CN112179882A - Methods for the detection of organophosphorus pesticides using MOFs@QDs materials in farmland environments - Google Patents
Methods for the detection of organophosphorus pesticides using MOFs@QDs materials in farmland environments Download PDFInfo
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- CN112179882A CN112179882A CN202011011558.1A CN202011011558A CN112179882A CN 112179882 A CN112179882 A CN 112179882A CN 202011011558 A CN202011011558 A CN 202011011558A CN 112179882 A CN112179882 A CN 112179882A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- 239000000575 pesticide Substances 0.000 title claims abstract description 20
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 33
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002096 quantum dot Substances 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 7
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000003987 organophosphate pesticide Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 9
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- 239000000203 mixture Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001917 fluorescence detection Methods 0.000 claims description 4
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
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- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- SRTQKANXPMBQCX-UHFFFAOYSA-N 4-[2,4,5-tris(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=C(C=2C=CC(=CC=2)C(O)=O)C=C1C1=CC=C(C(O)=O)C=C1 SRTQKANXPMBQCX-UHFFFAOYSA-N 0.000 claims description 2
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
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- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000000447 pesticide residue Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
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- 238000010791 quenching Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- XLNZEKHULJKQBA-UHFFFAOYSA-N terbufos Chemical compound CCOP(=S)(OCC)SCSC(C)(C)C XLNZEKHULJKQBA-UHFFFAOYSA-N 0.000 description 4
- 239000005958 Fenamiphos (aka phenamiphos) Substances 0.000 description 3
- 239000005949 Malathion Substances 0.000 description 3
- BXNANOICGRISHX-UHFFFAOYSA-N coumaphos Chemical compound CC1=C(Cl)C(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 BXNANOICGRISHX-UHFFFAOYSA-N 0.000 description 3
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 3
- ZCJPOPBZHLUFHF-UHFFFAOYSA-N fenamiphos Chemical compound CCOP(=O)(NC(C)C)OC1=CC=C(SC)C(C)=C1 ZCJPOPBZHLUFHF-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229960000453 malathion Drugs 0.000 description 3
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 description 3
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 102000012440 Acetylcholinesterase Human genes 0.000 description 2
- 108010022752 Acetylcholinesterase Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229940022698 acetylcholinesterase Drugs 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- YFVOXLJXJBQDEF-UHFFFAOYSA-N isocarbophos Chemical compound COP(N)(=S)OC1=CC=CC=C1C(=O)OC(C)C YFVOXLJXJBQDEF-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- RTSZQXSYCGBHMO-UHFFFAOYSA-N 1,2,4-trichloro-3-prop-1-ynoxybenzene Chemical compound CC#COC1=C(Cl)C=CC(Cl)=C1Cl RTSZQXSYCGBHMO-UHFFFAOYSA-N 0.000 description 1
- 239000005760 Difenoconazole Substances 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005961 Ethoprophos Substances 0.000 description 1
- JHJOOSLFWRRSGU-UHFFFAOYSA-N Fenchlorphos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Cl)C=C1Cl JHJOOSLFWRRSGU-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 208000010476 Respiratory Paralysis Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- VJYFKVYYMZPMAB-UHFFFAOYSA-N ethoprophos Chemical compound CCCSP(=O)(OCC)SCCC VJYFKVYYMZPMAB-UHFFFAOYSA-N 0.000 description 1
- 229950009006 fenclofos Drugs 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- KVGLBTYUCJYMND-UHFFFAOYSA-N fonofos Chemical compound CCOP(=S)(CC)SC1=CC=CC=C1 KVGLBTYUCJYMND-UHFFFAOYSA-N 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
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- 238000004445 quantitative analysis Methods 0.000 description 1
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- 230000009897 systematic effect Effects 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
本发明公开了一种在农田环境中利用MOFs@QDs材料检测有机磷农药的方法。将4‑羧基苯基苯、氯化锆、苯甲酸的材料加入二甲基甲酰胺和水中超声混合，反应釜中反应，自然冷却后洗涤，再使用甲醇洗涤，过夜烘干制得Zr‑MOFs材料；再溶于水中超声混合均匀后加入量子点混合超声离心，洗涤烘干获得Zr‑MOFs@QDs传感器；取Zr‑MOFs@QDs传感器用PBS稀释后加入有机磷农药，混匀后在微孔板检测仪中检测荧光强度。本发明能高灵敏度进行农药残留快速检测，对甲基对硫磷及对硫磷具有良好的选择性检测能力，检测限非常宽从0.005mg/L～2mg/L，提高了检测效率，应用广泛。
The invention discloses a method for detecting organophosphorus pesticides by using MOFs@QDs material in farmland environment. The materials of 4-carboxyphenylbenzene, zirconium chloride, and benzoic acid are added to dimethylformamide and ultrasonically mixed in water, reacted in a reaction kettle, washed after natural cooling, washed with methanol, and dried overnight to obtain Zr-MOFs Material; redissolved in water and mixed uniformly, then added quantum dots, mixed with ultrasonic centrifugation, washed and dried to obtain Zr-MOFs@QDs sensor; Zr-MOFs@QDs sensor was diluted with PBS and then added with organophosphorus pesticides, and after mixing, it was placed in the micropores. Fluorescence intensity was detected in a plate detector. The invention can carry out rapid detection of pesticide residues with high sensitivity, has good selective detection ability for methyl parathion and parathion, the detection limit is very wide from 0.005mg/L to 2mg/L, the detection efficiency is improved, and the application is wide. .
Description
Technical Field
The invention relates to a method for detecting organophosphorus pesticide by using MOFs @ QDs material in farmland environment
Background
Organophosphorus pesticides (OPPs) are a class of pesticides widely used in agricultural production, and are mainly used for preventing and treating plant diseases and insect pests. Because the half-life of OPPs is long, if the OPPs are improperly used, residual agricultural products of OPs, environment and water can pollute serious systems. OPPs have an irreversible inhibitory ability on acetylcholinesterase (AChE) activity, interfere with the function of important organs, and finally cause respiratory paralysis and thus poisoning. The organophosphorus pesticide residue in water is mainly sprayed by the field, and the pesticide is infiltrated into a ditch, underground water and a river by the flushing of rainwater. Water is used as a main natural resource for human life, and the damage of the water body has great harm to organisms.
At present, the conventional detection methods for OPPs include large-scale instruments such as liquid chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry and the like, immunoassay, enzyme-linked immunosorbent assay, enzyme inhibition assay, biosensor method and the like. Most of the traditional large-scale instrument methods are time-consuming, require specially trained technicians and are not suitable for field detection; although the immunological method can accurately identify the organophosphorus pesticide in the sample and simultaneously measure a plurality of samples, the immunological method is only operated in a laboratory and cannot be operated under field conditions; the biosensor has high selectivity, short time consumption and small instrument volume, is suitable for field measurement, but still has the problems of insufficient stability and accuracy at present, and needs further research.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides a method for detecting organophosphorus pesticides by using MOFs @ QDs materials in a farmland environment. The method has good detection capability and high detection sensitivity on the organophosphorus pesticide.
The MOFs @ QDs material is innovatively combined with MOFs and QDs, has two fluorescence emission peaks, has good detection capability on both high-toxicity organophosphorus pesticides methyl parathion and parathion, and has the properties of rapidness, high sensitivity and visualization.
The technical scheme adopted by the invention is as follows:
1) preparation of Zr-MOFs:
adding materials of 4-carboxyphenylbenzene, zirconium chloride and benzoic acid into Dimethylformamide (DMF) and water for ultrasonic mixing, putting the mixture into a polytetrafluoroethylene reaction kettle for reaction, naturally cooling, washing the mixture for 2 times by using the DMF, and then washing the mixture for 1 time by using methanol; then, drying at the temperature of 60-80 ℃ overnight to prepare the Zr-MOFs material;
2) preparing Zr-MOFs @ QDs materials:
dissolving 1-50 mg of Zr-MOFs material in water, carrying out ultrasonic mixing uniformly, adding Quantum Dots (QDs) for mixed ultrasonic, centrifuging, washing with water for 3 times, and drying to obtain a metal-organic framework Material (MOFs) and Quantum Dot (QDs) combined material, namely the Zr-MOFs @ QDs sensor;
3) fluorescence detection:
diluting the Zr-MOFs @ QDs sensor by PBS (phosphate buffer solution) to a certain concentration, adding 90 mu L of organophosphorus pesticide (0.005 mg/L-2 mg/L) with a certain mass concentration into 10 mu L of the sensor, uniformly mixing, and detecting fluorescence intensity in a micropore plate detector.
In the step 1), the 4-carboxyphenylbenzene is 1, 3, 5-tris (4-carboxyphenyl) benzene or 1, 2, 4, 5-tetrakis (4-carboxyphenyl) benzene.
In the step 1), the molar ratio of 4-carboxyphenylbenzene, zirconium tetrachloride and benzoic acid is 1: 1-5: 40 to 300.
The 1) Quantum Dots (QDs) are red QDs-625, which are abbreviated as QDs.
In the step 1), the volume ratio of the dimethyl formamide DMF to the water is 1 mL-10 mL:1 mL.
In the step 1), the reaction is carried out in a reaction kettle in polytetrafluoroethylene for 6 to 48 hours at the temperature of between 100 and 120 ℃.
In the step 2), the volume ratio of Zr-MOFs (concentration of 1mg/ml) and QDs (concentration of 8 mu M) which are metal-organic framework materials is 1 ml:1 to 50 μ L.
In the step 3), the concentration of the PBS solution is 0.01-0.2 mol/L, and the pH value is 6.0-8.0.
The concentration of Zr-MOFs @ QDs in said 3) was made 25. mu.g/mL by dilution before detection.
The organophosphorus pesticide is methyl parathion or parathion.
In the specific implementation of the invention, specificity detection is carried out, the product material of Zr-MOF @ Qds is mixed with different pesticides (0.25ppm) (taking systematic phosphorus, triazophos, sulfotep, fenamiphos, methyl isosulforaphane, omethoate, isocarbophos, methamidophos, phorate, malathion, coumaphos, fenamiphos, terbufos and fonofos) to be compared with the test results of methyl parathion and parathion, and PBS is taken as a control group.
In the invention, Zr4+And H4TCPB generates Zr-MOFs under the condition of a hot solvent. The prepared Zr-MOFs has strong blue fluorescence under the ultraviolet irradiation condition as shown in FIG. 1A, and the Zr-MOFs @ QDs are purple fluorescence due to wrapping of the QDs as shown in FIG. 1B.
As the concentration of the organophosphorus pesticide increases, the fluorescence of the MOFs @ QDs is gradually attenuated, and the concentration of the organophosphorus pesticide (methyl parathion and parathion) is inversely proportional to the fluorescence intensity of the MOFs @ QDs, so that the organophosphorus pesticide quantitative analysis optical sensing system based on the MOFs @ QDs is established.
The invention has the beneficial effects that:
the porous material of Zr-MOFs @ QDs prepared by the invention is a high-sensitivity sensor for rapidly detecting pesticide residues.
Based on sensitive fluorescence quenching, the experiment of the invention finds that MOF @ QDs have good detection capability on methyl parathion and parathion, and the concentration of the organophosphorus pesticide can be intuitively judged through the change of fluorescence color. The method provided by MOF @ QDs has a very wide linear detection range (0.005 mg/L-2 mg/L), and the lower detection limits of methyl parathion and parathion are 0.0019mg/L and 0.0049mg/L respectively.
The method can be effectively applied to the determination of methyl parathion and parathion in the farmland environment, and has potential application value in the aspect of rapid detection of pesticides in environmental samples.
Drawings
FIG. 1 is a graph showing the results of a solution test tube according to an embodiment of the present invention;
in FIG. 1, A is Zr-MOFs under ultraviolet light, and B is a Zr-MOFs @ QDs solution under ultraviolet light;
a and B in FIG. 2 are respectively a scanning electron microscope image and a transmission electron microscope image of Zr-MOFs and Zr-MOFs @ QDs;
FIG. 3A is a fluorescence emission spectrum of Zr-MOFs @ QDs added with 0-2 mg/L of methyl parathion, and B is a fluorescence emission spectrum of Zr-MOFs @ QDs added with 0-2 mg/L of parathion;
FIG. 4 is a graph of the standard for detecting methyl parathion and parathion by MOFs @ QDs in accordance with an embodiment of the present invention;
FIG. 5 is a diagram of a method-specific assay.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
The examples of the invention are as follows:
1. materials and methods
1.1 materials and instruments
Negative controls of field water, tap water and river water were collected.
Selecting and purchasing organophosphorus pesticide standard solutions such as systemic phosphorus, azophos, sulfotep, fenamiphos, methyl isosulforaphane, omethoate, methamidophos, phorate, malathion, coumaphos, fenclofos, terbufos, difenoconazole and the like.
4-carboxyphenylbenzene was purchased from Sigma Aldrich, benzoic acid and N, Dimethylformamide (DMF) was purchased from Sangon Biotech. Hydroxyl water-soluble quantum dot-625 (red fluorescence) selected as the quantum dot is purchased from Wuhan Jia source quantum dot technology development Limited liability company.
When tested, the fluorescence spectrum and the UV-Vis spectrum are recorded
M5 multimode microplate reader (molecular device). Scanning Electron Microscope (SEM) images and Transmission Electron Microscope (TEM) were obtained using SU8010 field emission scanning electron microscope (hitachi, japan) and F20 XT field emission transmission electron microscope (usa).
1.2 Experimental methods
1.2.1 Synthesis of Metal organic framework materials
Preparation of Zr-MOFs in general, H is450mg of TCPB, 70mg of zirconium chloride, 2700mg of benzoic acid, DMF and 30mL of water (V: 2:1) were ultrasonically mixedMixing for 15min, placing into a reaction kettle in polytetrafluoroethylene for reaction at 120 ℃ for 24h, naturally cooling, washing with DMF for 2 times, and washing with methanol for 1 time. Oven drying at 60 deg.C overnight to obtain white powder.
1.2.2 preparation of Zr-MOFs @ QDs.
Dissolving a proper amount of Zr-MOFs in water, carrying out ultrasonic mixing uniformly, adding QDs (quantum dots per second) for mixed ultrasonic, centrifuging, washing with water for three times, and drying for later use.
1.2.3 fluorescence detection
The material is diluted to a certain concentration by PBS (0.1mol/mL, pH is 6.0), then 90 muL of organophosphorus pesticide (0.005 mg/L-2 mg/L) with a certain concentration is added into 10 muL of aqueous solution of the Zr-MOFs @ QDs sensor, and after mixing, the fluorescence intensity is detected in a micropore plate detector.
Test conditions and results of the examples:
1. characterization of MOFs and Zr-MOFs @ QDs
A in FIG. 2 is the appearance of the Zr-MOFs represented by a scanning electron microscope and a transmission electron microscope, and shows a flower-shaped MOFs material with the average size of 0.6 μm, and B, the scanning electron microscope can see that a layer of substance is wrapped on the surface of the Zr-MOFs, the original appearance characteristics of the Zr-MOFs are lost, and a large number of QDs particles are embedded into the Zr-MOFs, so that the synthesis of MOF @ QDs is proved to be successful.
2. As the concentration of the pesticide is increased, the fluorescence of MOFs @ QDs at 400nm is remarkably reduced, the fluorescence of QDs at 625nm also has a descending trend, the fluorescence intensity is reduced along with the increase of the concentration of the pesticide overall, and the conversion from purple red to red is finally shown, and the result is shown in figure 3
3. The calculation formula for the quenching efficiency amount is (I)0-I)/I0，I0The initial emission peak intensity and I the emission peak intensity after addition of the analyte, the results are shown in FIG. 3. The quenching efficiency increases with increasing methyl parathion and the logarithm of the parathion concentration. Linear fitting of the equation methyl parathion to y 33.112x +83.235 (R)20.9936) parathion y 35.174x +83.906 (R)20.9927) to yield a linear curve of log quenching efficiency at final concentration in the range of 0.005mg/L to 2mg/L, x and y representing OPP, respectivelys concentration logarithm and quenching efficiency amount.
The limit of detection LOD was determined to be 0.0019mg/L for methyl parathion and 0.0049mg/L for parathion using the equation LOD ═ 3n/S, where n is the standard deviation of the response at the lowest concentration and S is the slope of the calibration curve.
4. Selectivity of Zr-MOFs @ QDs sensor to OPPs
In order to prove the specific selectivity of the prepared Zr-MOFs @ QDs sensor on 10 OPPs (ethoprophos, methyl isoxaphos, omethoate, isocarbophos, methamidophos, phorate, malathion, coumaphos, parathion and methyl parathion). Under the same conditions, the same concentration of each organophosphorus pesticide 0.25mg/L was measured.
FIG. 4 shows the response of fluorescence intensity to these OPPs. The result shows that the fluorescence signal is obviously changed due to the existence of 0.25mg/L methyl parathion and parathion, and the reduction range of other OPPs is small. Mainly due to quenching effect caused by fluorescence energy transfer effect of nitrobenzene in methyl parathion and parathion on Zr-MOF @ QDs.
Therefore, the sensor has higher sensitivity and selectivity for detecting the methyl parathion and the parathion.
5. Actual sample detection
The Zr-MOFs @ QDs sensor is used for detecting practical samples of OPPs.
The contents of methyl parathion and parathion in the sample are measured by adopting a standard addition method. Methyl parathion and parathion (0.01, 0.1 and 1mg/L) with different concentrations are respectively introduced into three samples of river water, field water and tap water, and fluorescence detection is carried out by using Zr-MOFs @ QDs.
The results are shown in Table 1, the average RSD of the methyl parathion recovery rate is between 93.23% and 116.46%, the average RSD is between 89.85% and 107.83%, and the average RSD is 5.75%.
TABLE 1 results of the detection of methyl parathion and parathion in the actual samples
Therefore, the Zr-MOFs @ QDs sensor has good reliability and is suitable for OPPs analysis of actual samples.
Claims (10)
1. A method for detecting organophosphorus pesticide by using MOFs @ QDs material in farmland environment is characterized by comprising the following steps:
1) preparation of Zr-MOFs:
adding materials of 4-carboxyphenylbenzene, zirconium chloride and benzoic acid into Dimethylformamide (DMF) and water for ultrasonic mixing, putting the mixture into a reaction kettle for reaction, naturally cooling, washing the mixture for 2 times by using the DMF, and then washing the mixture for 1 time by using methanol; then, drying at the temperature of 60-80 ℃ overnight to prepare the Zr-MOFs material;
2) preparing Zr-MOFs @ QDs materials:
dissolving 1-50 mg of Zr-MOFs material in water, carrying out ultrasonic mixing uniformly, adding Quantum Dots (QDs) for mixed ultrasonic, centrifuging, washing with water for 3 times, and drying to obtain a metal-organic framework Material (MOFs) and Quantum Dot (QDs) combined material, namely the Zr-MOFs @ QDs sensor;
3) fluorescence detection:
diluting the Zr-MOFs @ QDs sensor by PBS (phosphate buffer solution) to a certain concentration, adding 90 mu L of organophosphorus pesticide (0.005 mg/L-2 mg/L) with a certain mass concentration into 10 mu L of the sensor, uniformly mixing, and detecting fluorescence intensity in a micropore plate detector.
2. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: in the step 1), the 4-carboxyphenylbenzene is 1, 3, 5-tris (4-carboxyphenyl) benzene or 1, 2, 4, 5-tetrakis (4-carboxyphenyl) benzene.
3. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: in the step 1), the molar ratio of 4-carboxyphenylbenzene, zirconium tetrachloride and benzoic acid is 1: 1-5: 40 to 300.
4. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: the 1) Quantum Dots (QDs) are red QDs-625.
5. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that:
in the step 1), the volume ratio of the dimethyl formamide DMF to the water is 1 mL-10 mL:1 mL.
6. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: in the step 1), the reaction is carried out in a reaction kettle in polytetrafluoroethylene for 6 to 48 hours at the temperature of between 100 and 120 ℃.
7. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: in the step 2), the volume ratio of the metal organic framework materials Zr-MOFs and QDs is 1 ml:1 to 50 μ L.
8. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: in the step 3), the concentration of the PBS solution is 0.01-0.2 mol/L, and the pH value is 6.0-8.0.
9. The method for detecting organophosphorus pesticides by utilizing MOFs @ QDs material in farmland environment according to claim 1, which is characterized in that: the concentration of Zr-MOFs @ QDs in said 3) was made 25. mu.g/mL by dilution before detection.
10. The method for detecting organophosphorus pesticide in water body by using combination of MOF and Qds, according to claim 1, wherein: the organophosphorus pesticide is methyl parathion or parathion.
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