CN106905537A - The synthetic method of the metal-organic framework material with fluorescence property and its application - Google Patents
The synthetic method of the metal-organic framework material with fluorescence property and its application Download PDFInfo
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Abstract
The application of parathion, as follows the step of synthetic method the invention discloses a kind of synthetic method of metal-organic framework material with good fluorescence property and its in residues of pesticides are detected：Take the porphyrin with big conjugated structure, 1,2,4,5 4 (4 carboxyl phenyl) benzene and Zn (NO3)2·6H2O adds N in beaker, and N dimethylformamides, ultrasound mixes it；Well mixed solution is poured into reactor to be reacted；By reacted product centrifugation removal supernatant liquid, ethanol repeated centrifugation is added to wash more than 3 times；High temperature drying obtains final product MOFs solid powders.Parathion has specific quenching to MOFs fluorescence signals, and the parathion that adds it is more when, fluorescent quenching is also more obvious；In parathion concentration in 5ppb to 1000ppb, fluorescence intensity is inversely proportional with the logarithm of parathion concentration, realizes the highly sensitive high specific detection of parathion.
Description
Technical field
The invention belongs to Detecting Pesticide field, and in particular to a kind of metal with fluorescence property-have machine frame
The synthetic method of frame material (MOFs), further relate to a kind of metal-organic framework materials (MOFs) detection residues of pesticides on
Application.
Background technology
Parathion (O, O- diethyl-O- (4- nitrobenzophenones) thiophosphate), is a kind of organic phosphoric acid of wide spectrum high poison
Esters Insecticidal and acaricidal agent, parathion is high to the toxicity of people and animals, and the seasonal exceeded situation of residual quantity in food and vegetables compared with
Many so that poisoning often has generation, widely using parathion can cause harm to the mankind and environment.Therefore, many countries and
Area has disabled parathion, and is classified as the important detection object of crop residues of pesticides.
Traditional analysis method of parathion included in currently available technology gas chromatography, high pressure lipuid chromatography (HPLC) and
TLC etc..These methods generally require extraction and the decontamination procedure of complexity, and its measure is also required to valuable analytical instrument,
It is difficult to the conventional detection for carrying out a large amount of samples.
The features such as analyzing detecting method based on material photoluminescent property is with its high sensitivity, high selectivity, high stability day
Benefit attracts attention.Metal-organic framework materials (Metal-Organic Frameworks, MOFs) because its uniqueness composition, can
The structure of design and cut-out and abundant host-guest interactions and turn into one of study hotspot of fluoroscopic examination material.The present invention
The MOFs materials with good fluorescence performance are exactly make use of, and have studied its preparation method and the fluoroscopic examination to parathion
Purposes.
The content of the invention
The present invention is for extracting in existing detection method and decontamination procedure is complicated, and analytical instrument needed for determining is valuable etc.
Shortcoming, there is provided the synthetic method and the utilization metal of a kind of metal-organic framework materials (MOFs) with fluorescence property-
Organic framework materials (MOFs) quickly and easily carry out the application of Detecting Pesticide.
The technical scheme that the present invention is provided is as follows：
The invention provides a kind of synthetic method of the metal-organic framework materials (MOFs) with fluorescence property, step
It is as follows：
Step 1, take the porphyrin with big conjugated structure, (4- carboxyl phenyls) benzene of 1,2,4,5- tetra- and Zn (NO3)2·6H2O
In beaker, DMF (DMF) is added, ultrasound makes it be mixed into uniform dispersion；
Step 2, the well mixed dispersion liquid is poured into reactor, 24~48h is reacted at 100~120 DEG C of temperature；
Step 3, by step 2 reacted product centrifugation removal supernatant liquid, add ethanol repeated centrifugation wash 3 times with
On；
Step 4, the reacted product of step 3 is dried into 12-24h at 60-100 DEG C of temperature, you can obtain rufous
MOFs solid powders.
In the step 1 ,-four during the porphyrin with big conjugated structure is preferred-(4- carboxyl phenyls) porphines；It is described
In-four (4- carboxyl phenyls) porphines：1,2,4,5- tetra- (4- carboxyl phenyls) benzene：Zn(NO3)2·6H2The mass ratio of O for (150~
180)：(200~250)：(100~150), the mass ratio is preferably 160：223：131；The N,N-dimethylformamide
Addition is 34mL；The time of the ultrasound is 10~20min, preferably 15min.
In the step 2, the temperature is preferably 110 DEG C, and the time of the reaction is preferably 32~40h, most preferably
36h。
In the step 3, the rotating speed of the centrifugation is 6000~10000r/min, preferably 8000r/min；The centrifugation
Time be 4~6min, preferably 5min.
In the step 4, the temperature is preferably 70~90 DEG C, most preferably 80 DEG C；The dry time be 16~
20h, most preferably 18h.
The present invention has synthesized a kind of metal-organic framework materials (MOFs), through lot of experiments, present invention discover that this material
Material has good fluorescence property, and the fluorescence signal specific can be quenched by parathion；Other its fluorescent quenching degree
Amount with parathion is relevant, and the parathion of addition is more, and fluorescent quenching is also more obvious, and its fluorescence intensity and parathion concentration
Logarithm is presented linear relationship.
Using above-mentioned performance, the invention also discloses a kind of metal-organic framework materials (MOFs) using synthesis
Quickly and easily to the application of parathion detection in residues of pesticides.
Contain zinc in the alcoholic solution of the metal-organic framework materials.
The application has specificity well, big with MOFs because parathion contains nitrobenzene and hales electron group
Produce energy transfer between conjugated structure porphyrin, cause fluorescent quenching, thus when in agricultural chemicals remain parathion just have it is very strong
Fluorescent quenching is responded.
The concentration of metal-organic framework materials 0.4mgmL the most-1When, detection obtains optimal effectiveness.
Parathion detection in residues of pesticides is comprised the following steps：By testing sample and the metal-organic framework materials
Alcoholic solution mixing after fluorescence intensity；Parathion in testing sample is obtained according to fluorescence intensity level and predetermined standard curve
Concentration；Wherein, the standard curve is the relation curve of fluorescence intensity and parathion log concentration.
The range of linearity of the standard curve is 5ppb~1000ppb.
The present invention compared with prior art, has the advantage that and has the beneficial effect that：
(1) MOFs preparation method is simples of the invention, stable performance, it is adaptable to parathion residue detection in food security；
The MOFs for using this material can synthesize in advance, and the MOFs of single sintering can be used for multiple times.
(2) present invention utilizes parathion to the specific quenching of MOFs fluorescence signals, when the parathion for adding is more,
Fluorescent quenching is also more obvious；In parathion concentration in 5ppb to 1000ppb, the logarithm of fluorescence intensity and parathion concentration is into anti-
Than realizing the highly sensitive high specific detection of parathion；And detecting step simple and fast, it is only necessary to the time of several seconds,
Without well-trained professional operation, it is adaptable to Site Detection；Detection process is realized in homogeneous, reaction speed
Hurry up, reduce the complexity of operation, realize quick parathion, simplicity, sensitive detection.
(3) merely with this reagent of MOFs in experiment of the invention, it is to avoid because cumbersome experimental implementation bring it is a lot
Disturbing factor.
Brief description of the drawings
Fig. 1 is fluorescence response intensity maps of the MOFs in different material solution；
Fig. 2 for various concentrations MOFs in the standard liquid of same concentrations parathion fluorescence response intensity and signal to noise ratio
Figure；
Fig. 3 A are fluorescence response intensity maps of the MOFs in the parathion standard liquid of various concentrations；Fig. 3 B are emission peak
MOFs fluorescence intensities (F) in the parathion standard liquid of various concentrations are right with parathion concentration of standard solution (C) at 395nm
Several standard curves；
Fig. 4 is interference of the variety classes agricultural chemicals to the fluorescence response intensity of MOFs；
Fig. 5 is the thermogravimetric analysis figure of MOFs prepared by synthetic method of the present invention；
Fig. 6 is MOFs prepared by synthetic method of the present invention and the XRD for weighing molten MOFs in ethanol；
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with the drawings and specific embodiments to synthetic method of the invention and
Detection method to residues of pesticides is described in further detail：
A kind of synthetic method of the metal-organic framework materials (MOFs) with fluorescence property, step is as follows：
Embodiment 1
Step 1, take in-four (4- carboxyl phenyls) porphines 160mg or 0.201mmol, 1,2,4,5- tetra- (4- carboxyl phenyls)
Benzene 223mg or 0.399mmol and Zn (NO3)2·6H2O 131mg or 0.440mmol add N, N- dimethyl methyls in beaker
Acid amides 34mL, ultrasonic 15min make it be mixed into uniform dispersion；
Step 2, the dispersion liquid described in step 1 is poured into reactor, 36h is reacted at 110 DEG C of temperature；
Step 3, by step 2 reacted product centrifugation removal supernatant liquid, add ethanol repeated centrifugation wash 3 times with
On；The rotating speed is 8000r/min, and the rotating speed time is 5min；
Step 4, the reacted product of step 3 is dried into 18h at 80 DEG C of temperature, you can obtain rufous MOFs solid powder
End.
Embodiment 2
Step 1, take in-four (4- carboxyl phenyls) porphines 160mg or 0.201mmol, 1,2,4,5- tetra- (4- carboxyl phenyls)
Benzene 223mg or 0.399mmol and Zn (NO3)2·6H2O 131mg or 0.440mmol add N, N- dimethyl methyls in beaker
Acid amides 34mL, ultrasonic 15min make it be mixed into uniform dispersion；
Step 2, the dispersion liquid described in step 1 is poured into reactor, 24h is reacted at 100 DEG C of temperature；
Step 3, by step 2 reacted product centrifugation removal supernatant liquid, add ethanol repeated centrifugation wash 3 times with
On；The rotating speed is 6000r/min, and the rotating speed time is 4min；
Step 4, the reacted product of step 3 is dried into 12h under temperature 60 C, you can obtain rufous MOFs solid powder
End.
Embodiment 3
Step 1, take in-four (4- carboxyl phenyls) porphines 160mg or 0.201mmol, 1,2,4,5- tetra- (4- carboxyl phenyls)
Benzene 223mg or 0.399mmol and Zn (NO3)2·6H2O 131mg or 0.440mmol add N, N- dimethyl methyls in beaker
Acid amides 34mL, ultrasonic 15min make it be mixed into uniform dispersion；
Step 2, the dispersion liquid described in step 1 is poured into reactor, 48h is reacted at 120 DEG C of temperature；
Step 3, by step 2 reacted product centrifugation removal supernatant liquid, add ethanol repeated centrifugation wash 3 times with
On；The rotating speed is 10000r/min, and the rotating speed time is 6min；
Step 4, the reacted product of step 3 is dried into 24h at 100 DEG C of temperature, you can obtain rufous MOFs solids
Powder.
A kind of quick inspection of metal-organic framework materials (MOFs) parathion in residues of pesticides with fluorescence property
Application in survey, the detection method step of the quick detection is as follows：
Step 1, weigh 0.4mg above-described embodiments 1 preparation MOFs in the centrifuge tube of 2mL, add 1mL absolute ethyl alcohols,
It is configured to 0.4mgmL-1MOFs dispersion liquids；
Step 2, the parathion standard liquid for taking 100ppm, with absolute ethyl alcohol as solvent, configure the parathion standard of 10ppm
Solution；
Step 3, to numbering be A1, A2, A3, A4 96 microwell plates in add 0.4mgmL-1The μ L of MOFs solution 90,
, to the μ L of parathion standard liquid 10 that 10ppm is added in the A2 of hole, added in the A3 of hole to the μ L of ethanol 10 are added in the A1 of hole respectively again
The μ L of MTMC 10 of 40ppm, in the A4 of hole add 16ppm the μ L of phoxim solution 10, using ELIASA detection 325nm~
Fluorescence spectrum under 500nm wave-length coverages is simultaneously compared to fluorescence intensity size；Obtain going out at 395nm, fluorescence spectrum reaches
To peak-peak.
As shown in Figure 1, curve a is fluorescence response when being added without any agricultural chemicals to the fluorescence contrast of hole A1, A2, A3, A4,
Curve b is fluorescence response when adding parathion, and curve c is fluorescence response when adding MTMC, and curve d is to add phoxim
When fluorescence response.Result shows, when not having agricultural chemicals, the fluorescence intensity of MOFs is most strong, and most strong peak is at 395nm；When
When having the insecticides such as MTMC or phoxim or farm chemical ingredients, the fluorescence intensity of MOFs slightly has decrease, i.e., when using other agricultural chemicals
During instead of parathion, the fluorescence response of MOFs will not be subject to too big influence；When the ultimate density of parathion is 1ppm, MOFs's
Fluorescence is quenched.
1) under identical parathion concentration environment, the influence of the concentration of MOFs to its fluorescence response intensity and signal to noise ratio
Step 1, weigh 1mg above-described embodiments 1 preparation MOFs in the centrifuge tube of 2mL, add 1mL absolute ethyl alcohols, match somebody with somebody
It is set to 1mgmL-1MOFs solution, then be diluted to concentration respectively for 0.8mgmL-1, 0.6mgmL-1, 0.4mgmL-1,
0.2mg·mL-1MOFs dispersion liquids, and reference numeral be B1/C1, B2/C2, B3/C3, B4/C4, B5/C5；
Step 2, the parathion standard liquid for taking 100ppm, with absolute ethyl alcohol as solvent, configure the parathion standard of 10ppm
Solution；
Step 3, to numbering be B1, C1 96 microwell plates in add 1mgmL-1MOFs 90 μ L, it is micro- to the 96 of B2, C2
0.8mgmL is added in orifice plate-1The μ L of MOFs 90, to adding 0.6mgmL in 96 microwell plates of B3, C3-1The μ L of MOFs 90,
To adding 0.4mgmL in 96 microwell plates of B4, C4-1The μ L of MOFs 90, to adding 0.2mg in 96 microwell plates of B5, C5
mL-1MOFs90 μ L, to the μ L of ethanol 10 are added in hole B1, B2, B3, B4, B5, to adding 10ppm in hole C1, C2, C3, C4, C5
The μ L of parathion standard liquid 10, using ELIASA detection 275nm excitation wavelengths under fluorescence spectrum, record maximum fluorescence emission
The fluorescence intensity of peak 395nm or so；
Step 4, the fluorescence response set when being not added with parathion are F0, plus fluorescence response during parathion is F, calculates each volume
Corresponding (the F of MOFs in number centrifuge tube0-F)/F0Value, can find out the MOFs concentration that blank response signal can be made with the biggest gap.
Its result as shown in Figure 2, from figure 2 it can be seen that when concentration be 0.4mgmL-1When, the signal to noise ratio of MOFs is most
It is high；When concentration is 0.2mgmL-1When, the signal to noise ratio of MOFs is taken second place；When concentration is 1mgmL-1When, the signal to noise ratio of MOFs is most
It is low.
2) influence of the parathion of various concentrations to the fluorescence response intensity of MOFs
Step 1, weigh 0.4mg above-described embodiments 1 preparation MOFs in the centrifuge tube of 2mL, add 1mL absolute ethyl alcohols,
It is configured to 0.4mgmL-1MOFs dispersion liquids；
Step 2, the parathion standard liquid for taking 100ppm, with absolute ethyl alcohol as solvent, configure the parathion standard of 10ppm
Solution；
Step 3, to numbering be D1, D2, D3, D4, D5, D6, D7, D8, D9, D10, D11, D12 96 microwell plates in plus
Enter 0.4mgmL-1The μ L of MOFs dispersion liquids 90, then be separately added into 10 μ L initial concentrations successively for 10ppm, 7.5ppm, 5ppm,
The parathion standard liquid of 2.5ppm, 1ppm, 0.75ppm, 0.5ppm, 0.25ppm, 0.1ppm, 75ppb, 50ppb and 10 μ L
Ethanol, using the fluorescence spectrum under ELIASA detection 275nm excitation wavelengths, record maximum fluorescence emission peak 395nm's or so
Fluorescence intensity.
As shown in Figure 3, a-l distinguishes the corresponding final concentration of 1000ppb of parathion standard liquid to its result in accompanying drawing 3A,
750ppb, 500ppb, 250ppb, 100ppb, 75ppb, 50ppb, 25ppb, 10ppb, 7.5ppb, 5ppb, 0ppb；Experiment hair
Existing, fluorescence intensity is reduced with the increase of parathion concentration of standard solution.
From accompanying drawing 3B as can be seen that in parathion concentration of standard solution in 5ppb to 1000ppb, emission peak 395nm
Place's fluorescence intensity is inversely proportional with the logarithm of parathion concentration of standard solution, fluorescence intensity (F) and parathion concentration of standard solution (C)
Relation be：F=-3110.04logC+10344.27, its linearly dependent coefficient is 0.988；When parathion concentration of standard solution
During less than 5ppb, fluorescence intensity change is not obvious, reaches Monitoring lower-cut.
3) interference of the variety classes agricultural chemicals to the fluorescence response intensity of MOFs
Step 1, weigh 0.4mg above-described embodiments 1 preparation MOFs in the centrifuge tube of 2mL, add 1mL absolute ethyl alcohols,
It is configured to 0.4mgmL-1MOFs dispersion liquids；
Step 2, the parathion standard liquid for taking 100ppm, with absolute ethyl alcohol as solvent, configure the parathion standard of 10ppm
Solution；
Step 3, it is the 96 of E1, E2, E3, E4, E5, E6, E7, E8, E9, E10, E11, E12, F1, F2, F3, F4 to numbering
0.4mgmL is added in microwell plate-1The μ L of MOFs solution 90, then ethanol, the parathion for being separately added into 10 μ L successively
(10ppm), dimehypo (40ppm), Bassa (40ppm), MTMC (40ppm), Mobucin (40ppm), 4-chlorophenoxyacetic acid
Sodium (40ppm), carbendazim (16ppm), chlorfluazuron (16ppm), emamectin benzoate (16ppm), thimet sulfone (16ppm), phoxim
(16ppm), Acetamiprid (16ppm), 3- hydroxyls carbofuran (16ppm), Prochloraz (16ppm), metalaxyl (100ppm) are (right respectively
Answer the a-p in accompanying drawing 4), using the fluorescence spectrum under ELIASA detection 275nm excitation wavelengths, record maximum fluorescence emission peak
The fluorescence intensity of 395nm or so.
Its result as shown in Figure 4, figure 4, it is seen that parathion can be quenched the fluorescence of MOFs, and other agricultural chemicals
The fluorescence of MOFs can not be then quenched, shows that influence of the parathion to the fluorescence response intensity of MOFs has good specificity.
4) MOFs detects application to the mark-on of parathion in the sewage of farmland
Step 1, weigh 0.4mg above-described embodiments 1 preparation MOFs in the centrifuge tube of 2mL, add 1mL absolute ethyl alcohols,
It is configured to 0.4mgmL-1MOFs dispersion liquids；
Step 2, to take 5 centrifuge tubes and number respectively be 1-5, and farmland sewage sample is not only had so that absolute ethyl alcohol dilutes ten times
Have and cook the pretreatment fluid that other pretreatments form farmland sewage, the pretreatment fluid with the farmland sewage, respectively will be right as solvent
Sulphur phosphorus solution configures a series of concentration respectively 1000ppb, 750ppb, 500ppb, 250ppb in being added to farmland sewage sample,
The parathion standard liquid of 100ppb；
Step 3, to numbering be G1, G2, G3, G4, G5 96 microwell plates in add 0.4mgmL-1MOFs dispersion liquids
90 μ L, then the standard liquid final concentration point of the sample for being added with agricultural chemicals and μ L, G1~G5 parathion of ethanol 10 is separately added into successively
Not Wei 100ppb, 75ppb, 50ppb, 25ppb, 10ppb, using ELIASA detection 275nm excitation wavelengths under fluorescence spectrum, note
The fluorescence intensity of record maximum fluorescence emission peak 395nm or so；
The testing result of its fluorescence and the rate of recovery is listed in table 1, such as can be seen that this method can be with effective detection agriculture in table 1
Parathion concentration in the sewage sample of field, and numbering G1~G5 achieves the good rate of recovery, and the rate of recovery averagely reaches
More than 95%, by not adding before the sewage of farmland original parathion standard liquid and determining parathion concentration in the sewage sample of farmland
Measurement contrast, illustrate this detection application with wide potential application foreground；The concentration that the rate of recovery=this method is determined/
Spiked levels；The spiked levels refer to the concentration (ppb) for not adding parathion standard liquid before the sewage of farmland；The measure
Concentration refers to the concentration (ppb) for adding parathion in sample after the sewage of farmland, can be used successfully to the detection of actual farmland sewage.
Table 1
Table 1：The actual sample detection of parathion
5) heat endurance of MOFs is characterized
To study the heat endurance of the MOFs materials, thermogravimetric sign, the heat are carried out to MOFs materials prepared by embodiment 1
The experiment condition of weight：0-600 DEG C of temperature, is heated up under nitrogen atmosphere with the speed of 10 DEG C/min；Experimental result as shown in Figure 5,
The MOFs materials have preferable stability, i.e. weight at 410 DEG C>The 90% of weight before experiment；It is weightless at 410-525 DEG C
Substantially；It is warming up to 600 DEG C of weightlessness to the 48.7% of the preceding weight of experiment.
6) MOFs stability in ethanol is characterized
Further to probe into the crystalline structure and stability in ethanol of MOFs materials, it is prepared by embodiment 1 and
The molten MOFs materials of weight have carried out the sign of XRD, sweep interval in ethanol：5°<2θ<50°.The heavy molten step：To implement
MOFs materials prepared by example 1 disperse 24h in ethanol, are dried after centrifugation removal supernatant liquor.
Experimental result as shown in Figure 6, from fig. 6 it can be seen that embodiment 1 prepare MOFs be typical polycrystalline knot
Structure, and do not show that obvious crystal formation changes after weight is molten, the structure for indicating MOFs in ethanol has very strong stability, together
When also illustrate that detection is carried out to parathion as solvent with ethanol will not produce interference to the structure of MOFs.
Although last it should be noted that described in detail to the present invention above, above-mentioned reality in conjunction with the embodiments
The exhaustion of example not specific embodiment is applied, above-described embodiment is intended to indicate that the present invention, the protection being not intended to limit the present invention
Scope, for a person skilled in the art, without departing from the principles and spirit of the present invention, can be to these tools
Body implementation method or embodiment carry out various changes, modification, replacement and modification, these designed without performing creative labour with
The same or analogous structure of inventive technique scheme, device, equipment or product and preparation method thereof, application method and/or purposes,
Should be included within the scope of the present invention.
Claims (10)
1. a kind of synthetic method of the metal-organic framework materials with fluorescence property, it is characterised in that：Step is as follows：
Step 1, take the porphyrin with big conjugated structure, (4- carboxyl phenyls) benzene of 1,2,4,5- tetra- and Zn (NO3)2·6H2O is in burning
In cup, DMF (DMF) is added, ultrasound makes it be mixed into uniform dispersion；
Step 2, the dispersion liquid is poured into reactor, 24~48h is reacted at 100~120 DEG C of temperature；
Step 3, by step 2 reacted product centrifugation removal supernatant liquid, add ethanol repeated centrifugation to wash more than 3 times；
Step 4, the reacted product of step 3 is dried into 12~24h at 60~100 DEG C of temperature, you can obtain rufous MOFs
Solid powder.
2. the synthetic method of the metal-organic framework materials with fluorescence property according to claim 1, its feature exists
In：In the step 1, the porphyrin with big conjugated structure be in-four-(4- carboxyl phenyls) porphines；(4--four in described
Carboxyl phenyl) porphines：1,2,4,5- tetra- (4- carboxyl phenyls) benzene：Zn(NO3)2·6H2The mass ratio of O is (150~180):(200
~250):(100~150)；The addition of the N,N-dimethylformamide is 34mL；The time of the ultrasound for 10~
20min。
3. the synthetic method of the metal-organic framework materials with fluorescence property according to claim 1, its feature exists
In：In the step 2, the temperature is 110 DEG C, and the time of the reaction is 32~40h.
4. the synthetic method of the metal-organic framework materials with fluorescence property according to claim 1, its feature exists
In：In the step 3, the rotating speed of the centrifugation is 6000~10000r/min；The time of the centrifugation is 4~6min.
5. the synthetic method of the metal-organic framework materials with fluorescence property according to claim 1, its feature exists
In：In the step 4, the temperature is 70~90 DEG C；The dry time is 16~20h.
6. application of the metal-organic framework materials described in a kind of utilization claim any one of 1-5 to Detecting Pesticide.
7. application according to claim 6, it is characterised in that the alcoholic solution of the metal-organic framework materials contains zinc.
8. application according to claim 6, it is characterised in that the concentration of the metal-organic framework materials is the most
0.4mg·mL-1When, detection obtains optimal effectiveness.
9. application according to claim 6, it is characterised in that comprise the following steps：By testing sample
Fluorescence intensity after mixing with the alcoholic solution of the metal-organic framework materials；According to fluorescence intensity level and predetermined
Standard curve obtains the concentration of parathion in testing sample；Wherein, the standard curve is fluorescence intensity and parathion concentration pair
Several relation curves.
10. application according to claim 6, it is characterised in that the range of linearity of the standard curve be 5ppb~
1000ppb。
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| WO2019036140A1 (en) | 2017-07-17 | 2019-02-21 | Zymergen Inc. | Metal-organic framework materials |
| CN109916864A (en) * | 2019-01-28 | 2019-06-21 | 浙江省农业科学院 | Stable fluorescence metal-organic framework compounds preparation and the method for detecting organophosphorus pesticide in water |
| CN110411996A (en) * | 2019-07-19 | 2019-11-05 | 长沙理工大学 | Method based on organic metal framework detection phoxim |
| 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 |
| CN111548505A (en) * | 2020-04-21 | 2020-08-18 | 安徽国防科技职业学院 | Synthesis of trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity detection of chlorpyrifos |
| CN114920950A (en) * | 2022-06-14 | 2022-08-19 | 浙江省农业科学院 | Bimetal organic framework material and preparation and application thereof |
| CN115181279A (en) * | 2022-06-08 | 2022-10-14 | 渤海大学 | Fluorescent metal-organic framework material for detecting human biomarker 3-nitrotyrosine and application thereof |
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| WO2019036140A1 (en) | 2017-07-17 | 2019-02-21 | Zymergen Inc. | Metal-organic framework materials |
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| CN111548505A (en) * | 2020-04-21 | 2020-08-18 | 安徽国防科技职业学院 | Synthesis of trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity detection of chlorpyrifos |
| CN111548505B (en) * | 2020-04-21 | 2021-01-12 | 安徽国防科技职业学院 | Synthesis of trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity detection of chlorpyrifos |
| CN115181279A (en) * | 2022-06-08 | 2022-10-14 | 渤海大学 | Fluorescent metal-organic framework material for detecting human biomarker 3-nitrotyrosine and application thereof |
| CN115181279B (en) * | 2022-06-08 | 2023-05-12 | 渤海大学 | Fluorescent metal-organic framework material for detecting biomarker 3-nitrotyrosine of human body and application thereof |
| CN114920950A (en) * | 2022-06-14 | 2022-08-19 | 浙江省农业科学院 | Bimetal organic framework material and preparation and application thereof |
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