CN104001486A - Preparation method of hydrophilic sulfa drug molecularly imprinted solid-phase extraction column - Google Patents
Preparation method of hydrophilic sulfa drug molecularly imprinted solid-phase extraction column Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical detection, and particularly relates to a preparation method of a hydrophilic sulfa drug molecularly imprinted solid-phase extraction column. The preparation method of the hydrophilic sulfa drug molecularly imprinted solid-phase extraction column comprises the following steps: (1) synthesizing a hydrophilic sulfa molecularly imprinted polymer by a bulk polymerization method; (2) characterizing the imprinted polymer obtained in the step (1), and determining the presence of an imprinted binding site; and (3) filling in the polypropylene solid-phase extraction column. The prepared hydrophilic solid-phase extraction column has powerful adsorption function, relatively strong specificity, high recovery rate and relatively low preparation cost, besides, improves the disadvantage of large required solvent amount in a traditional sample pretreatment technology, can be directly used for detection of ten sulfa veterinary drugs in animal-derived foods, and has the characteristics of high selective adsorption and high-efficiency enrichment on the sulfa drugs; and moreover, the solid-phase extraction column can be used for detection of sulfa veterinary drugs in a completely aqueous phase.
Description
Technical field
The invention belongs to chemical detection technique field, be specifically related to a kind of preparation method of hydrophily sulfa drugs molecularly imprinted solid phase extraction column, especially its in animal derived food to the enrichment of sulfamethyldiazine, sulfamethazine, sulphathiazole, sulfamethyldiazine, sulfadoxine, cistosulfa, 5-methoxysulfadiazine, sinomin, 10 kinds of sulfa drugs of kynix and NU-445 with separate.
Background technology
Sulfonamides is one of antimicrobial of current use amount maximum; be widely used for protection and controlled biological disease with its wide spectrum, the feature that efficient, consumption is few; but there is at present research to point out that excessive use Sulfonamides can cause its residual in edible tissue; and then the health of human body is produced to harm; for example, allergic reaction, the harm that suppresses Leukocytopoiesis and urinary system etc.So, increasing scholar's concern that the residue detection in food produces height to it.In order to ensure the healthy of the security of food and the mankind, it is residual that many countries have customized in food the maximum limitation of Sulfonamides in the world, and wherein European Union and China specify that the total amount of Sulfonamides in food can not exceed 100 μ g/L.
Residual in food of Sulfonamides is trace, due to the complexity of food substrate, when Sulfonamides is detected, needs more complicated pretreatment process simultaneously, brought certain difficulty to the detection of sample.At present Sulfonamides being detected to the maximum pre-treating method of application is SPE.But current solid-phase extraction column exist poor specificity, in a large number with an organic solvent, the shortcoming such as complex steps, bioaccumulation efficiency be poor.Molecular imprinting is to have one of method of high selectivity, high adsorption molecular material according to the principle preparation of bionic antibody.For Sulfonamides molecular imprinting, current preparation method is prepared in organic phase, and the adsorptivity in water is poor.And the prepared molecularly imprinted polymer of method can only be confined to that a certain Sulfonamides is had to special adsorptivity at present.So, study and a kind ofly can have compared with profound significance with the molecularly imprinted solid phase extraction column separating for multiple Sulfonamides enrichment in complete water.
At present about the invention of sulfa drugs molecularly imprinted solid phase extraction column has two, one is the method (application publication number: CN102344527A) of utilizing molecularly imprinted polymer purifying sulpha drugs, and another is preparation method and the application (application publication number: CN103289005A) of sulfa drugs molecular imprinted solid phase extraction cartridge.Prepared sulfa drugs molecularly imprinted polymer in these two inventions, can only detect 3 kinds of sulfa drugs, and can not be completely for the detection of aqueous sample.
Summary of the invention
Having the object of the invention is to overcome the shortcoming of traditional solid phase extraction techniques, is the preparation method who has been to provide a kind of hydrophily sulfa drugs molecularly imprinted solid phase extraction column.The prepared hydrophily solid-phase extraction column of the method has powerful adsorption function, the stronger high and lower preparation cost of specificity, the rate of recovery, has improved the large shortcoming of required quantity of solvent of traditional Sample Pretreatment Technique simultaneously.
Another object of the present invention be to provide a kind of hydrophily sulfa drugs molecularly imprinted solid phase extraction column in animal derived food to sulfamethazine, sulphadiazine, sulfamethyldiazine, the application that other sulfa drugs such as sulphathiazole detect, experimental results show that, this solid-phase extraction column can be directly used in sulfamethazine in animal derived food, sulphadiazine, sulfamethyldiazine, sulphathiazole, sulfadoxine, 5-methoxysulfadiazine, sinomin, ten kinds of sulfa drugs of kynix NU-445 and cistosulfa, it has the feature of high selectivity absorption and efficiently concentrating to sulfa drugs, and, this solid-phase extraction column can be for the detection of Sulfonamides in complete water.
The present invention realizes by following scheme:
A preparation method for hydrophily sulfa drugs molecularly imprinted solid phase extraction column, comprises the steps:
(1), first by template molecule, function monomer and crosslinking agent, mix according to the ratio of mol ratio 0.1:4:6, by mass polymerization synthesis hydrophilic sulfamido molecularly imprinted polymer;
(2) imprinted polymer of step (1) gained is characterized, determine the existence of trace binding site;
(3) take sulfa drugs molecularly imprinted polymer particulate 0.050-0.200g, be filled in the polypropylene solid-phase extraction column of 5mL, load onto respectively polyethylene sieve plate at the two ends of filler, sieve plate is covered tightly, to obtain final product.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described template molecule is sulfamethazine and sulphathiazole, and both molar ratios are 1:1.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described function monomer is methacrylic acid (MAA) and hydrophily function monomer hydroxyethyl methacrylate (HEMA), and both molar ratios are 1:1; Described crosslinking agent is ethylene glycol dimethacrylate and 3-(trimethoxysilyl) a kind of in propyl group acrylate or two kinds.。
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described characterizing method comprises Dynamic Adsorption, Static Adsorption and specific adsorption.
The main implementation step of above-mentioned Staticadsorption experiment, Dynamic Adsorption experiment and specific adsorption is as follows:
1) Staticadsorption experiment: using the aqueous solution of the sulfamethazine of 30mg/L as adsorption liquid, accurately take 5 parts of the molecularly imprinted polymers of 25mg, add the adsorption liquid of 5mL, 5min, 10min, 30min, 120min, 240min vibrate respectively.Centrifugation, gets supernatant, under 268nm condition, on ultraviolet-visible spectrophotometer, measure supernatant in the concentration of sulfamethazine.
2) Dynamic Adsorption experiment: the volumetric flask that accurately takes 25mg hydrophily sulfonamide molecularly imprinted polymer and be placed in 25mL, add respectively the sulfamethazine aqueous solution of 5mL variable concentrations, after shaking table vibration 30min, centrifugation, under 268nm condition, test supernatant in the concentration of sulfamethazine.And simultaneously parallelly do non-imprinted polymer and do control experiment.To the mapping of template molecule concentration, draw isothermal adsorption curve with adsorbance.
3) specific adsorption experiment: select the MTMC with template molecule structural similarity, chlorine sulphur is grand, estriol is as the competition thing of sulfa drugs, accurately take imprinted polymer and the non-imprinted polymer of 25.00 mg, be placed in the volumetric flask of 25 mL, respectively add the sulphathiazole of 10 mg/L, sulphadiazine, sulfamethazine, sulfamethyldiazine, NU-445, kynix, 5-methoxysulfadiazine, MTMC, mixed aqueous solution 5 mL of the grand and estriol of chlorine sulphur, centrifugal 15 min of 3000 rpm after 30 min vibrate, each analyte concentration record supernatant on HPLC-DAD detector in, recording wavelength sulfa drugs is 270 nm, MTMC is 210 nm, estriol and chlorine sulphur are grand is 230 nm.According to the comparison of supernatant and concentration of standard solution before and after absorption, calculate adsorbance, distribution coefficient (Kd), selectivity factor (K) and the relative selectivity coefficient (K) of every kind of material.
In the preparation method of above-mentioned hydrophily Sulfonamides molecularly imprinted solid phase extraction column, the preparation process of described hydrophily sulfa drugs molecularly imprinted polymer is as follows:
(1) using the sulphathiazole of the sulfamethazine of 0.05mmol and 0.05mmol as template, be dissolved in pore-foaming agent, by mixed solution ultrasonic degas, it is mixed;
(2) the function monomer methacrylic acid of 2mmol is joined in the prepared even mixed liquor of step (1), on oscillator, vibrate, obtain prepolymerization system;
(3) in step 2) add hydrophily function monomer hydroxyethyl methacrylate (HEMA), vibration 1h in the prepolymerization system that obtains; Then add crosslinking agent, vibration 1h; Finally add initator, vibration 0.5h, passes into nitrogen deoxygenation 5min, and at the atmosphere lower seal of nitrogen;
(4) bathe 24h at 60 DEG C of Water Unders, heat causes the described polymerization system of step (3), obtains the block molecularly imprinted polymer of hydrophily sulfonamide;
(5) after being ground, the block molecularly imprinted polymer of gained in step (4) sieves, sub-sieve obtains the particle diameter between 30-60 μ m, underproof particle is removed, wrap up with qualitative filter paper, then in apparatus,Soxhlet's, the extractant with 250 mL extracts 50h-110h, then use hydrochloric acid and the methanol wash 5h of 1mmol, dry to constant weight for 75 DEG C, obtain imprinted polymer particle.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described pore-foaming agent is acetonitrile, and its consumption is 6mL.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, the speed of described vibration is 160 turn/min, and duration of oscillation is 3h.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described hydrophily function monomer is hydroxyethyl methacrylate (HEMA), and its consumption is 2mmol.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described crosslinking agent is the ethyleneglycol dimethacrylate (EDMA) of 3mmol and the 3-(trimethoxysilyl of 3mmol) propyl group acrylate (γ-MAPS), described initator is azodiisobutyronitrile (AIBN), and consumption is 25mg.
In the preparation method of above-mentioned hydrophily sulfa drugs molecularly imprinted solid phase extraction column, described extractant is that volume ratio is methyl alcohol and the formic acid mixed solution of 9:1.
In use, the using method of hydrophily sulfa drugs molecularly imprinted solid phase extraction column of the present invention is as follows:
1) by after SPE column filling, with the methyl alcohol of 3mL and the activation of the water of 3mL and balance solid-phase extraction column;
2), under the condition vacuumizing, add sample 50mL;
3), with the distilled water drip washing solid-phase extraction column of 3mL, remove object and other impurity of not being adsorbed;
4) by the methanol-eluted fractions of 3mL 1 time, collect eluent, to be detected.
Beneficial effect of the present invention is:
(1) the prepared hydrophily sulfa drugs molecularly imprinted solid phase extraction column of the present invention all has specific adsorption function to sulfa drugs in sulphathiazole, sulfamethazine, sulfamethyldiazine, sulphadiazine, sulfadoxine, cistosulfa, 5-methoxysulfadiazine, kynix, sulfamoxole and NU-445 10, can be for this retention analysis of ten kinds of Sulfonamides in animal derived food.
(2) hydrophily sulfa drugs molecularly imprinted solid phase extraction column of the present invention can be for the retention analysis of sulfa drugs in the sample of complete water sample, the synthetic non-hydrophilic material of conventional method all carries out in whole testing process in organic solvent, solvent used can be up to milliliters up to a hundred, and the prepared hydrophilic material of this method does not need to use organic solvent in testing process, all can in the aqueous solution, carry out, solve the large difficult problem of organic solvent use amount in traditional detection method.
(3) the more commercial solid-phase extraction column of hydrophily sulfa drugs molecularly imprinted solid phase extraction column of the present invention, for example C18, neutral alumina, Oasis HLB solid-phase extraction column is compared, its synthetic cost is lower, and can recycled for multiple times, solve high price and a disposable difficult problem for commercialization solid-phase extraction column.
Brief description of the drawings
The curve of adsorption kinetics of the aqueous solution of the sulfamethazine of Fig. 1: 5mL30mg/L on 25mg molecular engram material
Fig. 2: imprinted polymer and the non-imprinted polymer isothermal adsorption curve to sulfamethazine
Fig. 3: the Scatchard of imprinted polymer and non-imprinted polymer analyzes.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
(1) preparation of hydrophily sulfanilamide (SN) molecularly imprinted polymer
First the sulphathiazole of the sulfamethazine of 0.05mmol and 0.05mmol is dissolved in the acetonitrile of 6mL, after ultrasonic 15min, adds the function monomer methacrylic acid of 2mmol.On oscillator, with the speed oscillation 3h of 160 turn/min, form pre-polymer solution.Subsequently, in above-mentioned pre-polymer solution system, add after 2mmol hydrophily function monomer hydroxyethyl methacrylate (HEMA) vibration 1h; Then add crosslinking agent (the 3-(trimethoxysilyl of the ethyleneglycol dimethacrylate of 3mmol and 3mmol) the propyl group acrylate of 6mmol), vibration 1h; Finally add the initator azodiisobutyronitrile (AIBN) of 25mg, vibration 0.5h.Pass into nitrogen deoxygenation 5min, and at the atmosphere lower seal of nitrogen; Under 60 DEG C of conditions of water-bath, by thermal-initiated polymerization, the water-bath time is 24h.After finishing, reaction obtains bulk polymer.After polymer is ground, with qualitative filter paper parcel, be then methyl alcohol with apparatus,Soxhlet's extraction 80h(extractant: formic acid is 9:1), until detect without template molecule.Then use the hydrochloric acid of 20mL1mmol and the methanol wash 5h of 20mL, dry to constant weight for 75 DEG C, obtain imprinted polymer particle.The preparation of non-imprinted polymer is not except adding template molecule, and other step is identical with above-mentioned steps.
(2) sign of hydrophilic molecular imprinting polymer
2.1 using the aqueous solution of the sulfamethazine of 30mg/L as adsorption liquid, accurately takes 5 parts of the molecularly imprinted polymers of 25mg, adds the adsorption liquid of 5mL, and 5min, 10min, 30min, 120min, 240min vibrate respectively.Centrifugation, gets supernatant, under 270nm condition, on ultraviolet-visible spectrophotometer, measure supernatant in the concentration of sulfamethazine.As shown in Figure 1, the synthetic imprinted polymer of this method has the good rate of adsorption and mass transfer rate to sulfamethazine.In the time that adsorption time is 5min, adsorbance is saturated extent of adsorption 51.25%; In the time that adsorption time is 30min, adsorbance 91.19% of the adsorbance that can reach capacity, reaches adsorption equilibrium substantially.And the synthetic polymer of conventional method reach adsorption equilibrium time need several hours, the method has shortened adsorption time greatly, has obviously improved the mass transfer rate of material.
In order to determine the rate-limiting step of polymer in adsorption process, the data of experiment gained are carried out to one-level adsorption dynamics adsorption kinetics, secondary absorption dynamics, particle diffusion equation and the simulation of Elovich equation curve.Data are brought in each equation, pass through R
2size judge whether whether analog result conform to theoretical model.Analog result is in table 1.Its curve of adsorption kinetics is shown in Fig. 1.
As shown in Table 1, compared with other model, the linear dependence of secondary absorption dynamics simulation curve is best, can reach R
2be 0.9985, present utmost point significant correlation level.Accurate secondary absorption kinetic model is thought, in adsorption process, two reactions can occur: the one, reach fast the reaction of balance, and the 2nd, the long response time in whole reaction time of control, these two reactions may be carried out successively, also may carry out simultaneously.
2.2 accurately take 25mg hydrophily sulfonamide molecularly imprinted polymer is placed in the volumetric flask of 25mL, add respectively the sulfamethazine aqueous solution of 5mL variable concentrations, after shaking table vibration 30min, centrifugation, under 270nm condition, test supernatant in the concentration of sulfamethazine.And simultaneously parallelly do non-imprinted polymer and do control experiment.To the mapping of template molecule concentration, draw isothermal adsorption curve with adsorbance.Adsorption equilibrium curve as shown in Figure 2, as seen from Figure 2, when the concentration of adsorption liquid is during in very low concentration range, the adsorbance difference of imprinted polymer and non-imprinted polymer is less, but along with the increase of adsorption liquid concentration, both adsorbances all have increase in various degree, and its difference is also more and more obvious.In the time that the concentration of the sulfamethazine aqueous solution is 30mg/L, the adsorbance of imprinted polymer is 0.658mg/g, the adsorbance of non-imprinted polymer is 0.232mg/g, and the adsorbance of imprinted polymer is approximately 2.83 times of non-imprinted polymer adsorbance, illustrates that the trace effect of this material is better.
2.3 Scatchard analyze
Obtained data are analyzed for the Scatchard of imprinted polymer and non-imprinted polymer.Analysis result is shown in Fig. 3.
Scatchard equation: Q/C=Q/b+Qmax/b
In equation, C refers to the initial concentration of solution, adsorption capacity when Q refers to reach adsorption equilibrium, and Qmax refers to maximum saturation adsorption capacity, with Q/C, Q is mapped and obtains Scatchard equation.Can be obtained Qmax and the Kd of polymer by Scatchard slope of a curve and intercept.
As seen from the figure, the Scatchard of imprinted polymer is a curve that linearity is good, and regression equation is y=-0.0024x+0.0273, and coefficient correlation is 0.9924.Wherein, Qmax is 11.37mg/g, and Kd is 4.17mg/mL.Illustrate that the synthetic imprinted polymer of the method has certain binding site, has specific absorption affinity to template molecule.But not imprinted polymer is due to the scrambling in conjunction with strength, so can not get linear equation.
2.4 competitive Adsorption experiments
Select the MTMC with template molecule structural similarity, chlorine sulphur is grand, estriol is as the competition thing of sulfa drugs, accurately take imprinted polymer and the non-imprinted polymer of 25.00 mg, be placed in the volumetric flask of 25 mL, respectively add the sulphathiazole of 10 mg/L, sulphadiazine, sulfamethazine, sulfamethyldiazine, NU-445, kynix, 5-methoxysulfadiazine, MTMC, mixed aqueous solution 5 mL of the grand and estriol of chlorine sulphur, centrifugal 15 min of 3000 rpm after 30 min vibrate, each analyte concentration record supernatant on HPLC-DAD detector in, recording wavelength sulfa drugs is 270 nm, MTMC is 210 nm, estriol and chlorine sulphur are grand is 230 nm.According to the comparison of supernatant and concentration of standard solution before and after absorption, calculate adsorbance, the distribution coefficient (K of every kind of material
d), selectivity factor (K) and relative selectivity coefficient (K
,).The results are shown in Table 2.
As can be seen from Table 2, imprinted polymer will be far longer than the adsorption capacity of non-imprinted polymer to sulfa drugs to the adsorbance of sulfa drugs.And imprinted polymer is less to MTMC, chlorine sulphur adsorbance grand and estriol, be starkly lower than the adsorbance of non-imprinted polymer and estriol grand to MTMC, chlorine sulphur.The sorbing material that this method synthesized is described has stronger selective recognition to 10 kinds of sulfa drugs.
(3) preparation of solid-phase extraction column
Take sulfa drugs molecularly imprinted polymer particulate 0.050-0.200g, be filled in the polypropylene solid-phase extraction column of 5mL, load onto respectively polyethylene sieve plate at the two ends of filler, sieve plate is covered tightly, to obtain final product.
The application of hydrophily sulfa drugs solid-phase extraction column prepared by embodiment 2
(1) extraction of ten kinds of sulfa drugs in pork
Bought pork sample is placed in to mixer homogeneous to be placed on-20 DEG C of refrigerators and to preserve.Accurately take 1.00 g pork samples and be placed in 100 mL beakers, ten kinds of analyte mixed solutions of mark-on variable concentrations.With 3 mL methyl alcohol, ultrasonic 15 min make protein denaturation, except the interference of deproteinize to analyte detection.In triplicate.Collect supernatant centrifugal 15 min under 3000 r/min rotating speeds.Get supernatant through 0.22 μ m membrane filtration, proceed in 50 mL volumetric flasks, treat Solid phase extraction after being settled to scale.
(2) purify
Before loading, first activate successively and balance solid-phase extraction column by 3 mL methyl alcohol and 3 mL deionized waters, using the 50 mL10 kind sulfonamide hybrid standard aqueous solution as sample liquid, loading enrichment purifies.Target analytes is attracted on MISPE post, and the part not being adsorbed flows out with waste liquid.MISPE post with 2.00 mL methanol solutions with 1.00 mL/min flow velocity wash-out MISPE solid-phase extraction columns, collect eluent, at room temperature dry up the methanol solution redissolution of rear use 1.0 mL with nitrogen stream, after 0.45 μ m membrane filtration, get 20 μ L direct injected HPLC and detect.Enrichment is thoroughly washed with methyl alcohol and the 5 mL distilled waters of 5 mL MISPE post after purifying, and uses in order to next preenrichment.
(3) rate of recovery of 10 kinds of sulfonamides of high effective liquid chromatography for measuring
Chromatographic condition: chromatographic column ThermoC18 post (5um, 4.6mm × 250mm) mobile phase A: the aqueous solution of methanol as mobile phase B:0.1%, the ratio of mobile phase A and Mobile phase B is 25:75.Detecting wavelength is 270 nm.
After measured, the recovery of standard addition of 10 kinds of sulfa drugs in pork, at 73.9%-85.4%, the results are shown in Table 3.
Claims (10)
1. a preparation method for hydrophily sulfa drugs molecularly imprinted solid phase extraction column, comprises the steps:
(1), first by template molecule, function monomer and crosslinking agent, mix according to the ratio of mol ratio 0.1:4:6, by mass polymerization synthesis hydrophilic sulfamido molecularly imprinted polymer;
(2) imprinted polymer of step (1) gained is characterized, determine the existence of trace binding site;
(3) take sulfa drugs molecularly imprinted polymer particulate 0.050-0.200g, be filled in the polypropylene solid-phase extraction column of 5mL, load onto respectively polyethylene sieve plate at the two ends of filler, sieve plate is covered tightly, to obtain final product.
2. the preparation method of hydrophily sulfa drugs molecularly imprinted solid phase extraction column according to claim 1, is characterized in that, described template molecule is sulfamethazine and sulphathiazole, and both molar ratios are 1:1.
3. the preparation method of a kind of hydrophily sulfa drugs molecularly imprinted solid phase extraction column according to claim 1, it is characterized in that, described function monomer is methacrylic acid (MAA) and hydrophily function monomer hydroxyethyl methacrylate (HEMA), and both molar ratios are 1:1; Described crosslinking agent is ethylene glycol dimethacrylate and 3-(trimethoxysilyl) a kind of in propyl group acrylate or two kinds.
4. the preparation method of a kind of hydrophily sulfa drugs molecularly imprinted solid phase extraction column according to claim 1, is characterized in that, described characterizing method comprises Dynamic Adsorption, Static Adsorption and specific adsorption.
5. the preparation method of a kind of hydrophily sulfa drugs molecularly imprinted solid phase extraction column according to claim 1, is characterized in that, the preparation process of described hydrophily sulfa drugs molecularly imprinted polymer is as follows:
(1) using the sulphathiazole of the sulfamethazine of 0.05mmol and 0.05mmol as template, be dissolved in pore-foaming agent, by mixed solution ultrasonic degas, it is mixed;
(2) the function monomer methacrylic acid of 2mmol is joined in the prepared even mixed liquor of step (1), on oscillator, vibrate, obtain prepolymerization system;
(3) in step 2) add hydrophily function monomer hydroxyethyl methacrylate (HEMA), vibration 1h in the prepolymerization system that obtains; Then add crosslinking agent, vibration 1h; Finally add initator, vibration 0.5h, passes into nitrogen deoxygenation 5min, and at the atmosphere lower seal of nitrogen;
(4) bathe 24h at 60 DEG C of Water Unders, heat causes the described polymerization system of step (3), obtains the block molecularly imprinted polymer of hydrophily sulfonamide;
(5) after being ground, the block molecularly imprinted polymer of gained in step (4) sieves, sub-sieve obtains the particle diameter between 30-60 μ m, underproof particle is removed, wrap up with qualitative filter paper, then in apparatus,Soxhlet's, the extractant with 250 mL extracts 50h-110h, then use hydrochloric acid and the methanol wash 5h of 1mmol, dry to constant weight for 75 DEG C, obtain imprinted polymer particle.
6. the preparation process of hydrophily sulfa drugs molecularly imprinted polymer according to claim 5, is characterized in that, described pore-foaming agent is acetonitrile, and its consumption is 6mL.
7. the preparation process of hydrophily sulfa drugs molecularly imprinted polymer according to claim 5, is characterized in that, the speed of described vibration is 160 turn/min, and duration of oscillation is 3h.
8. the preparation process of hydrophily sulfa drugs molecularly imprinted polymer according to claim 5, is characterized in that, described hydrophily function monomer is hydroxyethyl methacrylate (HEMA), and its consumption is 2mmol.
9. the preparation process of hydrophily sulfa drugs molecularly imprinted polymer according to claim 5, it is characterized in that, described crosslinking agent is the ethyleneglycol dimethacrylate (EDMA) of 3mmol and the 3-(trimethoxysilyl of 3mmol) propyl group acrylate (γ-MAPS), described initator is azodiisobutyronitrile (AIBN), and consumption is 25mg.
10. the preparation process of hydrophily sulfa drugs molecularly imprinted polymer according to claim 5, is characterized in that, described extractant is that volume ratio is methyl alcohol and the formic acid mixed solution of 9:1.
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| CN104277190B (en) * | 2014-09-17 | 2016-08-24 | 兰州大学 | The preparation of a kind of core-shell type Ultraluminescence molecular engram material and material application in sulfanilamide detects |
| CN106810638A (en) * | 2016-12-23 | 2017-06-09 | 齐鲁工业大学 | The preparation method and application of Sulfonamides hydrophilic magnetic molecular engram material |
| CN107233873A (en) * | 2017-07-24 | 2017-10-10 | 齐鲁工业大学 | There is the preparation method of specific solid-phase micro-extraction fibre to sulfa drugs |
| CN107233873B (en) * | 2017-07-24 | 2019-03-29 | 齐鲁工业大学 | There is the preparation method of the solid-phase micro-extraction fibre of specificity to sulfa drugs |
| CN109180864A (en) * | 2018-07-18 | 2019-01-11 | 江苏全给净化科技有限公司 | Molecularly imprinted polymer material and application for sulfa drugs in purified water |
| CN109180864B (en) * | 2018-07-18 | 2021-05-18 | 江苏全给净化科技有限公司 | Molecularly imprinted polymer material for purifying sulfonamides in water and application thereof |
| EP3721985A1 (en) * | 2019-04-08 | 2020-10-14 | Tallinn University of Technology | Molecularly imprinted polymers sensors for sulfonamides |
| CN112090411A (en) * | 2020-08-06 | 2020-12-18 | 河南科技学院 | Magnetic material for analyzing sulfonamide antibiotics and detection method of sulfonamide antibiotics |
| CN113686832A (en) * | 2021-08-20 | 2021-11-23 | 江南大学 | Ultrasensitive recognition dot matrix array detection method for sulfonamide antibiotics |
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