CN102585281B - Fluorescent ion imprinted sensor and application thereof in methyl mercury ion detection - Google Patents
Fluorescent ion imprinted sensor and application thereof in methyl mercury ion detection Download PDFInfo
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- CN102585281B CN102585281B CN 201110460517 CN201110460517A CN102585281B CN 102585281 B CN102585281 B CN 102585281B CN 201110460517 CN201110460517 CN 201110460517 CN 201110460517 A CN201110460517 A CN 201110460517A CN 102585281 B CN102585281 B CN 102585281B
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- 239000012528 membrane Substances 0.000 claims abstract description 32
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 8
- ZGMNAIODRDOMEK-UHFFFAOYSA-N 1,1,1-trimethoxypropane Chemical compound CCC(OC)(OC)OC ZGMNAIODRDOMEK-UHFFFAOYSA-N 0.000 claims description 7
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 7
- BABMCXWQNSQAOC-UHFFFAOYSA-M methylmercury chloride Chemical compound C[Hg]Cl BABMCXWQNSQAOC-UHFFFAOYSA-M 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- ZDHHIJSLJCLMPX-UHFFFAOYSA-M methylmercury(1+);bromide Chemical compound C[Hg]Br ZDHHIJSLJCLMPX-UHFFFAOYSA-M 0.000 claims description 6
- JVDIOYBHEYUIBM-UHFFFAOYSA-M methylmercury(1+);iodide Chemical compound C[Hg]I JVDIOYBHEYUIBM-UHFFFAOYSA-M 0.000 claims description 6
- GBJVVSCPOBPEIT-UHFFFAOYSA-N AZT-1152 Chemical compound N=1C=NC2=CC(OCCCN(CC)CCOP(O)(O)=O)=CC=C2C=1NC(=NN1)C=C1CC(=O)NC1=CC=CC(F)=C1 GBJVVSCPOBPEIT-UHFFFAOYSA-N 0.000 claims description 5
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- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims 2
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides an ion imprinted fluorescent sensor for selectively detecting methyl mercury ions and a preparation method for the ion imprinted fluorescent sensor. The sensor is prepared by the following three processes of: (1) forming a pre-copolymer by using the methyl mercury ions, a functional monomer and a fluorescent material through coordination; (2) adding a cross linker and an initiator, and performing initiated polymerization under proper conditions by using a microporous membrane as a supporting medium to immobilize template molecules in the polymer in a complementary spatial structure form; and (3) removing the template molecules from the polymer in an acid or ethylene diamine tetraacetic acid (EDTA) eluting mode, leaving specific holes, and thus obtaining the fluorescent methyl mercury ion imprinted composite membrane sensor. The obtained imprinted composite membrane shows high selectivity and sensitivity to methyl mercury ions, and can be reused for multiple times; and the fluorescent sensor is easy and fast to prepare, and can be used for selective detection of the methyl mercury ions in samples of environment and the like.
Description
(1) technical field
The present invention relates to a kind of fluorescence ion blotting sensor for the methyl mercury ion detection and preparation method thereof.
(2) background technology
Mercury is the harmful element that extensively is present in environment, existence form is totally different, toxicity is also different, and generally speaking, organomercurial toxicity is stronger than inorganic mercury, and methyl mercury is one of the strongest existence form of organic mercury poisoning, after invading human body, can be to neural system, heart, kidney, skin etc. cause serious harm.The measuring method of methyl mercury mainly contains the methods such as atomic absorption spectrometry, atomic emission spectrometry, Gas chromatography, high performance liquid chromatography, ion chromatography and capillary electrophoresis, but these methods all require more expensive testing tool, and testing cost is higher.Fluorometry highly sensitive, easy to operate, cost is low, becomes the novel method that detects methyl mercury.
The ion blotting technology adopts metal ion as the ion imprinted polymer of template preparation, have the advantages such as single-minded recognition site, high freedom from jamming and anti-extraneous mal-condition, be mainly used in the compartment analysis of metal ion in Solid-Phase Extraction and actual sample, but the report that is applied to the fluorescent optical sensor field seldom.Highly selective and the highly sensitive of fluorescence technique of ion blotting technology are combined, the methyl mercury ion blotting fluorescent optical sensor of preparation, have the characteristics such as selectivity is good, preparation is simple, the life-span is long, and can repeatedly recycle, and be easy to combine with optics.
(3) summary of the invention
The object of the invention be to provide a kind ofly prepare that simple, good stability, life-span are long, selectivity methyl mercury ion fluorescence sensor that easily preserve and preparation method thereof and analytical applications.
The technical solution used in the present invention is:
A kind of fluorescence ion blotting sensor, described fluorescence ion blotting sensor prepares by the following method:
(1) methyl mercury compound and fluorescent chemicals are dissolved in reaction solvent, mix, then add function monomer, linking agent and initiator, mix, obtain reaction soln;
Described methyl mercury compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Described fluorescent chemicals is the basic quinoline of 8-mercapto (hydroxyl), 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-vinylcarbazole or 2-naphthyl acrylate;
Described function monomer is one of following: methacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylamide;
Described linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Described initiator is Diisopropyl azodicarboxylate;
Described reaction solvent is dimethyl sulfoxide (DMSO), water or both mixtures.
The ratio of the amount of substance of described methyl mercury compound, fluorescent chemicals and function monomer is 1: 1～4: 4～250, and is preferred 1: 1～3: 4～200, and the ratio of the amount of substance of described function monomer and linking agent is 1: 2～8.
(2) millipore filtration is immersed in the reaction soln that step (1) obtains, take out after standing 1～60min, millipore filtration after soaking is sandwiched between sheet glass or quartz plate, degassed and the sealing, usually can seal with preservative film or freshness protection package bag sheet glass or quartz plate outside after degassed, then be placed under 60～70 ℃ of water-baths or UV-light and carried out polyreaction 4～32 hours, after reaction, millipore filtration is taken out from sheet glass or quartz plate, constant to the fluorescence intensity that film detected with the methyl mercury compound on elutriant wash-out film, again through washing, be drying to obtain described fluorescence ion blotting sensor,
Described elutriant is one or more in acetic acid, nitric acid, hydrochloric acid, sulfuric acid or the EDTA aqueous solution of 0.05～1M (preferred 0.1M).
Described millipore filtration is vinylidene fluoride film, cellulose acetate membrane, polypropylene screen or poly (ether sulfone) film.The thickness of described millipore filtration is generally 0.2～0.65 μ m, can select the millipore filtration of purchasing common on market to get final product.The large I of described millipore filtration is cut out as required voluntarily.
The concentration of described initiator in reaction solvent is 0.001～0.02g/ml.
The volumetric usage of described reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of methyl mercury compound usually.
The present invention also provides a kind of method for preparing described fluorescence ion blotting sensor, and described method is:
(1) methyl mercury compound and fluorescent chemicals are dissolved in reaction solvent, mix, then add function monomer, linking agent and initiator, mix, obtain reaction soln;
Described methyl mercury compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Described fluorescent chemicals is the basic quinoline of 8-mercapto (hydroxyl), 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-vinylcarbazole or 2-naphthyl acrylate;
Described function monomer is one of following: methacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylamide;
Described linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Described initiator is Diisopropyl azodicarboxylate;
Described reaction solvent is dimethyl sulfoxide (DMSO), water or both mixtures.
The ratio of the amount of substance of described methyl mercury compound, fluorescent chemicals and function monomer is 1: 1～4: 4～250, and is preferred 1: 1～3: 4～200, and the ratio of the amount of substance of described function monomer and linking agent is: 1: 2～8.
(2) millipore filtration is immersed in the reaction soln that step (1) obtains, take out after standing 1～60min, millipore filtration after soaking is sandwiched between sheet glass or quartz plate, degassed and the sealing, usually can seal with preservative film or freshness protection package bag sheet glass or quartz plate outside after degassed, then be placed under 60～70 ℃ of water-baths or UV-light and carried out polyreaction 4～32 hours, after reaction, remove preservative film or freshness protection package, millipore filtration is taken out from sheet glass or quartz plate, constant to the fluorescence intensity that film detected with the methyl mercury compound on elutriant wash-out film, again through washing, be drying to obtain described fluorescence ion blotting sensor,
Described elutriant be 0.05～1M acetic acid, nitric acid, hydrochloric acid, sulfuric acid or or the EDTA aqueous solution in one or more.
In described method, in described step (1), the described ultrasonic mixing 10～40min of preferred use that mixes.
In described method, in described step (2), be placed under 60～70 ℃ of water-baths or UV-light and carried out polyreaction 4～32 hours, preferably reacted 6～32 hours in 60～70 ℃ of water-baths or reacted under UV-light 20～32 hours.
In method of the present invention, the concentration of described initiator in reaction solvent is 0.001～0.02g/ml, and the volumetric usage of described reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of methyl mercury compound usually.
The present invention also provides the application of described fluorescence ion blotting sensor in the methyl mercury ion detection.
Further, the method for application of the present invention is:
Drawing standard curve: with the methyl mercury standardized solution of pH=7HCl-Tris damping fluid preparation different concns, fluorescence ion blotting sensor is placed in the methyl mercury standardized solution of different concns, standing 1～30min, take out after reaching adsorption equilibrium, suck the moisture on film surface with filter paper, detect the fluorescence intensity I of fluorescence ion blotting sensor after the absorption methyl mercury, excitation wavelength 250-350nm, detect wavelength 300-500nm, and detect the fluorescence intensity of blank fluorescence ion blotting sensor under similarity condition for contrast, be designated as I
0Take absorption methyl mercury concentration as X-coordinate, with (I/I
0-1) % is ordinate zou, draws to obtain typical curve;
testing sample solution is diluted with the pH=7HCl-Tris damping fluid, get test sample solution through 0.45 μ m filtering with microporous membrane, with fluorescence ion blotting sensor in deionized water fully after swelling, take out, suck the moisture on film surface with filter paper, be placed in the fluorescence orifice plate, getting described test sample solution adds in the fluorescence orifice plate that described fluorescence ion blotting sensor is housed, excitation wavelength 250-350nm, detect wavelength 300-500nm, the reference standard curve, obtain the methyl mercury ionic concn in described test sample solution, calculate again the methyl mercury ionic concn in testing sample solution.
methyl mercury ion blotting sensor of the present invention is the polymer type sensor that several functions monomer and fluorescent chemicals and template ion form by polymerization methods, coordination according to polymerization process intermediate ion and other compound, wash-out post polymerization thing inside can stay void structure and the chemical bonding effect with the complementation of template ion space structure, thereby realize the specific recognition to the target heavy metal, also have the following advantages simultaneously: prepare relatively simple, good stability, easily preserve, life-span is long, contaminated sample not, and be easy to combine with optics, has extensive practicality.
Effect of the present invention is mainly reflected in: the invention provides a kind of fluorescence ion blotting sensor for the methyl mercury ion detection, its form is the polymer compound film take commercial membranes as support membrane, preparation process is relatively simple, the sensor for preparing has the advantages such as specific recognition ability, anti-extraneous mal-condition, freedom from jamming, and recycle the performance that repeatedly still can keep good, having extensive practicality, is one of method of toxic metal ion in the rapid detection actual sample.
(4) description of drawings
Fig. 1 is the canonical plotting of embodiment 8.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
0.004mmol thiooxine and 0.002mmol Monomethyl mercury chloride are dissolved in the ultrasonic 20min of mixing in 1.5mlDMSO; Add the 0.008mmol methacrylic acid in said mixture, 0.04mmol ethylene glycol dimethacrylate and 0.015g Diisopropyl azodicarboxylate fully mix, and ultrasonic mixing 30min gets reaction soln; With 1cm length * 1cm wide * take out after the cellulose acetate membrane of 0.2 μ m thickness is placed in the standing 30min of above-mentioned reaction soln, clamp with quartz plate, drive out of after bubble with sealed membrane quartz plate wrapped after sealing 65 ℃ of lower heating in water bath 15 hours.After reacting completely, the methyl mercury ion blotting film of preparation is taken out, first use 0.1M EDTA aqueous solution wash-out, use again 0.1M sulphuric acid soln wash-out template ion, no longer change until fluorescence intensity detected, use again methyl alcohol and ultrapure water wash-out, at last that blotting membrane is dry, be fluorescence ion blotting sensor.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 2:
0.002mmol Monomethyl mercury chloride and 0.004mmol 2-naphthyl acrylate are dissolved in the ultrasonic 30min of mixing in 1mlDMSO, add again 4-vinylpridine 0.4mmol, 2mmol trimethoxy propane trimethyl acrylic ester and 0.01g Diisopropyl azodicarboxylate, ultrasonic mixing 20min gets reaction soln; With 1cm length * 1cm wide * take out after the polypropylene screen of 0.47 μ m thickness is placed in the standing 20min of above-mentioned reaction soln, clamp with quartz plate, made methyl mercury ion fluorescence blotting membrane with the sealed membrane sealing is rear in 10 hours at 65 ℃ of lower heating in water bath after driving bubble out of, film is taken out from quartz plate, use 0.1M HNO
3Template ion on the eluant solution blotting membrane until fluorescence intensity no longer changes, is then used the residual HNO of ultrapure water eccysis
3Solution, blotting membrane is dry, be fluorescence ion blotting sensor.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 3:
0.006mmol 1-allyl group-3-(1-naphthyl)-2-thiocarbamide and 0.002mmol methyl-mercuric bromide are mixed ultrasonic 30min in 1.5ml DMSO, add again 2-vinyl pyridine 0.4mmol, 3.2mmol ethylene glycol dimethacrylate linking agent and 0.02g Diisopropyl azodicarboxylate, ultrasonic mixing 30min gets reaction soln; With 1cm length * 1cm wide * take out after the cellulose acetate membrane of 0.65 μ m thickness is placed in the standing 10min of above-mentioned reaction soln, clamp with quartz plate, drive out of after bubble with after the sealed membrane sealing 65 ℃ of lower heating in water bath 6 hours, make methyl mercury ion fluorescence blotting membrane, film is taken out from quartz plate, use 0.1M HNO
3Template ion on the eluant solution blotting membrane is until fluorescence intensity is constant, and with the residual HNO of ultrapure water eccysis
3After, blotting membrane is dry, be fluorescence ion blotting sensor.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 4:
0.006mmol thiooxine and 0.002mmol methyl-mercuric bromide are dissolved in the ultrasonic 20min of mixing in 1.5mlDMSO; Add the 0.4mmol acrylamide in said mixture, 2mmol ethylene glycol dimethacrylate and 0.015g Diisopropyl azodicarboxylate fully mix, and ultrasonic mixing 30min gets reaction soln; With 1.5cm length * 1.5cm wide * take out after the polyvinylidene fluoride film of 0.65 μ m thickness is placed in the standing 40min of above-mentioned reaction soln, clamp with quartz plate, drive the bubble sealing out of, be placed under ultra violet lamp reaction 20 hours.After reacting completely, with the methyl mercury ion blotting film taking-up of preparation, with 0.1M HCl eluant solution, until fluorescence intensity no longer changes, with the residual HCl solution of ultrapure water eccysis, with the blotting membrane drying, be fluorescence ion blotting sensor at last.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 5:
0.002mmol methyl-mercuric iodide and 0.008mmol 1-allyl group-3-(1-naphthyl)-2-thiocarbamide are dissolved in 2ml DMSO and 1ml H
2Ultrasonic 15min in O solution, then add 2-vinyl pyridine 0.5mmol, 2mmol trimethoxy propane trimethyl acrylic ester and 0.015g Diisopropyl azodicarboxylate, ultrasonic mixing 20min gets reaction soln; With 2cm length * 2cm wide * take out after the polyvinylidene fluoride film of 0.45 μ m thickness is placed in the standing 50min of above-mentioned reaction soln, clamp with quartz plate, reacted 32 hours under ultra violet lamp after degassed sealing, make methyl mercury ion fluorescence blotting membrane, film is taken out from quartz plate, with the template ion on 0.1M HCl eluant solution blotting membrane until fluorescence intensity is stable, and with after the residual HCl of ultrapure water eccysis, blotting membrane is dry, be fluorescence ion blotting sensor.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 6:
0.004mmol N-vinylcarbazole and 0.002mmol methyl-mercuric iodide are mixed ultrasonic 30min in 1.5mlDMSO, add again 2-vinyl pyridine 0.4mmol,, 2mmol ethylene glycol dimethacrylate linking agent and 0.02g Diisopropyl azodicarboxylate, ultrasonic mixing 30min gets reaction soln; With 1cm length * 1cm wide * take out after the poly (ether sulfone) film of 0.22 μ m thickness is placed in the standing 20min of above-mentioned reaction soln, clamp with quartz plate, be placed on 65 ℃ of lower heating in water bath 24 hours with the sealed membrane sealing, make methyl mercury ion fluorescence blotting membrane, film is taken out from quartz plate, with the template ion on 0.1M HCl eluant solution blotting membrane until fluorescence intensity is stable, and with after the residual HCl solution of ultrapure water eccysis, at last that blotting membrane is dry, be fluorescence ion blotting sensor.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 7:
0.004mmol thiooxine and 0.004mmol Monomethyl mercury chloride are dissolved in the ultrasonic 10min of mixing in 2mlDMSO; Add the 0.016mmol methacrylic acid in said mixture, 0.032mmol trimethoxy propane trimethyl acrylic ester and 0.002g Diisopropyl azodicarboxylate fully mix, and ultrasonic mixing 35min gets reaction soln; With 1cm length * 1cm wide * take out after the cellulose acetate membrane of 0.65 μ m thickness is placed in the standing 60min of above-mentioned reaction soln, clamp with quartz plate, drive bubble out of, rear with the sealed membrane sealing, be placed on 65 ℃ of lower heating in water bath 32 hours.After reacting completely, the metal ion blotting membrane of preparation is first used 1M EDTA aqueous solution wash-out template ion, until the fluorescence intensity vary stable, then methyl alcohol and ultrapure water wash-out, dry with blotting membrane at last, is fluorescence ion blotting sensor.Gained fluorescence trace biosensor analysis detects the best pH=7 of methyl mercury ion, and 20 performances of service life cycle are constant.
Embodiment 8: Application Example 1
Drawing standard curve: with the methyl mercury ion standardized solution of pH=7HCl-Tris damping fluid preparation different concns.The fluorescence trace sensor of preparation in embodiment 1 is placed in the standing 5min of different methyl mercury solions, after reaching adsorption equilibrium, take out, filter paper blots the moisture on surface, detect the fluorescence intensity (fluorescence intensity adsorption equilibrium after be designated as I) of fluorescence blotting membrane after absorption methyl mercury ion, excitation wavelength 350nm detects wavelength 420nm, and the fluorescence intensity of fluorescence trace wet film under similarity condition of not adding the methyl mercury ion take blank (is designated as I as contrast
0), take absorption the methyl mercury ionic concn as X-coordinate, with (I/I
0-1) % is ordinate zou, drawing standard curve (seeing accompanying drawing 1).
Actual water sample product methyl mercury detects: get testing sample solution and dilute than 1: 1 with the pH=7HCl-Tris volume of buffer solution, through 0.45 μ m filtering with microporous membrane, get test sample solution.The fluorescence trace dry film that embodiment 1 is made is in deionized water fully after swelling, take out, suck the moisture on film surface with filter paper, be positioned in the fluorescence orifice plate, get the 300 above-mentioned test sample solution of μ l and add in the fluorescence microwell plate that contains the fluorescence blotting membrane, measure fluorescence intensity, reference standard curve by above-mentioned condition, record and contain methyl mercury 0.081mg/l (the gas Chromatographic Determination result is basically identical with adopting) in test sample solution, can be calculated testing sample, to contain methyl mercury be 0.162mg/l.
Claims (8)
1. fluorescence ion blotting sensor is characterized in that described fluorescence ion blotting sensor prepares by the following method:
(1) methyl mercury compound and fluorescent chemicals are dissolved in reaction solvent, then add function monomer, linking agent and initiator, mix, obtain reaction soln;
Described methyl mercury compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Described fluorescent chemicals is thiooxine, oxine, 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-vinylcarbazole or 2-naphthyl acrylate;
Described function monomer is one of following: methacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylamide;
Described linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Described initiator is Diisopropyl azodicarboxylate;
Described reaction solvent is dimethyl sulfoxide (DMSO), water or both mixtures;
The ratio of the amount of substance of described methyl mercury compound, fluorescent chemicals and function monomer is 1:1～4:4～250, and the ratio of the amount of substance of described function monomer and linking agent is 1:2～8;
(2) millipore filtration is immersed in the reaction soln that step (1) obtains, take out after standing 1～60min, millipore filtration after soaking is sandwiched between sheet glass or quartz plate, degassed and the sealing, then be placed under 60～70 ℃ of water-baths or UV-light and carried out polyreaction 4～32 hours, after reaction, millipore filtration is taken out from sheet glass or quartz plate, constant to the fluorescence intensity that film detected with the methyl mercury compound on elutriant wash-out film, then through washing, be drying to obtain described fluorescence ion blotting sensor;
Described elutriant is one or more in acetic acid, nitric acid, hydrochloric acid, sulfuric acid or the EDTA aqueous solution of 0.05～1M.
2. fluorescence ion blotting sensor as claimed in claim 1, is characterized in that described millipore filtration is vinylidene fluoride film, cellulose acetate membrane, polypropylene screen or poly (ether sulfone) film.
3. fluorescence ion blotting sensor as claimed in claim 1, it is characterized in that the concentration of described initiator in reaction solvent is 0.001～0.02g/ml, the volumetric usage of described reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of methyl mercury compound.
4. one kind prepares the method for fluorescence ion blotting sensor as claimed in claim 1, it is characterized in that described method is:
(1) methyl mercury compound and fluorescent chemicals are dissolved in reaction solvent, then add function monomer, linking agent and initiator, mix, obtain reaction soln;
Described methyl mercury compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Described fluorescent chemicals is thiooxine, oxine, 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-vinylcarbazole or 2-naphthyl acrylate;
Described function monomer is one of following: methacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylamide;
Described linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Described initiator is Diisopropyl azodicarboxylate;
Described reaction solvent is dimethyl sulfoxide (DMSO), water or both mixtures;
The ratio of the amount of substance of described methyl mercury compound, fluorescent chemicals and function monomer is: 1:1～4:4～250, and the ratio of the amount of substance of described function monomer and linking agent is: 1:2～8;
(2) millipore filtration is immersed in the reaction soln that step (1) obtains, take out after standing 1～60min, millipore filtration after soaking is sandwiched between sheet glass or quartz plate, degassed and the sealing, then be placed under 60～70 ℃ of water-baths or UV-light and carried out polyreaction 4～32 hours, after reaction, millipore filtration is taken out from sheet glass or quartz plate, constant to the fluorescence intensity that film detected with the methyl mercury compound on elutriant wash-out film, then through washing, be drying to obtain described fluorescence ion blotting sensor;
Described elutriant is one or more in acetic acid, nitric acid, hydrochloric acid, sulfuric acid or the EDTA aqueous solution of 0.05～1M.
5. the method for fluorescence ion blotting sensor as claimed in claim 4 is characterized in that described sealing after degassed is to wrap in sheet glass or the quartz plate outside seals with preservative film or freshness protection package.
6. the method for fluorescence ion blotting sensor as claimed in claim 4, it is characterized in that the concentration of described initiator in reaction solvent is 0.001～0.02g/ml, the volumetric usage of described reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of methyl mercury compound.
7. the application of fluorescence ion blotting sensor as claimed in claim 1 in the methyl mercury ion detection.
8. application as claimed in claim 7 is characterized in that the method for described application is:
Drawing standard curve: the methyl mercury standardized solution of preparing different concns with the HCl-Tris damping fluid of pH=7, fluorescence ion blotting sensor is placed in the methyl mercury standardized solution of different concns, standing 1～30min, take out after reaching adsorption equilibrium, suck the moisture on film surface with filter paper, detect the fluorescence intensity I of fluorescence ion blotting sensor after the absorption methyl mercury, excitation wavelength 250-350nm, detect wavelength 300-500nm, and detect the fluorescence intensity of blank fluorescence ion blotting sensor under similarity condition for contrast, be designated as I
0Take absorption methyl mercury concentration as X-coordinate, with (I/I
0– 1) % is ordinate zou, draws to obtain typical curve;
with the HCl-Tris damping fluid dilution of testing sample solution with pH=7, get test sample solution through 0.45 μ m filtering with microporous membrane, with fluorescence ion blotting sensor in deionized water fully after swelling, take out, suck the moisture on film surface with filter paper, be placed in the fluorescence orifice plate, getting described test sample solution adds in the fluorescence orifice plate that described fluorescence ion blotting sensor is housed, excitation wavelength 250-350nm, detect wavelength 300-500nm, the reference standard curve, obtain the methyl mercury ionic concn in described test sample solution, calculate again the methyl mercury ionic concn in testing sample solution.
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| Title |
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| Molecularly Imprinted Fluorescent Polymers as Chemosensors for the Detection of Mercury Ions in Aqueous Media;Orhan Guney et al.;《Journal of Applied Polymer Science》;20100413;第117卷;第2373-2379页 * |
| Orhan Guney et al..Molecularly Imprinted Fluorescent Polymers as Chemosensors for the Detection of Mercury Ions in Aqueous Media.《Journal of Applied Polymer Science》.2010,第117卷第2373-2379页. |
| 牟怀燕等.离子印迹荧光传感器选择性检测镉离子.《分析测试学报》.2011,第30卷(第7期),第795-798页. |
| 离子印迹荧光传感器选择性检测镉离子;牟怀燕等;《分析测试学报》;20110731;第30卷(第7期);第795-798页 * |
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