CN111548505B - Synthesis of trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity detection of chlorpyrifos - Google Patents
Synthesis of trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity detection of chlorpyrifos Download PDFInfo
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Abstract
The invention discloses synthesis of a trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity chlorpyrifos detection, and relates to the technical field of metal-organic pore polymers, wherein the structural formula of the trinuclear zinc cluster microporous compound is [ Zn ]3(DPA)(H2O)3]n·6H2O (1) wherein the ligand DPA is deprotonated 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid; firstly, the compound 1 has higher thermal stability, and the framework can be stabilized to about 250 ℃; secondly, water is used as a solvent for synthesizing the compound 1, so that the compound can stably exist in the water, and a foundation is laid for the practical application of the compound; in addition, the compound 1 is used for fluorescence detection of residual chlorpyrifos, and has important theoretical and practical significance for developing a novel chemical sensing analysis technology with high selectivity, high sensitivity, miniaturization and strong practicability.
Description
The technical field is as follows:
the invention relates to the technical field of metal-organic pore polymers, in particular to synthesis of a trinuclear zinc cluster microporous compound and high-sensitivity and high-selectivity chlorpyrifos detection.
Background art:
pesticide residues have hitherto been a serious environmental problem, since most pesticides are significantly and biologically toxic, and once introduced into the environment, their toxic, highly residual properties have an effect on interconversion, dispersion and enrichment processes (i.e. migration) in various forms. Chlorpyrifos (Chlorpyrifos) is an ideal pesticide for food, fruit trees, vegetables and other commercial crops. The mass production and use of chlorpyrifos has become a trend in agricultural development. The chlorpyrifos can enter a human body by contacting with skin, oral cavity, esophagus, respiratory tract and eyes, and is accumulated in certain organs of the human body to cause poisoning and harm to human health, so that people urgently need to develop a high-sensitivity and high-selectivity method for detecting the content of the chlorpyrifos in the environment, but the established rapid, high-sensitivity and high-selectivity pesticide residue detection method has important practical significance because the pesticide residue content in an actual sample is often less and coexisting substances are complex.
At present, the detection method of pesticide residues generally comprises the following steps: gas chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, electrochemical analysis, biological and nano-sensor, etc. The gas chromatography, the gas chromatography-mass spectrometry combined method, the liquid chromatography and the liquid chromatography-mass spectrometry combined method have the advantages of good selectivity, high sensitivity, wide selection range and the like, but have the defects of expensive equipment, complex pretreatment operation, long time consumption and the like, so that the method is limited in the aspects of continuous monitoring, real-time rapid detection and the like. The electrochemical analysis method is an instrumental analysis method based on the electrochemical property of a substance in a solution, has the advantages of high sensitivity and accuracy, wide measurement range, low equipment price, easiness in automation realization and the like, but the selectivity of the electrochemical analysis method is generally poor. The biosensor is a sensor which converts a sensed measured substance into a usable output signal by utilizing the molecular recognition function of bioactive substances (enzymes, eggs, DNA, antibodies, antigens, biological membranes and the like), and is an advanced detection method. The nano sensor also has the problems of short development time, unstable performance and the like. Therefore, in many important applications, there is a strong need for a simple, rapid, accurate, low-cost, and highly selective method for analyzing and detecting pesticide residues.
The fluorescence chemical sensor has been applied to the determination of part of pesticide residues, but due to the limitation of materials, the sensitivity, selectivity, reproducibility and the like are difficult to reach a new height all the time. Therefore, to make the fluorescence chemical sensor have better development in rapid detection of pesticide residue in the environment, new materials and methods must be added to change the characteristics of the sensor.
The metal-organic frameworks (MOFs) compound not only has excellent special properties, but also has the advantages of adjustable structure, wide color-developing spectrum range and the like. Therefore, the metal-organic framework compounds have been rapidly developed in terms of novel materials, particularly metal-organic framework compounds having active sites. For example, the structure has open metal sites, and the pore channels have independent cations or compounds with active functional groups and the like. MOFs with active sites can interact rapidly with targets, mainly because active sites can interact weakly or exchange with targets to allow the detection species to interact with the metal-organic framework. Therefore, the deep development of the combination of the metal-organic pore polymer and the fluorescence chemical sensing technology has important theoretical and practical significance for the development of a novel chemical/nano sensing analysis technology with high selectivity, high sensitivity, miniaturization and strong practicability. Meanwhile, the method has very important application prospect in the aspects of pesticide residue detection, monitoring and treatment.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a method for synthesizing the trinuclear zinc cluster microporous compound, the synthesis condition is mild, the operation is simple, the obtained trinuclear zinc cluster microporous compound belongs to a new compound, and the compound can be applied to the detection of chlorpyrifos and has the characteristics of high sensitivity and selectivity.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a trinuclear zinc cluster microporous compound with a molecular formula of [ Zn3(DPA)(H2O)3]n·6H2O (1), wherein the ligand DPA is deprotonated 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid.
The trinuclear zinc cluster microporous compound is of ortho-morphic crystal system, Pna21 space group and unit cell parameter
α＝90°，β＝90°，γ＝90°，
Z＝4，μ＝2.058mm-1，F(000)＝1472，R1＝0.0562,wR2＝0.1697[I>2σ(I)]。
The wave number of the infrared spectrum characteristic absorption peak of the trinuclear zinc cluster microporous compound is (KBr, cm)–1)：3377(m),2867(s),2735(m),1908(w),1694(m),1512(w),1397(s),1286(m),1210(w),1052(w),888(w),761(m),732(w),684(s),654(w),511(w),475(w)。
And confirming the structure of the trinuclear zinc cluster microporous compound through the test data of the crystal structure and the infrared spectrum.
The synthesis method of the trinuclear zinc cluster microporous compound comprises the steps of dissolving ligand 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid in water, stirring, adjusting the pH value with alkali liquor, filtering to obtain a solution, diffusing the solution into a zinc acetate dihydrate aqueous solution, and storing at room temperature to obtain colorless acicular crystals.
The pH value is 6-7, preferably 6.5.
The alkali liquor is preferably sodium hydroxide solution.
The molar ratio of the 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid to the zinc acetate dihydrate is 8:5-10, preferably 8: 10.
The trinuclear zinc cluster microporous compound can be successfully synthesized by adopting the synthesis method, and the trinuclear zinc cluster microporous compound cannot be obtained by adopting a conventional hydrothermal method.
The trinuclear zinc cluster microporous compound is applied to high-sensitivity and selective detection of chlorpyrifos. Researches prove that the trinuclear zinc cluster microporous compound can be used for fluorescence sensing of the pesticide residue chlorpyrifos with high sensitivity and high selectivity, and is suitable for detection of the pesticide residue chlorpyrifos.
The invention has the beneficial effects that:
structurally:
(1) compound 1 is a novel compound synthesized in an aqueous solution at room temperature;
(2) compound 1 is a zinc cluster compound having a trinuclear structure;
(3) the compound 1 contains an active site, and the compound with the active site often has special properties;
(4) compound 1 has a honeycomb cell structure.
In nature:
(1) the compound 1 has higher thermal stability, and the framework can be stabilized to about 250 ℃;
(2) the synthesis of the compound 1 takes water as a solvent, so that the compound can stably exist in water, which lays a foundation for the practical application of the compound;
(3) the compound 1 is used for fluorescence detection of residual chlorpyrifos, and has important theoretical and practical significance for developing a novel chemical sensing analysis technology with high selectivity, high sensitivity, miniaturization and strong practicability.
Description of the drawings:
FIG. 1 is a coordination pattern of three zinc atoms in Compound 1;
FIG. 2 is the trinuclear zinc cluster structure of Compound 1;
fig. 3 is a honeycomb three-dimensional cell structure of compound 1;
FIG. 4 is a thermogravimetric plot of Compound 1;
FIG. 5 shows fluorescence sensing of Compound 1 for various pesticides;
FIG. 6 is a detailed titration of the pesticide chlorpyrifos.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
1. Compound [ Zn ]3(DPA)(H2O)3]n·6H2Synthesis of O (1):
0.08mmol (39.5mg) of 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid ligand was dissolved in 4mL of purified water, stirred in a beaker for 1h, adjusted to pH 6.5 with 1M sodium hydroxide and then filtered to give a pure clear solution which was diffused to 5mL of a solution containing 0.10mmol (22.2mg) of Zn (CH)3COOH)2·2H2And (4) storing the mixture in an O aqueous solution at room temperature for 3d to obtain colorless needle-shaped crystals with the yield of 50 percent. C24H26Zn3O21Elemental analysis calculated (%): c, 34.08; h, 3.08. Experimental values: c, 32.36; h,3.17. Infrared analysis (KBr, cm)–1)：3377(m),2867(s),2735(m),1908(w),1694(m),1512(w),1397(s),1286(m),1210(w),1052(w),888(w),761(m),732(w),684(s),654(w),511(w),475(w)。
2. Compound [ Zn ]3(DPA)(H2O)3]n·6H2Measurement of O (1):
selecting crystals with regular and bright shapes and proper sizes, placing the crystals on a Bruker Smart-APEXII CCD single crystal X-ray diffractometer at room temperature, scanning the crystals in an omega scanning mode by using Mo-Kalpha rays (lambda is 0.071073nm) purified by a graphite monochromator in a monochromatic mode, and collecting diffraction data, wherein all intensity data are corrected by Lp and absorption. The crystal structure was solved by direct methods by SHELXTL software. All non-hydrogen atom coordinates, anisotropic temperature factors, hydrogen atom coordinates and isotropic temperature factors are subjected to full matrix least squares method F2And (5) fine-trimming and correcting to be convergent. All calculations were done using the SHELXL-97 package. The relevant crystallographic data for compound 1 are listed in table 1.
TABLE 1 Crystal data for Compound 1
aR1＝Σ||Fo|–|Fc|)/Σ|Fo|；wR2＝[Σw(Fo 2–Fc 2)2/Σw(Fo 2)2]1/2
3. Compound [ Zn ]3(DPA)(H2O)3]n·6H2Structural description of O (1)
One example of trinuclear zinc cluster microporous compound [ Zn ] is obtained under the condition of normal temperature3(DPA)(H2O)3]n·6H2O (1). Single crystal diffraction analysis showed that compound 1 has three independent zinc atoms involved in coordination, as shown in figure 1. The Zn1 atom is a penta-coordinated pattern with a spatial geometry of twisted trigonal bipyramids, in which five oxygen atoms participating in the coordination come from three DPA ligands and one oxygen atom from one water molecule. The coordination configuration of Zn2 atom is octahedral structure, four oxygen atoms participating in coordination come from different protonated DPA ligands, and two oxygen atoms participate in coordination with two water molecules. The Zn3 atom is in a hexacoordinated mode, in which one carboxyl group on a DPA ligand coordinates to a zinc atom in a bidentate chelating mode, the other two oxygen atoms are from two carboxyl groups on monodentate DPA ligands, and one oxygen atom is from one water molecule. As shown in FIG. 2, there are three different weak zinc-zinc interactions in Compound 1
Forming a triangular structure. The triangular structures are connected into one-dimensional zinc clusters through water molecules, and the distance between zinc and zinc is smaller than the Van der Waals radius of zinc
Also, it was observed that there was an uncoordinated oxygen atom in compound 1, which left an active site for compound 1. In addition, the compound 1 can form a honeycomb-shaped three-dimensional pore structure in space, as shown in fig. 3.
4. Compound [ Zn ]3(DPA)(H2O)3]n·6H2Stability of O (1)
The synthesized crystals were dried at room temperature for use, and the thermal stability of compound 1 was investigated, as shown in fig. 4. The thermogravimetric curve of compound 1 has two weight loss phases. The weight loss in the first step was 5.31%, corresponding to the loss of free water molecules (theoretical value: 12.78%). The frame then remains stable. When the temperature rose to 265 ℃, the sample began to decompose. The final sample residue was 23.36%. In addition, because the synthesis of the crystal takes water as a solvent, the stable existence of the compound in the water lays a foundation for the practical application of the compound.
5. Compound [ Zn ]3(DPA)(H2O)3]n·6H2O (1) detection of pesticide-residue chlorpyrifos
The trinuclear zinc cluster microporous compound 1 has better stability, large pore area and active sites. Therefore, the compound 1 is used for fluorescence detection of residual chlorpyrifos, and has important theoretical and practical significance for developing a novel chemical sensing analysis technology with high selectivity, high sensitivity, miniaturization and strong practicability. Meanwhile, the method has very important application prospect in the aspects of measuring the detection, monitoring and treatment of the residual chlorpyrifos.
5mg of Compound 1 was dispersed in 3mL of each pesticide at 0.1 mol/L: pyraclostrobin (PYR), Glyphosate (GLY), Glufosinate (GLA), Matrine (MAT), Acetamiprid (ACE), Difenoconazole (DIF) and Chlorpyrifos (CHL), and the fluorescence sensing effect of the composition on pesticides is researched. As can be seen from FIG. 5, the compound 1 has a good fluorescence quenching effect on chlorpyrifos, and the result proves that the compound 1 can be used for fluorescence sensing of residual chlorpyrifos in pesticide with high selectivity and high sensitivity.
In order to further refine the fluorescence process of the pesticide residual chlorpyrifos, a refinement titration experiment is also carried out. The chlorpyrifos solution was dropped into the aqueous solution containing compound 1, and then the change in fluorescence intensity was observed. As shown in FIG. 6, when the fluorescence intensity was quenched by 50%, the concentration of chlorpyrifos was 30 ppm.
Furthermore, we investigated the effect of compound 1 on chlorpyrifos detection in the presence of a co-existing pesticide. Compound 1 had little effect on the detection of chlorpyrifos before and after the addition of the interferent. Therefore, the compound 1 has good selectivity, anti-interference performance and high sensitivity on the detection of chlorpyrifos.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The application of the trinuclear zinc cluster microporous compound in the highly sensitive and selective detection of chlorpyrifos is characterized in that: the molecular formula of the trinuclear zinc cluster microporous compound is [ Zn ]3(DPA)(H2O)3]n·6H2O, wherein the ligand DPA is deprotonated 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid;
the trinuclear zinc cluster microporous compound is of ortho-morphic crystal system, Pna21 space group and unit cell parametera=14.53[Å]，b =11.94[Å]，c=20.56[Å]，α=90°，β=90°，γ=90°，V=3566.4[Å3]，Z=4，μ=2.058 mm-1，F(000)=1472，R 1 =0.0562, wR 2 =0.1697 [I>2σ(I)]。
2. The use of claim 1, wherein: the wave number of the infrared spectrum characteristic absorption peak of the trinuclear zinc cluster microporous compound is (KBr, cm)–1)：3377(m), 2867(s), 2735(m), 1908(w), 1694(m), 1512(w), 1397(s), 1286(m), 1210(w), 1052(w), 888(w), 761(m), 732(w), 684(s), 654(w), 511(w), 475(w)。
3. The use of claim 1, wherein: dissolving ligand 3, 4-di (3, 5-dicarboxyphenyl) phthalic acid in water, stirring, adjusting pH value with alkali solution, filtering to obtain solution, diffusing the solution into zinc acetate dihydrate aqueous solution, and storing at room temperature to obtain colorless needle crystal.
4. Use according to claim 3, characterized in that: the pH value is 6-7.
5. The use of claim 4, wherein: the pH was 6.5.
6. Use according to claim 3, characterized in that: the alkali liquor is sodium hydroxide solution.
7. Use according to claim 3, characterized in that: the molar ratio of the 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid to the zinc acetate dihydrate is 8: 5-10.
8. Use according to claim 7, wherein the molar ratio of 3, 4-bis (3, 5-dicarboxyphenyl) phthalic acid to zinc acetate dihydrate is 8: 10.
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