CN101907571A - Mesoporous carbon molecular imprinting detector for detecting trace environment hormones and application thereof - Google Patents
Mesoporous carbon molecular imprinting detector for detecting trace environment hormones and application thereof Download PDFInfo
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Abstract
The invention relates to a mesoporous carbon molecular imprinting detector for detecting trace environment hormones and application thereof. The mesoporous carbon molecular imprinting detector is manufactured by adopting the following steps of: selecting a trace environment hormone molecule as a template molecule; uniformly mixing the template molecule, a functional monomer, a cross-linking agent, an pore-forming agent, an initiating agent and an organic solvent in a certain mole ratio to prepare a molecular imprinting polymer; preparing mesoporous carbon into a mesoporous carbon solution; modifying the mesoporous carbon solution and the molecular imprinting polymer to the surface of a glass sheet; placing the glass sheet into a micropore plate, and sealing for several hours by using a preservative film so as to obtain the mesoporous carbon molecular imprinting detector for detecting the trace environment hormones. The manufactured mesoporous carbon molecular imprinting detector for detecting the trace environment hormones is applied to a micropore plate multifunctional analyzer and used for detecting the environment hormones contained in an environment sample by adding an HCL solution, a KMnO4 solution and a polysorbate-80 solution to the detector. The mesoporous carbon molecular imprinting detector has the advantages of higher selectivity and sensitivity, fast detection, high-flux fast detection, little using amount of reagents and reusability.
Description
Technical field
The present invention relates to environmental hormone detection technique field, a kind of molecular imprinting detector that detects trace environment hormones of more specifically saying so the invention still further relates to the application of described molecular imprinting detector in the testing environment hormone.
Background technology
Environmental hormone (Environmental hormone) is meant human some toxic chemical substance that is discharged in the environment in production, life process, hormone in they and the animal body has similar chemical constitution, bringing into play similar functions of hormones, they enter in the body, upset the normal secretion of hormone, the physiology program of animal is got muddled, cause function generation obstacles such as reproduction, immunity.
Environmental hormone has become global problem of environmental pollution at present.The known environment hormone has 70 kinds approximately at present, extensively is present in the surrounding mediums such as atmosphere, water, soil.In daily life; the compound that contains environmental hormone can be found everywhere, and discharges some adjuvant, electromagnetic wave pollution, the vehicle exhaust in a large amount of extremely toxic substance dioxin, agricultural chemicals, forest protection agent, washing agent, cosmetics, thinning agent, plastic products and the food and contains health medicine of hormone or the like as waste incineration.If environmental hormone can not obtain in time, detection exactly, they just may enter body, and the directly or indirectly normal hormone metabolism of influence in vivo, bring serious harm to human health.
Set up the method for a kind of high sensitivity and specific quick screening environmental hormone, just become current this research field and need one of problem of solution badly.Existing environment hormone detection at present or screening method mainly comprise in vivo studies, in vitro test, biomarker detection and instrument detecting method etc., and be not enough but these detections or screening method exist:
1. uterus weight test and uterus calbindin CaBP-9k mRNA detection of expression and analysis of protein are often adopted in vivo studies, and this method reaction sensitivity has selectivity, but its cost height, and sensitivity is low, is unsuitable for large-scale screening fast;
2. in vitro test mainly contains E-Screen method, receptor competition test etc., and the specificity of test itself is relatively poor, occurs false positive results easily;
3. the environmental hormone instrument detecting method of setting up by means of large-scale precision instruments such as HPLC or LC-MS coupling techniques, though the detection to environmental hormone has very high sensitivity, but this method can not once just identify the structure of analyte, need confirm structure with GC-MS toward contact, technical costs is higher, and required time of classic method is generally all longer, have in addition reach several hrs, complicated operation can not be used for on-the-spot fast detecting.
4. above several method is for the detection and the analysis of environmental hormone, have all generally that detection sensitivity is low, cost is high, as a result false positive, testing process complexity, detect single, reagent dosage big, be unsuitable for shortcoming such as field quick detection, therefore can not satisfy the needs of actual detected.
Application number is that the application documents of 200810138510.X have been announced a kind of molecular engram film substrate, is used for trace amount environment incretion jam object, has used nm of gold, carbon nano-tube or nanometer platinum, and cost is higher.
Summary of the invention
The technical problem to be solved in the present invention provided that a kind of reagent dosage is few, detection speed is fast, highly sensitive, and mesoporous carbon molecular imprinting detector that can the high throughput testing trace environment hormones.
The present invention also provides the application of mesoporous carbon molecular imprinting detector in the testing environment hormone that detects trace environment hormones.
The present invention realizes in the following manner.
A kind of mesoporous carbon molecular imprinting detector that detects trace environment hormones is characterized in that adopting following steps to make:
(1) selection function monomer, described function monomer can with the environmental hormone Synthesis of Molecular Imprinting Polymers;
(2) select for use the environmental hormone molecule as template molecule, by certain mol proportion template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and organic solvent are mixed and make molecularly imprinted polymer;
(3) mesoporous carbon is prepared into mesoporous carbon solution;
(4) utilize modification technique layer by layer, mesoporous carbon solution and molecularly imprinted polymer are modified glass sheet surface;
(5) glass sheet that mesoporous carbon and molecularly imprinted polymer are modified places in the microwell plate, seal a few hours up for safekeeping with preservative film after, obtain detecting the mesoporous carbon molecular imprinting detector of trace environment hormones.
The mesoporous carbon molecular imprinting detector of described detection trace environment hormones, its feature also is: described function monomer is acrylic acid, methacrylic acid or 4-vinylpridine; Described crosslinking chemical is trimethylol-propane trimethacrylate, N, N-methylene diacrylamine, 3,5-two (acrylamide) benzoic acid, ethylene glycol dimethacrylate, divinylbenzene or pentaerythritol triacrylate; Described initiating agent is an azoisobutyronitrile; Described pore-foaming agent adopts methylene chloride, chloroform, acetonitrile, methyl alcohol, isopropyl alcohol, phenixin, N, N-dimethylformamide or dimethyl sulfoxide (DMSO); Described organic solvent is methylene chloride or phenixin.
The mesoporous carbon molecular imprinting detector of described detection trace environment hormones, its feature also is: the mol ratio of described template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and organic solvent is 0.2～2: 1: 0.4～5: 35～60: 0.10～0.20: 3.0～30.
The mesoporous carbon molecular imprinting detector of described detection trace environment hormones, its feature also is: described mesoporous carbon solution and molecularly imprinted polymer are modified glass sheet surface, may further comprise the steps:
(a) used glass sheet is cleaned with NaOH solution, steam water with secondary then and clean drying;
(b) drip mesoporous carbon solution and drying on the glass sheet of in step (a), handling;
(c) drip molecularly imprinted polymer on the glass sheet that dries in step (b), drying is used the eluant, eluent wash-out, the template molecule in this layer is washed off drying;
(d) repeating step (b) makes the glass sheet that described mesoporous carbon and molecularly imprinted polymer are modified to step (c) process 3-6 time.
The mesoporous carbon molecular imprinting detector of described detection trace environment hormones, its feature also is: described eluant, eluent is methyl alcohol and acetate mixture.
The mesoporous carbon molecular imprinting detector of described detection trace environment hormones, its feature also is: described mesoporous carbon is CMK-3 mesoporous carbon or CMK-5 mesoporous carbon.
The mesoporous carbon molecular imprinting detector of described detection trace environment hormones, its feature also is: the glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours with preservative film.
The application of a kind of mesoporous carbon molecular imprinting detector of above-mentioned each described detection trace environment hormones in the testing environment hormone, it is characterized in that adopting following steps: the mesoporous carbon molecular imprinting detector of the detection trace environment hormones that will make by above-mentioned any one method is used for the microwell plate multi-functional analyzer, adds HCl solution, KMnO in detector
4Solution and Tween-80 solution detect the environmental hormone in the environmental sample.To molecularly imprinted polymer, with chemical illuminating reagent reaction, produce power, luminescence reagent absorbs the energy jump that produces and arrives excited state environmental hormone in the sample by specific adsorption.When excited state turned back to ground state, energy discharged with chemiluminescent form, is detected and record by the microwell plate multi-functional analyzer.
Beneficial effect of the present invention:
1. the environmental hormone mesoporous carbon molecular imprinting detector is incorporated into the meso-porous carbon material synergistic effect in the middle of the preparation of detector, makes prepared environmental hormone molecular imprinting detector have higher selectivity and sensitivity.
With the surface layer by layer modification technique be applied in the middle of the preparation of molecular imprinting detector, make the preparation of environmental hormone molecular imprinting detector of mesoporous carbon synergy have controllability, improved detector sensitivity, selectivity and accuracy.
3. the resulting mesoporous carbon molecular imprinting detector of the present invention can be realized high specific, high sensitivity, the high flux fast detecting of environmental hormone in the sample.
4. the high specificity of mesoporous carbon molecular imprinting detector of the present invention, other non-specific molecules does not have influence to testing result in the sample; Highly sensitive, can reach the nanogram level; Detection speed is fast, finishes the time that a basic testing process only needs 1-2 minute, can realize the high flux screening of great amount of samples at short notice, and reagent dosage is few, and detecting a sample only needs tens microlitre reagent.
5. microwell plate is reusable.When detector reaches serviceable life, only need replacing to place the mesoporous carbon of detector microwell plate and the glass sheet that molecularly imprinted polymer is modified, just can constitute new molecular imprinting detector.Method is simple, has saved the detection cost greatly, has reduced the pollution of teflon, makes to detect greenization.
Embodiment
Embodiment 1 (dioxin is as dioxin, TCDD)
A kind of mesoporous carbon molecular imprinting detector that detects the trace dioxin, the preparation method may further comprise the steps:
(1) select can with the function monomer acrylic acid of dioxin Synthesis of Molecular Imprinting Polymers;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-3, sonicated 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule dioxin, function monomer acrylic acid, the crosslinking chemical trimethylol-propane trimethacrylate, the pore-foaming agent methylene chloride, the initiating agent azoisobutyronitrile, organic solvent dichloromethane 0.2: 1: 0.4 in molar ratio: mix at 35: 0.1: 3, obtain the dioxin molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size are cleaned glass sheet with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, dry 10min under the room temperature; Drip the dioxin molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule dioxin molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips the dioxin molecularly imprinted polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule dioxin molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful dioxin mesoporous carbon molecular imprinting detector with preservative film.
The dioxin mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the dioxin in the environmental sample extract, and testing result sees Table 1.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common dioxin molecular engram microwell plate, and the dioxin molecule in the sample is carried out actual detected, testing result sees Table 1.
Table 1 dioxin mesoporous carbon molecular imprinting detector of the present invention and common dioxin molecular engram microwell plate detect effect comparison
The result as can be seen from table 1: the dioxin molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common dioxin molecular engram microwell plate (not adding mesoporous carbon modifies).
A kind of mesoporous carbon molecular imprinting detector that detects trace TCDD, the preparation method is with the mesoporous carbon molecular imprinting detector preparation method of above-mentioned dioxin, the TCDD mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the TCDD in the environmental sample extract, and testing result sees Table 2.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution, preparation general T CDD molecular engram microwell plate carries out actual detected to the TCDD molecule in the sample, and testing result sees Table 2
Table 2 TCDD mesoporous carbon molecular imprinting detector of the present invention and general T CDD molecular engram microwell plate detect effect comparison
The result as can be seen from table 2: the TCDD molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than general T CDD molecular engram microwell plate (not adding mesoporous carbon modifies).
Embodiment 2 (insecticide, as metrifonate, decis, DDT)
A kind of mesoporous carbon molecular imprinting detector that detects trace metrifonate, the preparation method may further comprise the steps:
(1) select can with the function monomer methacrylic acid (MAA) of metrifonate Synthesis of Molecular Imprinting Polymers;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-3, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule metrifonate, function monomer methacrylic acid (MAA), crosslinking chemical N, N-methylene diacrylamine, the pore-foaming agent chloroform, the initiating agent azoisobutyronitrile, organic solvent phenixin 0.5: 1: 1.0 in molar ratio: mix at 40: 0.12: 4.0, obtain the metrifonate molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip the metrifonate molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule metrifonate molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips the metrifonate molecularly imprinted polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule metrifonate molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful metrifonate mesoporous carbon molecular imprinting detector with preservative film.
The metrifonate mesoporous carbon molecular imprinting chemiluminescence detector that makes is connected to the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the metrifonate in the environmental sample extract, and testing result sees Table 3.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common metrifonate molecular engram microwell plate, and the metrifonate molecule in the sample is carried out actual detected, testing result sees Table 3.
Table 3 metrifonate mesoporous carbon molecular imprinting detector of the present invention and common metrifonate molecular engram microwell plate detect effect comparison
Detector preparation method of the present invention compares with other method, has better choice, higher sensitivity, and detection speed improves greatly, and can high throughput testing.The result as can be seen from table 3: the metrifonate molecular imprinting detector that meso-porous carbon material is modified has the wideer range of linearity and lower detectability than common metrifonate molecular engram microwell plate (not adding mesoporous carbon modifies).
A kind of mesoporous carbon molecular imprinting detector that detects the trace amounts of bromine Cyano chrysanthemate; the preparation method is with the mesoporous carbon molecular imprinting detector preparation method of above-mentioned metrifonate; the decis mesoporous carbon molecular imprinting chemiluminescence detector that makes is connected to the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the decis in the environmental sample extract, and testing result sees Table 4.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common decis molecular engram microwell plate, and the decis molecule in the sample is carried out actual detected, testing result sees Table 4.
Table 4 decis mesoporous carbon molecular imprinting detector of the present invention and common decis molecular engram microwell plate detect effect comparison
The result as can be seen from table 4: the decis molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common decis molecular engram microwell plate (not adding mesoporous carbon modifies).
A kind of mesoporous carbon molecular imprinting chemiluminescence detector that detects trace DDT; the preparation method is with above-mentioned metrifonate mesoporous carbon molecular imprinting detector preparation method; the DDT molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the DDT in the environmental sample extract, and testing result sees Table 5.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common DDT molecular engram microwell plate, and the DDT molecule in the sample is carried out actual detected, testing result sees Table 5.
Table 5 DDT mesoporous carbon molecular imprinting detector of the present invention and common DDT molecular engram microwell plate detect effect comparison
The result as can be seen from table 5: the DDT molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common DDT molecular engram microwell plate (not adding mesoporous carbon modifies).
(classes of herbicides is as Atrazine, polychlorinated biphenyl, 2,4-D) for embodiment 3
A kind of mesoporous carbon molecular imprinting detector that detects the trace Atrazine, the preparation method may further comprise the steps:
(1) select can with the function monomer 4-vinylpridine of Atrazine Synthesis of Molecular Imprinting Polymers;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-5, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule Atrazine, function monomer 4-vinylpridine (4-VP), crosslinking chemical 3,5-two (acrylamide) benzoic acid, the pore-foaming agent isopropyl alcohol, initiating agent azoisobutyronitrile, organic solvent dichloromethane 2: 1: 5 in molar ratio: mix at 60: 0.2: 30, obtain the Atrazine molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip the Atrazine molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule Atrazine molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips Aunar again and draws molecularly imprinted polymer on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule Atrazine molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful Atrazine mesoporous carbon molecular imprinting detector with preservative film.
The Atrazine mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMn0
4Solution and Tween-80 solution detect the Atrazine in the environmental sample extract, and testing result sees Table 6.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common Atrazine molecular engram microwell plate, and the Atrazine molecule in the sample is carried out actual detected, testing result sees Table 6.
Table 6 Atrazine mesoporous carbon molecular imprinting detector of the present invention and common Atrazine molecular engram microwell plate detect effect comparison
Detector preparation method of the present invention compares with other method, has better choice, higher sensitivity, and detection speed improves greatly, and can high throughput testing.The result as can be seen from table 6: the Atrazine molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common Atrazine molecular engram microwell plate (not adding mesoporous carbon modifies).
A kind of mesoporous carbon molecular imprinting detector that detects the trace polychlorinated biphenyl, the preparation method is with the mesoporous carbon molecular imprinting detector preparation method of above-mentioned Atrazine, pore-foaming agent is selected dimethyl sulfoxide (DMSO) for use, the pcb molecule trace detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the polychlorinated biphenyl in the environmental sample extract, and testing result sees Table 7.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common pcb molecule trace microwell plate, and the pcb molecule in the sample is detected, testing result sees Table 7.
Table 7 polychlorinated biphenyl mesoporous carbon molecular imprinting detector of the present invention and common pcb molecule trace microwell plate detect effect comparison
The result as can be seen from table 7: the pcb molecule trace detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common pcb molecule trace microwell plate (not adding mesoporous carbon modifies).
A kind of detection trace 2, the mesoporous carbon molecular imprinting detector of 4-D, the preparation method is with the mesoporous carbon molecular imprinting detector preparation method of above-mentioned Atrazine, with make 2, the 4-D molecular imprinting detector is used for the microwell plate multi-functional analyzer, adds chemical illuminating reagent Solution H Cl solution, KMnO in detector
4Solution and Tween-80 solution, to 2 in the environmental sample extract, 4-D detects, and testing result sees Table 8.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution, prepare common 2,4-D molecular engram microwell plate, to 2 in the sample, the 4-D molecule carries out actual detected, testing result sees Table 8.
Table 8 the present invention 2,4-D mesoporous carbon molecular imprinting detector and common 2,4-D molecular engram microwell plate detects effect comparison
The result is as can be seen from table 8: mesoporous carbon modify 2, the 4-D molecular imprinting detector is than common 2,4-D molecular engram microwell plate (not adding mesoporous carbon modifies) has the wideer range of linearity and lower detectability.
Embodiment 4 (the forest protection agent is as the composition pentachloro-phenol)
A kind of mesoporous carbon molecular imprinting detector that detects the trace pentachloro-phenol, the preparation method may further comprise the steps:
(1) select can with the function monomer methacrylic acid (MAA) of pentachloro-phenol Synthesis of Molecular Imprinting Polymers;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-5, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule pentachloro-phenol, function monomer methacrylic acid (MAA), crosslinking chemical divinylbenzene (DVB), pore-foaming agent methyl alcohol, the initiating agent azoisobutyronitrile, organic solvent dichloromethane 1.5: 1: 4.5 in molar ratio: mix at 50: 0.15: 25, obtain the pentachloro-phenol molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip the pentachloro-phenol molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule pentachloro-phenol molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips the pentachloro-phenol molecularly imprinted polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule pentachloro-phenol molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful pentachloro-phenol mesoporous carbon molecular imprinting detector with preservative film.
The pentachloro-phenol mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the pentachloro-phenol in the environmental sample extract, and testing result sees Table 9.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common pentachloro-phenol molecular engram microwell plate, and the pentachloro-phenol molecule in the sample is carried out actual detected, testing result sees Table 9.
Table 9 pentachloro-phenol mesoporous carbon molecular imprinting detector of the present invention and common pentachloro-phenol molecular engram microwell plate detect effect comparison
The result as can be seen from table 9: the pentachloro-phenol molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common pentachloro-phenol molecular engram microwell plate (not adding mesoporous carbon modifies).
Embodiment 5 (washing agent is as the composition nonyl phenol)
A kind of mesoporous carbon molecular imprinting detector that detects the trace nonyl phenol, the preparation method may further comprise the steps:
(1) select can with the function monomer 4-vinylpridine (4-VP) of nonyl phenol molecule synthesis molecularly imprinted polymer;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-5, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule nonyl phenol, function monomer 4-vinylpridine (4-VP), crosslinking chemical pentaerythritol triacrylate (PETRA), the pore-foaming agent phenixin, the initiating agent azoisobutyronitrile, organic solvent phenixin 1.5: 1: 3 in molar ratio: mix at 25: 0.1: 20, obtain the nonyl phenol molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip the nonyl phenol molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule nonyl phenol molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips the nonyl phenol molecularly imprinted polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule nonyl phenol molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful nonyl phenol mesoporous carbon molecular imprinting detector with preservative film.
The nonyl phenol mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the nonyl phenol in the environmental sample extract, and testing result sees Table 10.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common nonyl phenol molecular engram microwell plate, and the nonyl phenol molecule in the sample is detected, testing result sees Table 10.
Table 10 nonyl phenol mesoporous carbon molecular imprinting detector of the present invention and common nonyl phenol molecular engram microwell plate detect effect comparison
The result as can be seen from table 10: the nonyl phenol molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common nonyl phenol molecular engram microwell plate (not adding mesoporous carbon modifies).Embodiment 6 (plastic products are as the composition bisphenol-A)
A kind of mesoporous carbon molecular imprinting detector that detects trace amount of bisphenol A, the preparation method may further comprise the steps:
(1) select can with the function monomer methacrylic acid (MAA) of bisphenol-A molecule synthesis molecularly imprinted polymer;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-5, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule bisphenol-A, function monomer methacrylic acid (MAA), crosslinking chemical ethylene glycol dimethacrylate (EGDMA), pore-foaming agent N, the N-dimethylformamide, initiating agent azoisobutyronitrile, organic solvent dichloromethane 0.9: 1: 1.5 in molar ratio: mix at 45: 0.1: 10, obtain bisphenol A molecular engram polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip bisphenol A molecular engram polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule bisphenol-A molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips bisphenol A molecular engram polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule bisphenol-A molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful bisphenol-A mesoporous carbon molecular imprinting detector with preservative film.
The bisphenol-A mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the bisphenol-A in the environmental sample extract, and testing result sees Table 11.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common bisphenol A molecular engram microwell plate, and the bisphenol-A molecule in the sample is carried out actual detected, testing result sees Table 11.
Table 11 bisphenol-A mesoporous carbon molecular imprinting detector of the present invention and common bisphenol A molecular engram microwell plate detect effect comparison
The result as can be seen from table 11: the bisphenol A molecular engram detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common bisphenol A molecular engram microwell plate (not adding mesoporous carbon modifies).
Embodiment 7 (metal species is as lead tetraethyl, tributyl tin)
A kind of mesoporous carbon molecular imprinting detector that detects the trace lead tetraethyl, the preparation method may further comprise the steps:
(1) select can with the function monomer methacrylic acid (MAA) of lead tetraethyl molecule synthesis molecularly imprinted polymer;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-5, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule lead tetraethyl, function monomer methacrylic acid (MAA), crosslinking chemical 3,5-two (acrylamide) benzoic acid, the pore-foaming agent acetonitrile, initiating agent azoisobutyronitrile, organic solvent dichloromethane 0.9: 1: 0.8 in molar ratio: mix at 42: 0.1: 5, obtain the lead tetraethyl molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip the lead tetraethyl molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule lead tetraethyl molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips the lead tetraethyl molecularly imprinted polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule lead tetraethyl molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful lead tetraethyl mesoporous carbon molecular imprinting detector with preservative film.
The lead tetraethyl mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the lead tetraethyl in the environmental sample extract, and testing result sees Table 12.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common lead tetraethyl molecular engram microwell plate, and the lead tetraethyl molecule in the sample is detected, testing result sees Table 12.
Table 12 lead tetraethyl mesoporous carbon molecular imprinting detector of the present invention and common lead tetraethyl molecular engram microwell plate detect effect comparison
The result as can be seen from table 12: the lead tetraethyl mesoporous carbon molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common lead tetraethyl molecular engram microwell plate (not adding mesoporous carbon modifies).
A kind of mesoporous carbon molecular imprinting detector that detects the trace tributyl tin, the preparation method is with the mesoporous carbon molecular imprinting detector preparation method of above-mentioned lead tetraethyl, the tributyl tin mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the tributyl tin in the environmental sample extract, and testing result sees Table 13.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common tributyl tin molecular engram microwell plate, and the tributyl tin molecule in the sample is detected, testing result sees Table 13.
Table 13 tributyl tin mesoporous carbon molecular imprinting detector of the present invention and common lead tetraethyl molecular engram microwell plate detect effect comparison
The result as can be seen from table 13: the tributyl tin molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common tributyl tin molecular engram microwell plate (not adding mesoporous carbon modifies).Embodiment 8 (the cosmetics steroids is as progestational hormone)
A kind of mesoporous carbon molecular imprinting detector that detects trace progestational hormone, the preparation method may further comprise the steps:
(1) select can with the function monomer 4-vinylpridine (4-VP) of progestational hormone molecule synthesis molecularly imprinted polymer;
(2) add the 5mL tetrahydrofuran in 0.0020g mesoporous carbon CMK-5, ultrasonic 20min obtains homodisperse mesoporous carbon solution;
(3) template molecule progestational hormone, function monomer 4-vinylpridine (4-VP), crosslinking chemical N, N-methylene diacrylamine, the pore-foaming agent isopropyl alcohol, the initiating agent azoisobutyronitrile, organic solvent dichloromethane 1.2: 1: 2.5 in molar ratio: mix at 50: 0.1: 8, obtain the progestational hormone molecularly imprinted polymer;
(4) cutting and the similar glass sheet of microwell plate bottom surface size.Glass sheet is cleaned with 1mol/L NaOH, steam water with secondary then and thoroughly clean for several times, dry up;
(5) on glass sheet, drip 10 μ L mesoporous carbon solution, at room temperature dry 10min; Drip the progestational hormone molecularly imprinted polymer again on glass sheet, drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the template molecule progestational hormone molecule in this one deck being washed fully off at room temperature dry 10min.Drip 10 μ L mesoporous carbon solution again on glass sheet, at room temperature dry 10min drips the progestational hormone molecularly imprinted polymer again on glass sheet, and drying is 10 minutes under the room temperature.Use methyl alcohol and acetate mixed liquor wash-out glass sheet surface 25 minutes then, until the masterplate molecule progestational hormone molecule in this one deck is washed off at room temperature dry 10min fully.So circulation repeats said process 6 times.
(6) glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours, prepare successful progestational hormone mesoporous carbon molecular imprinting detector with preservative film.
The progestational hormone mesoporous carbon molecular imprinting detector that makes is used for the microwell plate multi-functional analyzer, in detector, adds chemical illuminating reagent Solution H Cl solution, KMnO
4Solution and Tween-80 solution detect the progestational hormone in the environmental sample extract, and testing result sees Table 14.
Utilize above-mentioned same quadrat method, but glass sheet surface unmodified mesoporous carbon solution prepares common progestational hormone molecular engram microwell plate, and the progestational hormone molecule in the sample is detected, testing result sees Table 14.
Table 14 progestational hormone mesoporous carbon molecular imprinting detector of the present invention and common progestational hormone molecular engram microwell plate detect effect comparison
The result as can be seen from table 15: the progestational hormone molecular imprinting detector that mesoporous carbon is modified has the wideer range of linearity and lower detectability than common progestational hormone molecular engram microwell plate (not adding mesoporous carbon modifies).
Claims (8)
1. mesoporous carbon molecular imprinting detector that detects trace environment hormones is characterized in that adopting following steps to make:
(1) selection function monomer, described function monomer can with the environmental hormone Synthesis of Molecular Imprinting Polymers;
(2) select for use the environmental hormone molecule as template molecule, by certain mol proportion template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and organic solvent are mixed and make molecularly imprinted polymer;
(3) mesoporous carbon is prepared into mesoporous carbon solution;
(4) utilize modification technique layer by layer, mesoporous carbon solution and molecularly imprinted polymer are modified glass sheet surface;
(5) glass sheet that mesoporous carbon and molecularly imprinted polymer are modified places in the microwell plate, seal a few hours up for safekeeping with preservative film after, obtain detecting the mesoporous carbon molecular imprinting detector of trace environment hormones.
2. according to the mesoporous carbon molecular imprinting detector of the described detection trace environment hormones of claim 1, it is characterized in that: described function monomer is acrylic acid, methacrylic acid or 4-vinylpridine; Described crosslinking chemical is trimethylol-propane trimethacrylate, N, N-methylene diacrylamine, 3,5-two (acrylamide) benzoic acid, ethylene glycol dimethacrylate, divinylbenzene or pentaerythritol triacrylate; Described initiating agent is an azoisobutyronitrile; Described pore-foaming agent adopts methylene chloride, chloroform, acetonitrile, methyl alcohol, isopropyl alcohol, phenixin, N, N-dimethylformamide or dimethyl sulfoxide (DMSO); Described organic solvent is methylene chloride or phenixin.
3. according to the mesoporous carbon molecular imprinting detector of the described detection trace environment hormones of claim 1, it is characterized in that: the mol ratio of described template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and organic solvent is 0.2～2: 1: 0.4～5: 35～60: 0.10～0.20: 3.0～30.
4. according to the mesoporous carbon molecular imprinting detector of the described detection trace environment hormones of claim 1, it is characterized in that: described mesoporous carbon solution and molecularly imprinted polymer are modified glass sheet surface, may further comprise the steps:
(a) used glass sheet is cleaned with NaOH solution, steam water with secondary then and clean drying;
(b) drip mesoporous carbon solution and drying on the glass sheet of in step (a), handling;
(c) drip molecularly imprinted polymer on the glass sheet that dries in step (b), drying is used the eluant, eluent wash-out, the template molecule in this layer is washed off drying;
(d) repeating step (b) makes the glass sheet that described mesoporous carbon and molecularly imprinted polymer are modified to step (c) process 3-6 time.
5. according to the mesoporous carbon molecular imprinting detector of the described detection trace environment hormones of claim 4, it is characterized in that: described eluant, eluent is methyl alcohol and acetate mixture.
6. according to the mesoporous carbon molecular imprinting detector of the described detection trace environment hormones of claim 1, it is characterized in that: described mesoporous carbon is CMK-3 mesoporous carbon or CMK-5 mesoporous carbon.
7. according to the mesoporous carbon molecular imprinting detector of the described detection trace environment hormones of claim 1, it is characterized in that: the glass sheet of modifying is placed in the microwell plate, sealed up for safekeeping 12 hours with preservative film.
8. the application of mesoporous carbon molecular imprinting detector in the testing environment hormone of each described detection trace environment hormones among the claim 1-7, it is characterized in that adopting following steps: the mesoporous carbon molecular imprinting detector of the detection trace environment hormones that will make by above-mentioned any one method is used for the microwell plate multi-functional analyzer, adds HC1 solution, KMnO in detector
4Solution and Tween-80 solution detect the environmental hormone in the environmental sample.
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