 DEG C, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate again, mechanical stirring 18h��30h when being 55 DEG C��80 DEG C under nitrogen protection with temperature after ultrasonic disperse is even, obtains polymeric reaction product; Methyl alcohol is adopted polymeric reaction product to be carried out supersound washing 6 times��8 times, the sodium hydrate methanol solution that the solid obtained take concentration as 0.01mol/L��0.1mol/L carries out surname extraction for solvent, surname extraction 3d��5d, the extract obtained first adopts methanol wash, adopt distilled water wash again, finally adopting methanol wash again, the product after washing is vacuum-drying 24h��48h when temperature is 60 DEG C, obtains wetting ability bisphenol A molecular engram polymer; The quality of the grafting silica gel described in step 4 and the volume ratio of toluene are (2g��5g): 20mL; Described in step 4Quality and the volume ratio of toluene be (3g��7g): 400mL; The quality of the methacrylic chloride described in step 4 and the volume ratio of toluene are (1g��4g): 200mL; The quality of the beta-cyclodextrin after the modification described in step 4 and the volume ratio of toluene are (2g��5g): 20mL; The volume ratio of the Ethylene glycol dimethacrylate described in step 4 and toluene is (5��9): 20; The quality of the Diisopropyl azodicarboxylate described in step 4 and the volume ratio of toluene are (0.7g��1g): 200mL.
2. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that to be particle diameter the be amorphous silica gel of 20 ��m��100 ��m of the silica gel described in step one or particle diameter are the spherical silica gel of 20 ��m��100 ��m.
3. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that the quality of the silica gel described in step one and massfraction are the volume ratio of the hydrochloric acid soln of 1%��10% is 1g:(5.3mL��9.4mL).
4. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that the quality of the activated silica gel described in step 2 and the volume ratio of toluene are (2g��3g): 15mL.
5. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that the volume ratio of the vinyltrimethoxy silane described in step 2 and toluene is (5��8): 4.
6. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterized in that the quality of the beta-cyclodextrin described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (1g��2g): 5mL.
7. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterized in that the quality of the sodium hydroxide described in step 3 and anhydrous N, the volume ratio of N '-dimethyl methane amide is (3g��4g): 100mL.
8. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that the quality of the beta-cyclodextrin described in step 3 and the volume ratio of methyl alcohol are (1g��2g): 15mL.
9. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that the quality of the grafting silica gel described in step 4 and the volume ratio of toluene are (3g��4g): 20mL.
10. a kind of half covalent method according to claim 1 prepares the method for wetting ability bisphenol A molecular engram polymer, it is characterised in that beta-cyclodextrin and the volume ratio of toluene after the modification described in step 4 are (3g��4g): 20mL.
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