CN112179882A - Method for detecting organophosphorus pesticide by using MOFs @ QDs material in farmland environment - Google Patents
Method for detecting organophosphorus pesticide by using MOFs @ QDs material in farmland environment 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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- 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
Abstract
The invention discloses a method for detecting organophosphorus pesticide by using MOFs @ QDs material in farmland environment. Adding materials of 4-carboxyphenylbenzene, zirconium chloride and benzoic acid into dimethylformamide and water for ultrasonic mixing, reacting in a reaction kettle, naturally cooling, washing with methanol, and drying overnight to obtain the Zr-MOFs material; dissolving in water again, ultrasonically mixing uniformly, adding quantum dots, mixing, ultrasonically centrifuging, washing and drying to obtain the Zr-MOFs @ QDs sensor; taking a Zr-MOFs @ QDs sensor, diluting the sensor by PBS, adding organophosphorus pesticide, mixing uniformly, and detecting fluorescence intensity in a micropore plate detector. The invention can carry out high-sensitivity rapid detection on pesticide residues, has good selective detection capability on methyl parathion and parathion, has very wide detection limit from 0.005mg/L to 2mg/L, improves the detection efficiency and has wide application.
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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