CN109879896B - Metal-organic framework fluorescent probe for identifying paraquat as well as preparation method and application thereof - Google Patents
Metal-organic framework fluorescent probe for identifying paraquat as well as preparation method and application thereof Download PDFInfo
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- CN109879896B CN109879896B CN201910278979.1A CN201910278979A CN109879896B CN 109879896 B CN109879896 B CN 109879896B CN 201910278979 A CN201910278979 A CN 201910278979A CN 109879896 B CN109879896 B CN 109879896B
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Abstract
The invention discloses a water-stable metal-organic framework fluorescent probe with a chemical formula of [ Zn ]2(cptpy)(btc)(H2O)] n Wherein cptppy is 4- [4,2';6',4']-terpyridine-4' -benzoic acid monovalent anion, btc is 1,3, 5-benzenetricarboxylic acid trivalent anion. The compound belongs to a monoclinic system, and the space group isP21And c, the ratio of the total weight to the total weight of the product. The preparation method comprises mixing zinc nitrate hexahydrate, Hcptppy and H3btc was added to a mixed solvent of acetonitrile and water at 160 deg.CoC, after full reaction at constant temperature, filtering and washing to obtain the target product. The invention has the advantages that: the material can stably exist in water, shows sensitive identification on paraquat, and does not need pretreatment or has simple pretreatment. Meanwhile, the material is solid powder, is convenient to store and use, has a simple synthesis method and high yield, and has potential application value and good popularization and application prospects in the aspects of monitoring of environmental pollutants, food safety and the like.
Description
Technical Field
The invention relates to preparation and application of a metal-organic framework, in particular to a metal-organic framework fluorescent probe for identifying paraquat in a water body and a preparation method and application thereof.
Background
With the development of agricultural industrialization, the production of agricultural products increasingly depends on exogenous substances such as pesticides, antibiotics and hormones. The dosage of pesticides in grains, fruits, vegetables, tea leaves and the like in China is high, the pesticide residue in agricultural products exceeds the standard due to unreasonable use of the pesticides, the edible safety of people is affected, even the poisoning and death are caused, and meanwhile, the water and environment pollution problems are caused due to the pesticide residue exceeding the standard. Chemical control remains the most convenient, effective and inexpensive means of control in the foreseeable future, and agricultural production remains undisclosed. Currently, methods for detecting pesticide residues internationally are various, but are mainly divided into two main categories from the viewpoint of their principles: chromatographic assays and biochemical assays. Although these two methods have the advantages of strong specificity and high sensitivity, they have their own limitations, such as: the chromatographic method has high technical requirements on detection personnel, expensive detection equipment, complicated sample pretreatment, inconvenience in carrying and the like; although the rapid detection method for the residual toxicity of the pesticide has low requirements on the technical level of detection personnel, is easy to popularize in the basic level and the like, is the most widely applied detection method in China at present, the detection limit is generally higher than the standard value of the residual limit specified at home and abroad because the rapid detection method is only limited to the detection of organophosphorus and carbamate pesticides and can not give a quantitative detection result, so that the detection limit is greatly limited. In recent years, the problems of food safety, environmental pollution and the like caused by the overproof pesticide residues are more and more attracted by people, so that exploring and developing a technology for effectively and rapidly detecting the environmental pollutants such as the pesticides and the like becomes important research content in related fields such as environment and food safety and the like.
The fluorescence identification method has the advantages of simple operation, low technical level requirement, quick and convenient detection process, high sensitivity, quick response and the like, and is widely concerned by people. The metal-organic framework material is used as an important fluorescent probe material, has good crystallinity, is easy to determine the structural composition and the spatial configuration of the metal-organic framework material by the technologies such as X-ray single crystal diffraction and the like, and is beneficial to establishing clear correlation between the structure and the property. More importantly, the light-emitting performance of the metal-organic framework material is closely dependent on the spatial structure characteristics, the coordination environment of metal ions, the property of the pore surface and the interaction between the metal ions and guest molecules, so that the metal-organic framework material has a very attractive application prospect in the aspect of fluorescence recognition. In recent years, fluorescent metal-organic framework materials are widely used for identification and detection of different species such as anions, cations, organic small molecules, volatile organic compounds and explosives, however, few fluorescent probes for identifying pesticides are reported at present, especially in water. Therefore, the development of a fluorescent probe capable of sensitively recognizing pesticide residues in water is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a water-stable metal-organic framework fluorescent probe capable of sensitively identifying paraquat for technical analysis, which has the advantages of simple preparation process and high yield, is used for sensitively detecting paraquat in a water body, and has potential application value in the aspects of detection of environmental pollutants, food safety and the like.
The invention also aims to provide a preparation method and application of the water-stable metal-organic framework fluorescent probe capable of sensitively identifying paraquat.
The technical scheme adopted by the invention is as follows: a water-stable metal-organic framework material for sensitively recognizing paraquat has a chemical formula of [ Zn2(cptpy)(btc)(H2O)] n Wherein cptppy is 4- [4,2';6',4']-terpyridine-4' -benzoic acid monovalent anion, btc is 1,3, 5-benzenetricarboxylic acid trivalent anion;
the material belongs to a monoclinic system and has a space group ofP21N, unit cell parameter ofa = 10.5779(11) Å，b = 15.5178(14) Å，c = 18.2158(18) Å，βUnit cell volume 2910.8(5) A = 103.222(5) °3，Z = 4，Dc = 1.616 mg·mm-3；
And the compound contains two crystallographically independent Zn in the minimum asymmetric unit structure2+Ion, a cptpy-Ligand, one btc3-A ligand and one coordinated water molecule. In which the Zn1 ion adopts a four-coordinate tetrahedral geometry, with the ions coming from two btc3–2O atoms in the ligand, a cptpy–1O atom in the ligand and another cptpy–1N atom in the ligand coordinates; zn2 adopts a penta-coordinate tetragonal pyramid geometry, which is associated with a cubic pyramid from one btc3–2O atoms in the ligand, a cptpy–1O atom in the ligand, a cptpy–1N atom and one water molecule in the ligandA bit. Adjacent Zn1 and Zn2 ions pass through btc3–The ligands are alternately connected to form a one-dimensional chain structure, and meanwhile, Zn1 and Zn2 ions can pass through cptppy–The ligands are connected to form a two-dimensional layered structure, and the one-dimensional chain and the two-dimensional layer are further connected through Zn1 and Zn2 ions to form a three-dimensional framework structure with a novel topological structure.
A preparation method of a water-stable metal-organic framework material capable of sensitively identifying paraquat comprises the following steps:
1) zinc nitrate hexahydrate, Hcptpy and H3btc is added into a mixed solvent of acetonitrile and water to obtain a mixed solution; the zinc nitrate hexahydrate, Hcptpy and H3The molar ratio of bt to acetonitrile and water is 2: 2: 1: 1384: 8888;
2) putting the mixed solution into a container, and heating to 160 ℃ within 3 hoursoC, at 160 oCKeeping for 72 hours, and then cooling to 30 ℃ after 48 hoursoAnd C, obtaining light yellow cluster crystals, washing the crystals obtained by filtering with acetonitrile and water, and drying to obtain the target product.
The metal-organic framework material is applied to detection of environmental pollutants, food safety and the like.
The invention has the advantages that: (1) the metal-organic framework material has the advantages of simple preparation process, higher yield and lower cost; (2) the material has better water stability, and the frame is kept stable when the material is soaked in a water solution for a week, thereby being beneficial to practical application; (3) the material shows sensitive fluorescence quenching response to paraquat, and has good popularization and application prospects.
Drawings
FIG. 1 is [ Zn ]2(cptpy)(btc)(H2O)] n A structure of single crystal diffraction of (1), whereinnA natural number from 0 to positive infinity, wherein: (a) is a compound minimal asymmetric unit diagram; (b) is a coordination environment diagram of Zn1 ions in the compound; (c) is a coordination environment diagram of Zn2 ions in the compound; (d) passing Zn1 and Zn2 ions through btc in the compound3–A one-dimensional chain diagram formed by ligand connection; (e) is formed by the passage of Zn1 and Zn2 ions in the compoundcptpy–Ligands are connected to form a two-dimensional layered diagram; (f) is a three-dimensional framework diagram of the compound; (g) is a topological schematic diagram of the compound.
FIG. 2 is a graph showing the thermal stability test of the prepared compound.
Fig. 3 is a PXRD pattern for chemical stability of the prepared compound, including PXRD pattern after three months of air exposure, one week of immersion in water, immersion in an aqueous solution having a pH = 2-12.
FIG. 4 shows the resulting compound and ligand 1,3,5-H3btc and Hcptpy fluorescence spectra of solids at room temperature.
FIG. 5 is a graph showing fluorescence spectra of the prepared compound after being reacted with paraquat at different concentrations.
FIG. 6 shows the fluorescence intensity of compound (b) (ii)I 0/I-1) concentration variation with paraquat and fitting a graph.
Detailed Description
A water-stable metal-organic framework material for sensitively recognizing paraquat has a chemical formula of [ Zn2(cptpy)(btc)(H2O)] n Wherein cptppy is 4- [4,2';6',4']-terpyridine-4' -benzoic acid monovalent anion, btc is 1,3, 5-benzenetricarboxylic acid trivalent anion; the preparation method comprises the following steps:
1) 0.05 mmol of zinc nitrate hexahydrate, 0.05 mmol of Hcptpy and 0.025 mmol of H3btc was added to 2.0 ml acetonitrile and 4.0 ml distilled water to obtain a mixture;
2) transferring the mixed solution to a stainless steel reaction kettle with a lining of polytetrafluoroethylene (25 ml), and heating to 160 ℃ within 3 hoursoC, at 160 oCKeeping for 72 hours, and then cooling to 30 ℃ after 48 hoursoAnd C, obtaining light yellow block cluster crystals, washing the crystals obtained by filtering with acetonitrile and water for three times respectively, and drying to obtain the target product.
Crystal structure determination of the prepared compound: selecting a single crystal with proper size, placing the single crystal on a Bruker Smart Apex-II type X-ray single crystal diffractometer, and performing Mo-ionK αRay (C)λ= 0.71073A) as radiation source, at 296(2) K, at 2.30 carbon cyclesqDerivatives of less than 28.26Diffraction data were collected in the range of radiation, and all data collected wereLp-factor and empirical absorption correction. All non-hydrogen atom coordinates are analyzed by a direct method, all non-hydrogen atoms are corrected by adopting various anisotropic thermal parameters, and full matrix least square optimization is carried out. The coordinates of all hydrogen atoms are obtained by a geometric theory hydrogenation method, and all analysis works use the embedded typeSHELXLThe Olex2 software of the 1997 program was done on a computer.
The detection result shows that: the chemical formula of the compound is [ Zn ]2(cptpy)(btc)(H2O)] n Belonging to the monoclinic system, the space group isP21N, unit cell parameter ofa = 10.5779(11) Å，b = 15.5178(14) Å，c = 18.2158(18) Å，βUnit cell volume 2910.8(5) A = 103.222(5) °3，Z = 4，Dc = 1.616 mg·mm-3. The minimum asymmetric unit structure of the prepared compound comprises two crystallographically independent Zn2+Ion, a cptpy-Ligand, one btc3-Ligand and one coordinated water molecule, see FIG. 1 a. In which the Zn1 ion adopts a four-coordinate tetrahedral geometry, with the ions coming from two btc3–2O atoms in the ligand, a cptpy–1O atom in the ligand and another cptpy–1N atom in the ligand coordinates, see FIG. 1 b; zn2 adopts a penta-coordinate tetragonal pyramid geometry, which is associated with a cubic pyramid from one btc3–2O atoms in the ligand, a cptpy–1O atom in the ligand, a cptpy–1N atom in the ligand coordinates to a water molecule, see FIG. 1 c. Adjacent Zn1 and Zn2 ions pass through btc3–The ligands are alternately connected to form a one-dimensional chain structure, as shown in FIG. 1 d; meanwhile, Zn1 and Zn2 ions can pass through cptppy–Ligands are linked to form a two-dimensional layered structure, see fig. 1 e; the one-dimensional chains and the two-dimensional layers are further connected through Zn1 and Zn2 ions to form a three-dimensional framework structure with a novel topological structure, which is shown in figures 1f and 1 g.
The stability of the prepared compound is detected, and the detection method comprises the following steps:
1) passing the obtained target product through LaAnd (3) testing by a bsys NETZSCH TG 209 thermal analyzer, and FIG. 2 is a thermal stability test chart of the prepared complex. The thermal analysis results show that: the material exhibits a one-step weight loss process from room temperature to 180 deg.CoC has no obvious weightlessness till 340oThe weight loss around C was 2.62%, corresponding to the loss of 1 coordinated water molecule (theoretical value of 2.54%).
2) The obtained target product is exposed in the air for three months, and tested by a Bruker D8 advanced X-ray powder diffractometer, and the obtained PXRD experimental spectrogram can be well coincided with a single crystal simulated PXRD spectrogram, as shown in figure 3, which shows that the framework structure of the material is kept unchanged.
3) The obtained target product is soaked in distilled water for one week, then filtered and dried, and subjected to PXRD test, and the obtained PXRD experimental spectrogram can be well matched with a single crystal simulated PXRD spectrogram as shown in figure 3, which shows that the framework structure of the material can be stable in distilled water for at least one week.
4) After the obtained target product is soaked in the aqueous solution with the pH = 1-14 for three days, the target product is filtered and dried, and the PXRD test is carried out, wherein the PXRD experimental spectrum obtained after the target product is soaked in the aqueous solution with the pH = 3-11 can be well matched with the single crystal simulated PXRD spectrum shown in figure 3, and the framework structure of the material can be stable in the aqueous solution with the pH = 3-11 for at least three days.
Fluorescence property detection of the prepared compound:
1) solid fluorescence property test of compounds
The solid fluorescence spectrum data of the complex was collected using a fluorescence spectrophotometer model F4500, hitachi, japan. We first selected 340 nm as the excitation wavelength and tested ligands 1,3,5-H, respectively3btc and Hcptpy and the solid fluorescence emission spectra of the target product at room temperature (fig. 4). Ligand 1,3,5-H3btc shows a distinct emission peak near 388 nm, which can be assigned to ligand 1,3,5-H3btc ofπ* → nAnd/orπ* → πAnd (4) electron transition. The ligand Hcptpy presents a distinct emission peak near 422 nm, and can be assigned to the ligand Hcptpyπ* → πAnd (4) electron transition. Under the same conditions, the target product is 400 DEGSimilar emission peaks are exhibited around nm. These results indicate that the emission peak of the target product is derived from neither a metal-to-ligand transition (MLCT) nor a ligand-to-metal transition (LMCT), but rather from ligand 1,3,5-H3Internal to btc and Hcptpyπ* → πAnd/orπ* → nA transition, which may be due to havingd 10Zn in electronic configuration2+The ions are more difficult to oxidize or reduce. In addition, the emission peak of the target product is matched with ligand 1,3,5-H3btc is red-shifted by 12 nm; the blue shift was 22 nm compared to ligand Hcptppy, probably due mainly to Zn2+Ion and ligand 1,3,5-H3btc and Hcptpy.
2) Fluorescence performance test of compounds with different concentrations of paraquat
3.0 mg of the prepared ground crystals were weighed, added to 2.0 mL of distilled water, placed in an ultrasonic instrument for 30 minutes to render the system into a suspension, and then aqueous solutions containing paraquat in different volumes were added, respectively (the content of active ingredient of paraquat used was 20%, and the solution was diluted with water by 200 times and used). Fluorescence was measured at room temperature at an excitation wavelength of 310 nm, and the results are shown in FIG. 5, in which the fluorescence intensity of the compound gradually decreased until almost quenching as the concentration of paraquat increased, and the volume of paraquat added was 1000. mu.L (concentration of 1.296 mmol. multidot.L)-1) The fluorescence intensity is quenched by about 96.2%, and the results show that the compound has a fluorescence recognition effect on paraquat. The standard deviation is 15.86 calculated by testing the fluorescence intensity of a blank sample of 10 times, and the detection limit of the compound on paraquat is 9.73 multiplied by 10 by using a formula of 3 sigma/k-6mol·L-1. Using the Stern-Volmer (S-V) quenching equation:I 0/I = a*exp(k[M]) + bthe fluorescence intensity of the compound is fitted with the change of the concentration of paraquat, as shown in FIG. 6, and the quenching constant of the compound to paraquat can be calculated to be 1.04X 10 according to the fitting result3 L·mol-1。
Claims (3)
1. A kind ofThe metal-organic framework fluorescent probe for identifying paraquat is characterized by having a chemical formula of [ Zn ]2(cptpy)(btc)(H2O)] n Wherein cptppy is 4- [4,2';6',4']-terpyridine-4' -benzoic acid monovalent anion, btc is 1,3, 5-benzenetricarboxylic acid trivalent anion;
the metal-organic framework material belongs to a monoclinic system and has a space group ofP21N, unit cell parameter ofa = 10.5779(11) Å，b = 15.5178(14) Å，c = 18.2158(18) Å，βUnit cell volume 2910.8(5) A = 103.222(5) °3，Z = 4，Dc = 1.616 mg·mm-3；
And the compound has a minimum asymmetric unit structure comprising two crystallographically independent Zn2+Ion, a cptpy-Ligand, one btc3-Ligand and one coordinated water molecule, in which Zn1 ion adopts four-coordinate tetrahedral geometry, and is respectively linked with two btc3–2O atoms in the ligand, a cptpy–1O atom in the ligand and another cptpy–1N atom in the ligand coordinates; zn2 adopts a penta-coordinate tetragonal pyramid geometry, which is associated with a cubic pyramid from one btc3–2O atoms in the ligand, a cptpy–1O atom in the ligand, a cptpy–1N atom in the ligand is coordinated with one water molecule; adjacent Zn1 and Zn2 ions pass through btc3–The ligands are alternately connected to form a one-dimensional chain structure, and meanwhile, Zn1 and Zn2 ions can pass through cptppy–Ligands are connected to form a two-dimensional layered structure, and the one-dimensional chains and the two-dimensional layers are connected in an interactive manner to form a three-dimensional framework structure.
2. A method for preparing a metal-organic framework fluorescent probe capable of recognizing paraquat according to claim 1, comprising the steps of:
1) zinc nitrate hexahydrate, Hcptpy and H3btc is sequentially added into a mixed solvent of acetonitrile and water to obtain a mixed solution; the zinc nitrate hexahydrate, Hcptpy and H3The molar ratio of btc to acetonitrile and water is 2: 2: 1: 1384: 8888;
2) placing the mixture in a container at 160 deg.CoC, fully reacting at constant temperature to obtain light yellow color block cluster crystals, washing the crystals obtained by filtering with acetonitrile and water respectively, and drying to obtain the target product.
3. The use of the metal-organic framework fluorescent probe for identifying paraquat, as set forth in claim 1, in the detection of environmental pollutants and food safety.
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| CN107793440A (en) * | 2017-11-23 | 2018-03-13 | 秦皇岛天大环保研究院有限公司 | Fluorescence porous material, synthetic method and its application |
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