CN106905538B - A kind of zinc-containing metal organic framework materials and its preparation method and application - Google Patents
A kind of zinc-containing metal organic framework materials and its preparation method and application Download PDFInfo
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- CN106905538B CN106905538B CN201710101520.5A CN201710101520A CN106905538B CN 106905538 B CN106905538 B CN 106905538B CN 201710101520 A CN201710101520 A CN 201710101520A CN 106905538 B CN106905538 B CN 106905538B
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- parathion
- methyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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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- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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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- 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"
- G01N2021/6432—Quenching
Abstract
The present invention provides a kind of preparation methods of zinc-containing metal organic framework materials, comprising the following steps: mixes porphyrin, 4- carboxyl phenyl benzene, zinc nitrate and n,N-Dimethylformamide under ultrasound condition, obtains mixed solution；The mixed solution is subjected to hydro-thermal reaction, obtains zinc-containing metal organic framework materials.The present invention is that raw material prepares zinc-containing metal organic framework materials using porphyrin, benzene carboxyl benzene and zinc nitrate, preparation method is simple, step is few, and the fluorescence signal of obtained zinc-containing metal organic framework materials can be quenched by parathion-methyl, and fluorescent quenching degree and the logarithm of parathion-methyl content are linearly related, parathion-methyl is detected using zinc-containing metal organic framework materials, parathion-methyl may be implemented and quickly, simply, sensitively detect.
Description
Technical field
The present invention relates to a kind of technical fields of Detecting Pesticide, in particular to a kind of to utilize zinc-containing metal organic frame
The fluorescent method of material tests parathion-methyl.
Background technique
Parathion-methyl is a kind of high-toxic organic phosphorus esters of gallic acid pesticide, residual to ecological environment cause it is serious pollution with
Harm, after the mankind eat the vegetable food by pollution by pesticides, richness can be worked as in people's cylinder accumulation or enrichment by remaining in pesticide therein
When collecting a certain concentration, the acute or chronic poisoning of human body will be caused, causes a disease, is carcinogenic, it is even lethal.With mentioning for living standard
Height, people increasingly pay close attention to food hygiene and safety.In the foreign trade of food safety, environment and agricultural product, methyl pair
Sulphur phosphorus is classified as important soiling detector, and it is particularly important to establish quick, sensitive, reliable parathion-methyl detection method.
Currently, the detection method in relation to parathion-methyl mainly has spectroscopic methodology, immunoassay, chromatography, chromatography and matter
Combination method and ELISA method.These methods respectively have its advantage and disadvantage, and chromatography accurately still needs to configure expensive large-scale analyzer
Device, at the same it is high to the requirement of the technical quality of personnel, and general unit is extremely difficult to, and is unsuitable for quickly, easily carrying out large quantities of
The detection of sample is measured, the reagent that ELISA method is used is more, and cumbersome, time-consuming, influence factor is also more.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of quick, simplicity, sensitively utilizing zinc-containing metal organic frame material
The fluorescent method of material detection parathion-methyl
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of zinc-containing metal organic framework materials, which is characterized in that including following step
It is rapid:
Porphyrin, 4- carboxyl phenyl benzene, zinc nitrate and n,N-Dimethylformamide are mixed under ultrasound condition, mixed
Solution；
The mixed solution is subjected to hydro-thermal reaction, obtains zinc-containing metal organic framework materials.
Preferably, the porphyrin be in-four-(4- carboxyl phenyl) porphines, four (4- aminophenyl) porphyrins or four (4- nitros
Phenyl) porphyrin.
Preferably, the 4- carboxyl phenyl benzene is 1,3,5- tri- (4- carboxyl phenyl) benzene or 1,2,4,5- tetra- (4- carboxyl benzene
Base) benzene.
Preferably, the molar ratio of the porphyrin, 4- carboxyl phenyl benzene and zinc nitrate is 1:1.8~2.1:2.1~2.3；
The amount of the substance of the porphyrin and the volume ratio of N,N-dimethylformamide are 1mol:70~150ml.
Preferably, the temperature of the hydro-thermal reaction is 100~120 DEG C；The time of the hydro-thermal reaction is 24~48h.
The present invention provides a kind of zinc-containing metal organic framework materials of the preparation of preparation method described in above scheme.
The present invention provides zinc-containing metal organic framework materials described in a kind of above scheme in Fluorometric assay methyl pair
Application in sulphur phosphorus.
Preferably, it is described application the following steps are included:
Fluorescence intensity after sample to be tested is mixed with the alcoholic solution of zinc-containing metal organic framework materials；It is strong according to fluorescence
Angle value and scheduled standard curve obtain the concentration of parathion-methyl in sample to be tested；
The standard curve is the relation curve of fluorescence intensity and parathion-methyl log concentration.
Preferably, the standard curve is obtained by following steps:
Fluorescence is detected after standard solution containing parathion-methyl is mixed with the alcoholic solution of zinc-containing metal organic framework materials
Intensity draws the relation curve of fluorescence intensity and parathion-methyl log concentration, obtains standard curve.
Preferably, the range of linearity of the standard curve is 1ppb~10ppm.
The present invention provides a kind of preparation methods of zinc-containing metal organic framework materials, comprising the following steps: by porphyrin, 4-
Carboxyl phenyl benzene, zinc nitrate and n,N-Dimethylformamide mix under ultrasound condition, obtain mixed solution；The mixing is molten
Liquid carries out hydro-thermal reaction, obtains zinc-containing metal organic framework materials.The present invention is raw material using porphyrin, benzene carboxyl benzene and zinc nitrate
Zinc-containing metal organic framework materials are prepared, preparation method is simple, and step is few, and obtained zinc-containing metal organic framework materials is glimmering
Optical signal can be quenched by parathion-methyl, and fluorescent quenching degree and the logarithm of parathion-methyl content are linearly related, to be
The detection of parathion-methyl opens a new approaches.
The present invention also provides application of the zinc-containing metal organic framework materials in Fluorometric assay parathion-methyl.
Zinc-containing metal organic framework materials are applied in Fluorometric assay parathion-methyl by the present invention, utilize zinc-containing metal organic frame
Linear this related characteristic of the fluorescent quenching degree of material and the logarithm of parathion-methyl content, it is fast to realize parathion-methyl
Speed, simple, sensitively detection, the remaining detection of parathion-methyl suitable for food safety；And it only needs to utilize in the detection
A kind of this key reagents of zinc-containing metal organic framework materials are all realized in homogeneous in entire detection process, are avoided cumbersome
Operation, at the same avoid influence factor it is more caused by testing result inaccuracy problem, and the fluorescence detection speed is very
Fastly, it is only necessary to can be completed within 20 seconds or so, substantially increase detection efficiency.Test result shows fluorescent method pair of the present invention
The Monitoring lower-cut of parathion-methyl is 1ppb, upper limit of detection 10ppm, and testing result is accurate, and easy to operate, speed is fast.
Detailed description of the invention
Fig. 1 is the scanning electron microscopy of zinc-containing metal organic framework materials (ZnPO-MOF) prepared by the embodiment of the present invention 1
Mirror photo；
Fig. 2 is the X x ray diffration pattern x of zinc-containing metal organic framework materials (ZnPO-MOF) prepared by the embodiment of the present invention 1
Spectrum；
Fig. 3 is the thermogravimetric analysis figure of zinc-containing metal organic framework materials (ZnPO-MOF) prepared by the embodiment of the present invention 1；
Fig. 4 is the fluorescence response curve graph of sample in the embodiment of the present invention 2；
Fig. 5 is the photo that the sample in the embodiment of the present invention 2 is observed in the UV lamp；
Fig. 6 is the column relational graph of ZnPO-MOF concentration and fluorescence signal-to-noise ratio in 3 sample of the embodiment of the present invention；
Fig. 7 A is the fluorescence response curve graph of 4 sample of the embodiment of the present invention；
Fig. 7 B is the relational graph of the fluorescence intensity of 4 sample of the embodiment of the present invention and the logarithm of parathion-methyl concentration；
Fig. 8 is the fluorescence intensity histogram of sample in the embodiment of the present invention 5.
Specific embodiment
The present invention provides a kind of preparation methods of zinc-containing metal organic framework materials, comprising the following steps:
Porphyrin, 4- carboxyl phenyl benzene, zinc nitrate and n,N-Dimethylformamide are mixed under ultrasound condition, mixed
Solution；
The mixed solution is subjected to hydro-thermal reaction, obtains zinc-containing metal organic framework materials.
The present invention mixes porphyrin, benzene carboxyl benzene and zinc nitrate and n,N-Dimethylformamide under ultrasound condition, obtains
Mixed solution.In the present invention, the porphyrin be preferably in-four-(4- carboxyl phenyl) porphines, four (4- aminophenyl) porphyrins or
Four (4- nitrobenzophenone) porphyrins；The benzene carboxyl benzene is preferably (4- carboxyl phenyl) benzene of 1,3,5- tri- or (the 4- carboxylic of 1,2,4,5- tetra-
Base phenyl) benzene；The zinc nitrate is preferably nitric hydrate zinc, more preferably zinc nitrate hexahydrate.
In the present invention, the molar ratio of the porphyrin, benzene carboxyl benzene and zinc nitrate be preferably 1:1.8~2.1:2.1~
2.3, more preferably 1:2:2.2；The mole of the porphyrin and the volume ratio of N,N-dimethylformamide be preferably 1mol:70~
150ml, more preferably 1mol:70~100ml.
The present invention is decomposed using n,N-Dimethylformamide as solvent using n,N-Dimethylformamide in the synthesis process
Formamide promotes ligand to be easier to remove proton, to promote the combination of ligand and metal ion.
In the present invention, the time of the ultrasound is preferably 10~20min, more preferably 15min；The present invention is to ultrasonic temperature
No particular/special requirement is spent, ultrasound is carried out at room temperature, without being heated and being cooled down；The present invention does not have the power of ultrasound
With particular/special requirement, the ordinary power used when using this field ultrasound, preferably 300~500W, more preferably 350~
450W。
After obtaining mixed solution, the mixed solution is carried out hydro-thermal reaction by the present invention, obtains zinc-containing metal organic frame
Material (ZnPO-MOF).In the present invention, the temperature of the hydro-thermal reaction is preferably 100~120 DEG C, more preferably 105~
115℃；The time of the hydro-thermal reaction is preferably 24~48h, more preferably 30~40h, most preferably 32~38h；The present invention
It is preferable to use reaction kettles to carry out hydro-thermal reaction；The present invention does not have particular/special requirement to the concrete form of reaction kettle, using ability and often
The reaction kettle of rule.
After the completion of the hydro-thermal reaction, the present invention preferably post-processes hydro-thermal reaction product, and obtaining zinc-containing metal has
Machine frame frame material (ZnPO-MOF).The post-processing preferably successively includes centrifugation, washing and drying.The present invention is to centrifugation without spy
It is different to require, use conventional centrifugal method of the invention；The washing is preferably centrifuge washing, specially to obtaining after centrifugation
Sediment in be added ethyl alcohol after be centrifuged, the method for the centrifugation is consistent with above scheme；The number of the centrifuge washing
Preferably 3~5 times, more preferably 4 times.After the completion of the washing, preferably the product after washing is dried by the present invention；It is described
Drying temperature is preferably 50~70 DEG C, more preferably 55~65 DEG C, most preferably 60 DEG C；The time of the drying is preferably 10~
18h, more preferably 12~15h, most preferably 13~14h.
The present invention provides a kind of zinc-containing metal organic framework materials of the preparation of preparation method described in above scheme.In this hair
In bright, the zinc-containing metal organic framework materials crystal structure is polycrystalline heaped-up, and thermal stability is stronger, and thermal decomposition temperature is
380 DEG C or so, and zinc-containing metal organic framework materials of the present invention have good structural stability, have in ethyl alcohol etc.
Dispersion is carried out in solvent will not influence the structure and pore distribution of material.
In the present invention, the fluorescence signal of the zinc-containing metal organic framework materials can be quenched by parathion-methyl, fluorescence
Quenching degree and the logarithm of parathion-methyl content are linearly related, and the parathion-methyl amount of addition is more, fluorescent quenching degree
It is more obvious；This performance of zinc-containing metal organic framework materials provided by the invention is that the fluorescence detection method of parathion-methyl mentions
A new approaches are supplied.
The present invention provides zinc-containing metal organic framework materials described in above scheme in Fluorometric assay parathion-methyl
Application.In the present invention, it is described application the following steps are included:
Fluorescence intensity after sample to be tested is mixed with the alcoholic solution of zinc-containing metal organic framework materials；
The concentration of parathion-methyl in sample to be tested is obtained according to fluorescence intensity level and scheduled standard curve；The standard
Curve is the relation curve of fluorescence intensity and parathion-methyl log concentration.
In the present invention, the alcohol is preferably methanol or ethyl alcohol；The alcoholic solution of the zinc-containing metal organic framework materials
Concentration is preferably 9.8~10.2 μ g/ml, more preferably 10 μ g/ml.
In the present invention, the sample to be tested is from determinands such as sewage, food or agricultural product, before determinand is carried out
Handle obtained liquid phase sample to be tested, sample to be tested as of the present invention；The present invention does not have the pre-treating method of determinand
There is particular/special requirement, common processing method when using this field fluorescence detection.In the present invention, the sample to be tested and contain
The volume ratio of the alcoholic solution of zinc metal-organic framework material is preferably 8.5~9.5:1, more preferably 9:1.
In some embodiments of the invention, when determinand is the solid matters such as agricultural product or food, it can pass through
Following methods carry out pre-treatment: carrying out homogeneous after determinand is blended, obtain homogeneous object；Homogeneous object and extractant are mixed laggard
Row centrifugation, obtains supernatant, to avoid other solvents from influencing ZnPO-MOF bring, supernatant is taken to dilute ten times with ethyl alcohol
After carry out subsequent parathion-methyl content detection.
In the present invention, described to blend that it is preferable to use tissue mashing machine's progress；The present invention is not special to the degree blended
It is required that.In the present invention, the revolving speed of the homogeneous is preferably 8000~12000 turns/min, more preferably 9000~10000 turns/
min；The time of the homogeneous is preferably 1~3min, more preferably 1.5~2.5min.
In the present invention, the extractant is preferably one of ethyl alcohol, acetonitrile, ethyl acetate, acetone and methylene chloride
Or several mixture；The volume of the extractant and the mass ratio of homogeneous object are preferably 4~10ml:1g, more preferably 5~
8ml:1g.
In the present invention, the revolving speed of the centrifugation is preferably 3000~5000 turns/min, more preferably 3500~4500
Turn/min；The time of the centrifugation is preferably 4~8min, more preferably 5~6min.
It, can be without pre- when determinand is the liquids such as sewage in another part specific embodiment of the invention
Processing detects after directly mixing the alcoholic solution of the test substances such as sewage and zinc-containing metal organic framework materials；When sewage etc.
When parathion-methyl content is higher/lower in liquid, is detected, be not necessarily to again after can simply being diluted/being concentrated
Carry out other pretreatments.
In the present invention, the standard curve is obtained by following steps:
Fluorescence is detected after standard solution containing parathion-methyl is mixed with the alcoholic solution of zinc-containing metal organic framework materials
Intensity draws the relation curve of fluorescence intensity and parathion-methyl log concentration, obtains standard curve.
In the present invention, the alcoholic solution of the zinc-containing metal organic framework materials is consistent with above scheme, no longer superfluous herein
It states.In the present invention, the standard solution is the standard solution that the parathion-methyl using purity greater than 99% is prepared；The mark
The parathion-methyl concentration of quasi- solution is preferably 10ppb~100ppm；The concentration gradient of the standard solution is preferably 2~10
Times, it, can be molten as the standard of minimum concentration using the standard solution that concentration is 10ppb in some embodiments of the invention
Liquid, carried out later with 2~10 times of gradient it is incremental, maximum concentration control be 100ppm.In the present invention, the standard solution and
The volume ratio of zinc-containing metal organic framework materials alcoholic solution and the sample containing parathion-methyl and zinc-containing metal organic framework materials
Alcoholic solution volume ratio it is identical, details are not described herein.In the present invention, the range of linearity of the standard curve be 1ppb~
10ppm。
In a specific embodiment of the present invention, the standard solution for preferably preparing 8~10 groups of various concentrations, by standard solution and
The mixing of zinc-containing metal organic framework materials, obtains mixed solution, control parathion-methyl in mixed solution concentration be 1ppb~
10ppm detects the fluorescence intensity of mixed solution, draws the relational graph of the logarithm of fluorescence intensity and parathion-methyl concentration, as
Standard curve, in the range, the logarithm of fluorescence intensity and parathion-methyl concentration are inversely proportional.In the present invention, the detection
The fluorescence detection condition of fluorescence intensity is preferred are as follows: 250~280nm of excitation wavelength, 360~398nm of fluorescence emission wavelengths, more preferably
For 260~270nm of excitation wavelength, 370~398nm of fluorescence emission wavelengths, most preferably excitation wavelength 275nm, fluorescent emission wave
Long 398nm.
The present invention detects glimmering after mixing the sample containing parathion-methyl with the alcoholic solution of zinc-containing metal organic framework materials
Luminous intensity obtains the concentration of parathion-methyl in sample according to the numerical value of fluorescence intensity and standard curve, and combines pre-treatment
Journey calculates the total concentration of parathion-methyl, finally obtains parathion-methyl in determinand (sewage, food, agricultural product etc.)
Actual concentrations.
Below with reference to embodiment to zinc-containing metal organic framework materials provided by the invention and its preparation method and application into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Take porphyrin 182mg, 1,2,4,5 benzene carboxyl benzene 255mg and Zn (NO3)2·6H2DMF is added in beaker in O 150mg
25mL, ultrasonic 15min make it uniformly；Uniformly mixed solution is poured into reaction kettle, 100 DEG C of reactions are for 24 hours；Hydro-thermal reaction is completed
Product is centrifuged removal supernatant liquid afterwards, ethyl alcohol is centrifuged repeatedly washing 3 times；ZnPO-MOF solid can be obtained in 60 DEG C of dry 10h
Powder.
Electron-microscopic analysis is scanned to resulting ZnPO-MOF material, acquired results are as shown in Figure 1；According to Fig. 1
As can be seen that ZnPO-MOF prepared by the present invention is the crystal grain of polycrystalline heaped-up；
Gained ZnPO-MOF material is detected using X-ray diffractometer, gained XRD spectrum is as shown in Fig. 2；According to
Fig. 2 can be seen that XRD spectra peak type is preferable, and appearance is obvious, illustrate ZnPO-MOF material crystalline situation prepared by the present invention compared with
It is good, and can be seen that the ZnPO-MOF is a typical polycrystalline.
Thermogravimetric analysis is carried out to gained ZnPO-MOF material, gained thermogravimetric analysis figure is as shown in Figure 3；It can be seen according to Fig. 3
Out, ZnPO-MOF material thermal stability prepared by the present invention is good, has good thermostabilization within the temperature range of being lower than 380 DEG C
Property, it will not decompose.
Embodiment 2
A, the ZnPO-MOF material of the preparation of 1mg embodiment 1 is weighed in 2mL centrifuge tube, and 1mL dehydrated alcohol is added, is configured to
1mg mL-1ZnPO-MOF solution, dilution 100 times it is spare；
B, using dehydrated alcohol as solvent, the parathion-methyl standard solution of 100ppm is configured；
C, 10 μ g mL are separately added into 96 microwell plates that number is A1, A2, A3, A4-190 μ L of ZnPO-MOF, to
It is added to be added in 10 μ L, the Xiang Kong A3 of parathion-methyl that concentration is 100ppm in 10 μ L, Xiang Kong A2 of dehydrated alcohol in the A1 of hole and be added
The 10 μ L of phoxim that concentration is 100ppm is added in 10 μ L, the Xiang Kong A4 of MTMC that concentration is 100ppm, is detected in microplate reader
Fluorescence intensity (testing conditions: excitation wavelength 275nm, wavelength of fluorescence 398nm) draws fluorescence intensity curves, acquired results such as Fig. 4
Shown, wherein curve a is sample A1 (being added without any pesticide) fluorescence response curve, and curve b is that (methyl is added to sulphur in sample A2
Phosphorus) fluorescence response curve, curve c is the fluorescence response curve of sample A3 (be added MTMC), and curve d is that sample A4 (is added
Phoxim) fluorescence response curve；According to Fig. 4 as can be seen that when being added without any pesticide, the fluorescence intensity of ZnPO-MOF compared with
By force, when the total concentration of parathion-methyl in sample is 10ppm, the fluorescence of ZnPO-MOF is quenched completely；When with other pesticides
When instead of parathion-methyl, the fluorescence of ZnPO-MOF does not have significant change；
Solution in A1, A2 is transferred in centrifuge tube 1 and centrifuge tube 2, puts and observes in the UV lamp, observation result is as schemed
Shown in 5；According to Fig. 5 as can be seen that the fluorescence intensity of ZnPO-MOF is obviously lower after parathion-methyl is added；
The above test result explanation, the fluorescence of zinc-containing metal organic framework materials (ZnPO-MOF) prepared by the present invention are strong
Degree can be quenched by parathion-methyl, and not influenced by other type pesticides.
Embodiment 3
A, the ZnPO-MOF material of the preparation of 1mg embodiment 1 is weighed in 2mL centrifuge tube, and 1mL dehydrated alcohol is added, is configured to
1mg mL-1ZnPO-MOF solution, gradient dilution ZnPO-MOF solution, obtaining concentration is 1mg mL-1, 100 μ gmL-1, 10 μ g mL-1, 1 μ g mL-1, 0.1 μ g mL-1ZnPO-MOF solution；
B, using dehydrated alcohol as solvent, the parathion-methyl standard solution of 100ppm is configured；
C, 1mg mL is added into 96 microwell plates that number is B1, C1-190 μ L of ZnPO-MOF；It is B2, C2 to number
100 μ g mL are added in 96 microwell plates-190 μ L of ZnPO-MOF；10 μ gmL are added into 96 microwell plates that number is B3, C3- 1ZnPO-MOF 90μL；1 μ g mL is added into 96 microwell plates that number is B4, C4-190 μ L of ZnPO-MOF；It is to number
0.1 μ g mL is added in 96 microwell plates of B5, C5-190 μ L of ZnPO-MOF；Ethyl alcohol 10 is added into hole B1, B2, B3, B4, B5
The 10 μ L of parathion-methyl of 100ppm is added in μ L, hole C1, C2, C3, C4, C5, the fluorescence intensity size (inspection in microplate reader
Survey condition: excitation wavelength 275nm, wavelength of fluorescence 398nm)；
If fluorescence response when parathion-methyl is not added is F0, fluorescence response when methylate parathion is F, is calculated each
Corresponding (the F0-F1)/F0 of ZnPO-MOF, and histogram is drawn, acquired results are as shown in Figure 6；According to Fig. 6 as can be seen that 10 μ g
mL-1ZnPO-MOF signal-to-noise ratio highest use 10 μ g mL when detecting parathion-methyl-1ZnPO-MOF, acquired results are more
It is accurate to add, and error is smaller.
Embodiment 4
A, the ZnPO-MOF material of the preparation of 1mg embodiment 1 is weighed in 2mL centrifuge tube, and 1mL dehydrated alcohol is added, is configured to
1mg mL-1ZnPO-MOF solution, 100 times of dilution are spare；
B, using dehydrated alcohol as solvent, the parathion-methyl standard solution of 1000ppm, gradient dilution are configured；Obtain concentration
For 500ppm, 100ppm, 50ppm, 10ppm, 5ppm, 1ppm, 0.5ppm, 100ppb, 50ppb, the parathion-methyl of 10ppb
Standard solution；
C, 10 μ g are separately added into 96 microwell plates that number is D1, D2, D3, D4, D5, D6, D7, D8, D9, D10, D11
mL-190 μ L of ZnPO-MOF, sequentially add concentration be 1000ppm, 500ppm, 100ppm, 50ppm, 10ppm, 5ppm,
The 10 μ L of parathion-methyl of 1ppm, 0.5ppm, 100ppb, 50 ppb, 10ppb, are added dehydrated alcohol into 96 microwell plates of D12
10 μ L, fluorescence intensity (testing conditions: excitation wavelength 275nm, wavelength of fluorescence 398nm) in microplate reader；
Acquired results are as shown in Figure 7 A, and a~k is followed successively by the fluorescence response curve graph of D1~D12, corresponding methyl in Fig. 7 A
Parathion final concentration of 100ppm, 50ppm, 10ppm, 5ppm, 1ppm, 0.5ppm, 100ppb, 50ppb, 10ppb, 1ppb,
0ppb；Can be seen that fluorescence intensity according to Fig. 7 A reduces with the increase of parathion-methyl concentration；
Using fluorescence intensity as ordinate, the logarithm of parathion-methyl concentration draws curve as abscissa, as a result as schemed
Shown in 7B, when can be seen that parathion-methyl concentration within the scope of 1ppb~10ppm according to Fig. 7 B, fluorescence intensity and methyl pair
The logarithm of sulphur phosphorus concentration is inversely proportional, and can be fitted to obtain normal equation: F=-2547.39*logC+11270.94 (wherein F
Fluorescence intensity is represented, unit a.u., C represent parathion-methyl concentration, unit ppb), which is that standard of the invention is bent
Line is 1ppb~10ppm according to the range of linearity that Fig. 7 B can be seen that the standard curve.
Embodiment 5
A, the ZnPO-MOF material of the preparation of 1mg embodiment 1 is weighed in 2mL centrifuge tube, and 1mL dehydrated alcohol is added, is configured to
1mg mL-1ZnPO-MOF solution dilutes 100 times of uses；
B, using dehydrated alcohol as solvent, the parathion-methyl standard solution of 100ppm is configured；
C, to 96 micropores that number is E1, E2, E3, E4, E5, E6, E7, E8, E9, E10, E11, E12, F1, F2, F3, F4
10 μ g mL are separately added into plate-190 μ L of ZnPO-MOF, sequentially add dehydrated alcohol, parathion-methyl (100ppm), Zhong Ding
Prestige (40ppm), MTMC (40ppm), Mobucin (40ppm), carbendazim (16ppm), chlorfluazuron (16ppm), d ichlorbenzuron
(16ppm), thimet sulfone (16ppm), phoxim (16ppm), Acetamiprid (16ppm), 3- hydroxyl carbofuran (16ppm), miaow are fresh
Amine (16ppm), 10 μ L of metalaxyl (100ppm), etoxazole (40ppm) and Envidor (40ppm), detect fluorescence in microplate reader
Intensity size (testing conditions: excitation wavelength 275nm, wavelength of fluorescence 398nm)；
Acquired results are as shown in Fig. 8, and a~p is respectively the fluorescence intensity of sample in E1~F4 in Fig. 8, can be with according to Fig. 8
To find out, parathion-methyl can quench the fluorescence of ZnPO-MOF, and other pesticides then do not influence its fluorescence intensity significantly,
Show that detection method of the invention has preferable specificity to parathion-methyl.
Embodiment 6
A, the ZnPO-MOF material of the preparation of 1mg embodiment 1 is weighed in 2mL centrifuge tube, and 1mL dehydrated alcohol is added, is configured to
1mg mL-1ZnPO-MOF solution dilutes 100 times of uses；
B, with the pretreatment fluid of farmland sewage, (farmland sewage sample dilutes ten times divided by dehydrated alcohol and does not do other pre- places
Reason) it is solvent, 100ppm, 10ppm, 1ppm are configured, the solution of the parathion-methyl of 0.1ppm, being respectively placed in number is 1~4
In 4 centrifuge tubes；
C, 10 μ g mL are separately added into 96 microwell plates that number is G1, G2, G3, G4, G5-190 μ L of ZnPO-MOF,
The 100ppm prepared in step b, 10 ppm, 1ppm are separately added into G1~G4 microwell plate, the parathion-methyl of 0.1ppm
10 μ L of dehydrated alcohol is added into G5 microwell plate by 10 μ L of solution；G1-G4 parathion-methyl final concentration is respectively 10000ppb,
1000ppb, 100ppb, 10ppb, the fluorescence intensity size (testing conditions: excitation wavelength 278nm, fluorescence wave in microplate reader
Long 398nm), the parathion-methyl concentration that detection obtains is calculated according to standard curve obtained in fluorescence intensity and embodiment 4, and
The rate of recovery is calculated, by the results are shown in Table 1；
1 testing result of table
Can be seen that according to the testing result in table 1 can effectively detect methyl to sulphur using the method provided by the present invention
The concentration of phosphorus, and the preferable rate of recovery can be obtained, illustrate that precision of method provided by the invention is higher, methyl can be used successfully to
Parathion is quickly actually detected.
As seen from the above embodiment, provided by the invention to detect parathion-methyl using zinc-containing metal organic framework materials
Fluorescent method is easy to operate, high sensitivity, and the trace inspection of parathion-methyl in determinand may be implemented down to 1ppb in Monitoring lower-cut
It surveys.
As seen from the above embodiment, the present invention is the above is only a preferred embodiment of the present invention, it is noted that for
For those skilled in the art, without departing from the principle of the present invention, can also make it is several improvement and
Retouching, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (6)
1. a kind of preparation method of zinc-containing metal organic framework materials, which comprises the following steps:
Porphyrin, 4- carboxyl phenyl benzene, zinc nitrate and n,N-Dimethylformamide are mixed under ultrasound condition, obtain mixing molten
Liquid；
The mixed solution is subjected to hydro-thermal reaction, obtains zinc-containing metal organic framework materials；
The porphyrin be in-four-(4- carboxyl phenyl) porphines, four (4- aminophenyl) porphyrins or four (4- nitrobenzophenone) porphyrins；
The 4- carboxyl phenyl benzene is (4- carboxyl phenyl) benzene of 1,3,5- tri- or 1,2,4,5- tetra- (4- carboxyl phenyl) benzene；The porphyrin,
The molar ratio of 4- carboxyl phenyl benzene and zinc nitrate is 1:1.8~2.1:2.1~2.3；The amount and N of the substance of the porphyrin, N- bis-
The volume ratio of methylformamide is 1mol:70~150ml；The temperature of the hydro-thermal reaction is 100~120 DEG C；The hydro-thermal is anti-
The time answered is 24~48h.
2. the zinc-containing metal organic framework materials of the preparation of preparation method described in claim 1.
3. application of the zinc-containing metal organic framework materials as claimed in claim 2 in Fluorometric assay parathion-methyl.
4. application according to claim 3, which comprises the following steps:
Fluorescence intensity after sample to be tested is mixed with the alcoholic solution of zinc-containing metal organic framework materials；According to fluorescence intensity level
The concentration of parathion-methyl in sample to be tested is obtained with scheduled standard curve；
The standard curve is the relation curve of fluorescence intensity and parathion-methyl log concentration.
5. application according to claim 4, which is characterized in that the standard curve is obtained by following steps:
Fluorescence intensity after standard solution containing parathion-methyl is mixed with the alcoholic solution of zinc-containing metal organic framework materials,
The relation curve for drawing fluorescence intensity and parathion-methyl log concentration, obtains standard curve.
6. application according to claim 4 or 5, which is characterized in that the range of linearity of the standard curve be 1ppb~
10ppm。
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| CN109916864B (en) * | 2019-01-28 | 2022-03-01 | 浙江省农业科学院 | Preparation of fluorescent metal-organic framework compound stable in water and method for detecting organophosphorus pesticide |
| CN110411996B (en) * | 2019-07-19 | 2022-03-18 | 长沙理工大学 | Method for detecting phoxim based on organic metal framework |
| CN110749667B (en) * | 2019-09-20 | 2022-07-15 | 青岛理工大学 | Analysis and detection method of four neonicotinoid insecticides in water |
| CN110724522A (en) * | 2019-10-27 | 2020-01-24 | 浙江理工大学 | Preparation method of tetramethoxyphenyl manganese porphyrin-Zn-MOF fluorescent material |
| CN111337466A (en) * | 2020-03-24 | 2020-06-26 | 浙江省农业科学院 | Method for manufacturing metal-organic framework fluorescent material detection test strip for ultra-fast on-site detection of parathion |
| CN112179882B (en) * | 2020-09-23 | 2022-04-12 | 浙江省农业科学院 | Method for detecting organophosphorus pesticide by using MOFs @ QDs material in farmland environment |
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