CN102585281A - 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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- CN102585281A CN102585281A CN2011104605175A CN201110460517A CN102585281A CN 102585281 A CN102585281 A CN 102585281A CN 2011104605175 A CN2011104605175 A CN 2011104605175A CN 201110460517 A CN201110460517 A CN 201110460517A CN 102585281 A CN102585281 A CN 102585281A
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- methylquecksilber
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- 150000002500 ions Chemical class 0.000 title claims abstract description 51
- 238000001514 detection method Methods 0.000 title claims abstract description 8
- DBUXSCUEGJMZAE-UHFFFAOYSA-N methylmercury(1+) Chemical compound [Hg+]C DBUXSCUEGJMZAE-UHFFFAOYSA-N 0.000 title abstract 2
- -1 methyl mercury ions Chemical class 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012982 microporous membrane Substances 0.000 claims abstract description 4
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000010453 quartz Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- 239000007810 chemical reaction solvent Substances 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005357 flat glass Substances 0.000 claims description 11
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 11
- 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
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 238000007872 degassing Methods 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000013016 damping Methods 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- SLVJUZOHXPZVLR-UHFFFAOYSA-N naphthalen-2-yl prop-2-enoate Chemical compound C1=CC=CC2=CC(OC(=O)C=C)=CC=C21 SLVJUZOHXPZVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012488 sample solution Substances 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
- 238000001035 drying Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000003755 preservative agent Substances 0.000 claims description 4
- 230000002335 preservative effect Effects 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract description 2
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- 229960001484 edetic acid Drugs 0.000 abstract 2
- 239000004971 Cross linker Substances 0.000 abstract 1
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- 238000004458 analytical method Methods 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- 208000009507 Nervous System Mercury Poisoning Diseases 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
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- 238000005558 fluorometry Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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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 transmitter that is used for the Methylquecksilber ion detection and preparation method thereof.
(2) background technology
Mercury is the harmful element that extensively is present in the environment, and existence form is totally different, and toxicity also has nothing in common with each other; Generally speaking, organomercurial toxicity is stronger than inorganic mercury, and Methylquecksilber is one of the strongest existence form of organic mercury poisoning property; After invading human body, can be to neural system, heart; Kidney, skin etc. cause serious harm.The measuring method of Methylquecksilber mainly contains methods such as atomic absorption spectrometry, atomic emission spectrometry, Gas chromatography, HPLC, ion chromatography and capillary electrophoresis; But these methods all require relatively more expensive testing tool, and testing cost is higher.Fluorometry highly sensitive, easy to operate, cost is low, becomes the novel method that detects Methylquecksilber.
The ion blotting technology adopts the ion imprinted polymer of metals ion as the template preparation; Have advantages such as single-minded recognition site, high freedom from jamming and anti-extraneous mal-condition; Be mainly used in the compartment analysis of metals ion in SPE and the actual sample, but the report that is applied to the fluorescent optical sensor field seldom.The highly selective and the highly sensitive of fluorescence technique of ion blotting technology are combined; The Methylquecksilber ion blotting fluorescent optical sensor of preparation; Have 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 provide a kind ofly prepare that simple, good stability, life-span are long, the selectivity Methylquecksilber ion fluorescence transmitter that is prone to preserve and preparation method thereof and analytical applications.
The technical scheme that the present invention adopts is:
A kind of fluorescence ion blotting transmitter, said fluorescence ion blotting transmitter is prepared by following method:
(1) Methylquecksilber compound and fluorescent chemicals are dissolved in the reaction solvent, mix, add function monomer, linking agent and initiator again, mix, obtain reaction soln;
Said Methylquecksilber compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Said fluorescent chemicals is the basic quinoline of 8-mercapto (hydroxyl), 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-VCz or 2-naphthyl propenoate;
Said function monomer is one of following: methylacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylic amide;
Said linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Said initiator is a Diisopropyl azodicarboxylate;
Said reaction solvent is DMSO 99.8MIN., water or both mixtures.
The ratio of the amount of substance of said Methylquecksilber 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 said 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 leaving standstill 1～60min; Millipore filtration after the immersion is sandwiched between sheet glass or quartz plate, and the degassing is sealing also, usually can be with sealing outside preservative film or freshness protection package bag sheet glass or the quartz plate after the degassing; Place then under 60～70 ℃ of water-baths or the UV-light and carried out polyreaction 4～32 hours; After the reaction millipore filtration is taken out from sheet glass or quartz plate, constant with the Methylquecksilber compound on the elutriant wash-out film to the fluorescence intensity that detects film, again through washing, be drying to obtain said fluorescence ion blotting transmitter;
Said 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).
Said millipore filtration is vinylidene fluoride film, CAM, polypropylene screen or poly (ether sulfone) film.The thickness of said millipore filtration is generally 0.2～0.65 μ m, can select for use the millipore filtration of purchasing common on the market to get final product.The big I of said millipore filtration is cut out as required voluntarily.
The concentration of said initiator in reaction solvent is 0.001～0.02g/ml.
The volumetric usage of said reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of Methylquecksilber compound usually.
The present invention also provides a kind of method for preparing said fluorescence ion blotting transmitter, and said method is:
(1) Methylquecksilber compound and fluorescent chemicals are dissolved in the reaction solvent, mix, add function monomer, linking agent and initiator again, mix, obtain reaction soln;
Said Methylquecksilber compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Said fluorescent chemicals is the basic quinoline of 8-mercapto (hydroxyl), 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-VCz or 2-naphthyl propenoate;
Said function monomer is one of following: methylacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylic amide;
Said linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Said initiator is a Diisopropyl azodicarboxylate;
Said reaction solvent is DMSO 99.8MIN., water or both mixtures.
The ratio of the amount of substance of said Methylquecksilber 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 said function monomer and linking agent is: 1: 2～8.
(2) millipore filtration is immersed in the reaction soln that step (1) obtains, takes out after leaving standstill 1～60min, the millipore filtration after soaking is sandwiched between sheet glass or quartz plate; The degassing and sealing; Usually can place then under 60～70 ℃ of water-baths or the UV-light and carry out polyreaction 4～32 hours, after the reaction with sealing outside preservative film or freshness protection package bag sheet glass or the quartz plate after the degassing; Remove preservative film or freshness protection package; Millipore filtration is taken out from sheet glass or quartz plate, constant with the Methylquecksilber compound on the elutriant wash-out film to the fluorescence intensity that detects film, again through washing, be drying to obtain said fluorescence ion blotting transmitter;
Said elutriant be 0.05～1M acetic acid, nitric acid, hydrochloric acid, sulfuric acid or or the EDTA aqueous solution in one or more.
In the said method, in the said step (1), the said ultrasonic mixing 10～40min of preferred use that mixes.
In the said method, in the said step (2), place under 60～70 ℃ of water-baths or the UV-light and carried out polyreaction 4～32 hours, preferably in 60～70 ℃ of water-baths, reacted 6～32 hours or under UV-light, reacted 20～32 hours.
In the method for the present invention, the concentration of said 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 Methylquecksilber compound usually.
The present invention also provides the application of described fluorescence ion blotting transmitter in the Methylquecksilber ion detection.
Further, the method for application according to the invention is:
Drawing standard curve: with the Methylquecksilber standardized solution of pH=7HCl-Tris damping fluid preparation different concns; Fluorescence ion blotting transmitter is placed the Methylquecksilber standardized solution of different concns, leave standstill 1～30min, take out after reaching adsorption equilibrium; Inhale the moisture on striping surface with filter paper; Detect the fluorescence intensity I of fluorescence ion blotting transmitter behind the absorption Methylquecksilber, excitation wavelength 250-350nm detects wavelength 300-500nm; And detect the fluorescence intensity of blank fluorescence ion blotting transmitter under similarity condition for contrast, be designated as I
0Methylquecksilber concentration with absorption is X-coordinate, with (I/I
0-1) % is an ordinate zou, draws to obtain typical curve;
Testing sample solution with pH=7HCl-Tris damping fluid dilution, must be supplied test agent solution through 0.45 μ m filtering with microporous membrane, with fluorescence ion blotting transmitter in deionized water fully after the swelling; Take out, inhale the moisture on striping surface, place the fluorescence orifice plate with filter paper; Getting said confession test agent solution adding is equipped with in the fluorescence orifice plate of said fluorescence ion blotting transmitter; Excitation wavelength 250-350nm detects wavelength 300-500nm, the reference standard curve; Obtain the Methylquecksilber ionic concn in the said confession test agent solution, calculate the Methylquecksilber ionic concn in the testing sample solution again.
Methylquecksilber ion blotting transmitter of the present invention is the polymer type sensor that multiple function monomer and fluorescent chemicals and template ion form through polymerization methods; Coordination according to polymerization process intermediate ion and other compound; Wash-out post polymerization thing inside can stay and template ion space structure complementary void structure and chemically bonded effect, thereby realizes the specificity identification to the target heavy metal, also has the following advantages simultaneously: preparation is simple relatively, good stability, be prone to preserve; Life-span is long; Do not pollute sample, and be easy to combine, have extensive practicality with optics.
Effect of the present invention is mainly reflected in: the invention provides a kind of fluorescence ion blotting transmitter that is used for the Methylquecksilber ion detection; Its form is for being the polymer compound film of support membrane with the commercial membranes; The preparation process is simple relatively, and the transmitter for preparing has advantages such as specific recognition ability, anti-extraneous mal-condition, freedom from jamming, and recycles the performance that repeatedly still can keep good; Having extensive practicality, is one of toxic metal ionic method in the rapid detection actual sample.
(4) description of drawings
Fig. 1 is the canonical plotting of embodiment 8.
(5) embodiment
Below in conjunction with specific embodiment the present invention is described further, 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 among the 1.5mlDMSO; In said mixture, add the 0.008mmol methylacrylic acid, 0.04mmol ethylene glycol dimethacrylate and 0.015g Diisopropyl azodicarboxylate thorough mixing, ultrasonic mixing 30min gets reaction soln; With 1cm length * 1cm wide * take out after the CAM of 0.2 μ m thickness places above-mentioned reaction soln to leave standstill 30min, clamp with quartz plate, drive out of behind the bubble with sealing film quartz plate wrapped the sealing back 65 ℃ of following heating in water bath 15 hours.After reacting completely; The Methylquecksilber ion blotting film of preparation is taken out,, use 0.1M sulphuric acid soln wash-out template ion more earlier with 0.1M EDTA aqueous solution wash-out; No longer change until detecting fluorescence intensity; Use methyl alcohol and ultrapure water wash-out again, at last that blotting membrane is dry, be fluorescence ion blotting transmitter.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
Embodiment 2:
0.002mmol Monomethyl mercury chloride and 0.004mmol 2-naphthyl propenoate are dissolved in the ultrasonic 30min of mixing among the 1mlDMSO; Add 4-vinylpridine 0.4mmol again; 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 places above-mentioned reaction soln to leave standstill 20min; Clamp with quartz plate; After sealing film phonograph seal, made Methylquecksilber ion fluorescence blotting membrane in 10 hours after driving bubble out of at 65 ℃ of following heating in water bath; Film is taken out from quartz plate, use 0.1M HNO
3Template ion on the eluant solution blotting membrane no longer changes until fluorescence intensity, uses the residual HNO of ultrapure water eccysis then
3Solution, blotting membrane is dry, be fluorescence ion blotting transmitter.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
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 2-vinyl pyridine 0.4mmol again; 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 CAM of 0.65 μ m thickness places above-mentioned reaction soln to leave standstill 10min; Clamp with quartz plate; Drive out of behind the bubble with sealing behind the film phonograph seal 65 ℃ of following heating in water bath 6 hours; Make Methylquecksilber ion fluorescence blotting membrane, film is taken out from quartz plate, use 0.1M HNO
3Template ion on the eluant solution blotting membrane is constant until fluorescence intensity, and with the residual HNO of ultrapure water eccysis
3After, blotting membrane is dry, be fluorescence ion blotting transmitter.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
Embodiment 4:
0.006mmol thiooxine and 0.002mmol methyl-mercuric bromide are dissolved in the ultrasonic 20min of mixing among the 1.5mlDMSO; In said mixture, add the 0.4mmol acrylic amide, 2mmol ethylene glycol dimethacrylate and 0.015g Diisopropyl azodicarboxylate thorough mixing, 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 places above-mentioned reaction soln to leave standstill 40min, clamp with quartz plate, drive the bubble sealing out of, be placed on ultra violet lamp under and reacted 20 hours.After reacting completely, the Methylquecksilber ion blotting film taking-up with preparation with 0.1M HCl eluant solution, no longer changes until fluorescence intensity, and is at last that blotting membrane is dry with the residual HCl solution of ultrapure water eccysis, is fluorescence ion blotting transmitter.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
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 the O solution adds 2-vinyl pyridine 0.5mmol again, 2mmol trimethoxy propane trimethyl acrylic ester and 0.015g Diisopropyl azodicarboxylate, and ultrasonic mixing 20min gets reaction soln; With 2cm length * 2cm wide * take out after the polyvinylidene fluoride film of 0.45 μ m thickness places above-mentioned reaction soln to leave standstill 50min, clamp with quartz plate, reacted 32 hours under ultra violet lamp degassing sealing back; Make Methylquecksilber ion fluorescence blotting membrane; Film is taken out from quartz plate, stable with the template ion on the 0.1M HCl eluant solution blotting membrane until fluorescence intensity, and with behind the residual HCl of ultrapure water eccysis; Blotting membrane is dry, be fluorescence ion blotting transmitter.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
Embodiment 6:
0.004mmol N-VCz and 0.002mmol methyl-mercuric iodide are mixed ultrasonic 30min in 1.5mlDMSO; Add 2-vinyl pyridine 0.4mmol again,, 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 places above-mentioned reaction soln to leave standstill 20min, clamp with quartz plate, be placed on 65 ℃ of following heating in water bath 24 hours with sealing film phonograph seal; Make Methylquecksilber ion fluorescence blotting membrane; Film is taken out from quartz plate, stable with the template ion on the 0.1M HCl eluant solution blotting membrane until fluorescence intensity, and with behind the residual HCl solution of ultrapure water eccysis; At last that blotting membrane is dry, be fluorescence ion blotting transmitter.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
Embodiment 7:
0.004mmol thiooxine and 0.004mmol Monomethyl mercury chloride are dissolved in the ultrasonic 10min of mixing among the 2mlDMSO; In said mixture, add the 0.016mmol methylacrylic acid, 0.032mmol trimethoxy propane trimethyl acrylic ester and 0.002g Diisopropyl azodicarboxylate thorough mixing, ultrasonic mixing 35min gets reaction soln; With 1cm length * 1cm wide * take out after the CAM of 0.65 μ m thickness places above-mentioned reaction soln to leave standstill 60min, clamp with quartz plate, drive bubble out of, the back is with sealing film phonograph seal, is placed on 65 ℃ of following heating in water bath 32 hours.After reacting completely, earlier with 1M EDTA aqueous solution wash-out template ion, until the fluorescence intensity vary stable, methyl alcohol and ultrapure water wash-out are dry with blotting membrane at last then, are fluorescence ion blotting transmitter with the metals ion blotting membrane for preparing.Gained fluorescence trace biosensor analysis detects the best pH=7 of Methylquecksilber ionic, and it is constant to recycle life-span 20 performances.
Embodiment 8: application implementation example 1
Drawing standard curve: with the Methylquecksilber ion standardized solution of pH=7HCl-Tris damping fluid preparation different concns.Place different Methylquecksilber solions to leave standstill 5min the fluorescence trace transmitter of preparation among the embodiment 1; 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 behind absorption Methylquecksilber ion; Excitation wavelength 350nm detects wavelength 420nm, and not add the fluorescence intensity of Methylquecksilber ionic fluorescence trace wet film under similarity condition with blank be that contrast (is designated as I
0), with absorption the Methylquecksilber ionic concn be X-coordinate, with (I/I
0-1) % is an ordinate zou, drawing standard curve (seeing accompanying drawing 1).
Actual water sample article Methylquecksilber 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, must supply test agent solution.The fluorescence trace dry film that embodiment 1 is made after the abundant swelling, takes out in deionized water, inhales the moisture on striping surface with filter paper; Be positioned in the fluorescence orifice plate; Get the adding of the above-mentioned confession test agent of 300 μ l solution and contain in the fluorescence microwell plate of fluorescence blotting membrane, measure fluorescence intensity, reference standard curve by above-mentioned condition; Record and supply to contain in the test agent solution Methylquecksilber 0.081mg/l (with adopting gas Chromatographic Determination basically identical as a result), calculating can get testing sample, and to contain Methylquecksilber be 0.162mg/l.
Claims (8)
1. fluorescence ion blotting transmitter is characterized in that said fluorescence ion blotting transmitter is prepared by following method:
(1) Methylquecksilber compound and fluorescent chemicals are dissolved in the reaction solvent, add function monomer, linking agent and initiator again, mix, obtain reaction soln;
Said Methylquecksilber compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Said fluorescent chemicals is the basic quinoline of 8-mercapto (hydroxyl), 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-VCz or 2-naphthyl propenoate;
Said function monomer is one of following: methylacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylic amide;
Said linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Said initiator is a Diisopropyl azodicarboxylate;
Said reaction solvent is DMSO 99.8MIN., water or both mixtures.
The ratio of the amount of substance of said Methylquecksilber compound, fluorescent chemicals and function monomer is 1: 1～4: 4～250, and the ratio of the amount of substance of said 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 leaving standstill 1～60min; Millipore filtration after soaking is sandwiched between sheet glass or quartz plate; The degassing and sealing place then under 60～70 ℃ of water-baths or the UV-light and carried out polyreaction 4～32 hours, after the reaction millipore filtration are taken out from sheet glass or quartz plate; Methylquecksilber compound with on the elutriant wash-out film is constant to the fluorescence intensity that detects film, again through washing, be drying to obtain said fluorescence ion blotting transmitter;
Said 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 transmitter as claimed in claim 1 is characterized in that said millipore filtration is vinylidene fluoride film, CAM, polypropylene screen or poly (ether sulfone) film.
3. fluorescence ion blotting transmitter as claimed in claim 1; It is characterized in that the concentration of said initiator in reaction solvent is 0.001～0.02g/ml, the volumetric usage of said reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of Methylquecksilber compound.
4. one kind prepares the method for fluorescence ion blotting transmitter according to claim 1, it is characterized in that said method is:
(1) Methylquecksilber compound and fluorescent chemicals are dissolved in the reaction solvent, add function monomer, linking agent and initiator again, mix, obtain reaction soln;
Said Methylquecksilber compound is Monomethyl mercury chloride, methyl-mercuric bromide or methyl-mercuric iodide;
Said fluorescent chemicals is the basic quinoline of 8-mercapto (hydroxyl), 1-allyl group-3-(1-naphthyl)-2-thiocarbamide, N-VCz or 2-naphthyl propenoate;
Said function monomer is one of following: methylacrylic acid, vinylformic acid, 2-vinyl pyridine, 4-vinylpridine or acrylic amide;
Said linking agent is one of following or both mixtures: ethylene glycol dimethacrylate or trimethoxy propane trimethyl acrylic ester;
Said initiator is a Diisopropyl azodicarboxylate;
Said reaction solvent is DMSO 99.8MIN., water or both mixtures.
The ratio of the amount of substance of said Methylquecksilber compound, fluorescent chemicals and function monomer is: 1: 1～4: 4～250, and the ratio of the amount of substance of said 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 leaving standstill 1～60min; Millipore filtration after soaking is sandwiched between sheet glass or quartz plate; The degassing and sealing place then under 60～70 ℃ of water-baths or the UV-light and carried out polyreaction 4～32 hours, after the reaction millipore filtration are taken out from sheet glass or quartz plate; Methylquecksilber compound with on the elutriant wash-out film is constant to the fluorescence intensity that detects film, again through washing, be drying to obtain said fluorescence ion blotting transmitter;
Said elutriant is one or more in acetic acid, nitric acid, hydrochloric acid, sulfuric acid or the EDTA aqueous solution of 0.05～1M.
5. like the method for the said fluorescence ion blotting of claim 4 transmitter, it is characterized in that the sealing after the said degassing is to seal outside wrapping in sheet glass or quartz plate with preservative film or freshness protection package.
6. fluorescence ion blotting transmitter as claimed in claim 4; It is characterized in that the concentration of said initiator in reaction solvent is 0.001～0.02g/ml, the volumetric usage of said reaction solvent is counted 0.5～1.5mL/ μ mol with the amount of substance of Methylquecksilber compound.
7. the application of fluorescence ion blotting transmitter as claimed in claim 1 in the Methylquecksilber ion detection.
8. application as claimed in claim 7 is characterized in that the method for said application is:
Drawing standard curve: the Methylquecksilber standardized solution of preparing different concns with the HCl-Tris damping fluid of pH=7; Fluorescence ion blotting transmitter is placed the Methylquecksilber standardized solution of different concns, leave standstill 1～30min, take out after reaching adsorption equilibrium; Inhale the moisture on striping surface with filter paper; Detect the fluorescence intensity I of fluorescence ion blotting transmitter behind the absorption Methylquecksilber, excitation wavelength 250-350nm detects wavelength 300-500nm; And detect the fluorescence intensity of blank fluorescence ion blotting transmitter under similarity condition for contrast, be designated as I
0Methylquecksilber concentration with absorption is X-coordinate, with (I/I
0-1) % is an ordinate zou, draws to obtain typical curve;
Testing sample solution with the dilution of the HCl-Tris damping fluid of pH=7, must be supplied test agent solution through 0.45 μ m filtering with microporous membrane, with fluorescence ion blotting transmitter in deionized water fully after the swelling; Take out, inhale the moisture on striping surface, place the fluorescence orifice plate with filter paper; Getting said confession test agent solution adding is equipped with in the fluorescence orifice plate of said fluorescence ion blotting transmitter; Excitation wavelength 250-350nm detects wavelength 300-500nm, the reference standard curve; Obtain the Methylquecksilber ionic concn in the said confession test agent solution, calculate the Methylquecksilber ionic concn in the testing sample solution again.
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Cited By (2)
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| CN109438598A (en) * | 2018-09-28 | 2019-03-08 | 昆明理工大学 | It is a kind of using 2 mercaptopropionic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
| CN109663581A (en) * | 2018-12-03 | 2019-04-23 | 昆明理工大学 | A method of cobalt (II) ion blotting composite membrane is prepared with N- pyrrolidinyl acrylamide |
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| CN102060958A (en) * | 2010-11-11 | 2011-05-18 | 天津工业大学 | Method for preparing fudosteine molecularly imprinted polymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438598A (en) * | 2018-09-28 | 2019-03-08 | 昆明理工大学 | It is a kind of using 2 mercaptopropionic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
| CN109438598B (en) * | 2018-09-28 | 2020-09-25 | 昆明理工大学 | Preparation method and application of hexavalent chromium ion imprinted composite membrane with 2-mercaptopropionic acid as functional monomer |
| CN109663581A (en) * | 2018-12-03 | 2019-04-23 | 昆明理工大学 | A method of cobalt (II) ion blotting composite membrane is prepared with N- pyrrolidinyl acrylamide |
| CN109663581B (en) * | 2018-12-03 | 2022-01-14 | 昆明理工大学 | Method for preparing cobalt (II) ion imprinting composite membrane by using N-pyrrolidinylacrylamide |
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