CN111484511A - Molecular fluorescent probe crystalline material and application thereof in chromium (VI) and iron (III) ion detection - Google Patents
Molecular fluorescent probe crystalline material and application thereof in chromium (VI) and iron (III) ion detection Download PDFInfo
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- CN111484511A CN111484511A CN202010340533.XA CN202010340533A CN111484511A CN 111484511 A CN111484511 A CN 111484511A CN 202010340533 A CN202010340533 A CN 202010340533A CN 111484511 A CN111484511 A CN 111484511A
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 69
- 239000002178 crystalline material Substances 0.000 title claims abstract description 59
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001514 detection method Methods 0.000 title description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title description 8
- -1 iron (III) ions Chemical class 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- HBXLKHXFCBAVDO-UHFFFAOYSA-N 3,5-dipyridin-4-yl-1,2,4-triazol-4-amine Chemical group NN1C(C=2C=CN=CC=2)=NN=C1C1=CC=NC=C1 HBXLKHXFCBAVDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 3
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 description 1
- 108050008072 Cytochrome c oxidase subunit IV Proteins 0.000 description 1
- 108060006006 Cytochrome-c peroxidase Proteins 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 102100030856 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940077449 dichromate ion Drugs 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention discloses a molecular fluorescent probe crystalline material and a preparation method thereof, wherein the chemical formula of the material is { [ Zn ]2(FDA)2(4‑abpt)2(H2O)2]}nOf which FDA2‑Is 2, 5-furandicarboxylic acid dianion, 4-abpt is 4-amino-3, 5-di (4-pyridyl) -1,2, 4-triazole, and organic ligand H2FDA, 4-abpt and Zn (NO)3)2·6H2Dissolving O in the mixed solvent of N, N-dimethylacetamide and deionized water, and reacting and separating to obtain the product. The molecular fluorescent probe crystalline material can simultaneously express chromium (VI) and iron (III) ions in a water body environmentHigh selectivity and high sensitivity identification, simple and convenient synthesis, easy implementation, no need of pretreatment of samples, high yield, easy storage and the like, and has great potential application value.
Description
Technical Field
The invention relates to a molecular fluorescent probe crystalline material, in particular to a molecular fluorescent probe complex material, a preparation method and application thereof in identifying chromium (VI) and iron (III) ions in a water environment.
Background
Hexavalent chromium ions, particularly chromate ions and dichromate ions, are widely used in the industrial production field. However, this ion is also considered to be a non-biodegradable environmental pollutant, so that it is concentrated in the organism, and further, it causes a lesion to the organism's organ to cause cancer, malformation, and gene mutation. Iron is a trace element indispensable to many physiological processes of human body, is also the core part of hemoglobin, participates in the synthesis of hemoglobin, myoglobin, cytochrome oxidase, peroxidase and catalase, plays an important role in oxygen transfer and metabolic activity of human body, and is an indispensable substance in many physiological processes of human body. However, excessive iron ions in the environment not only cause pollution and affect the normal growth of animals and plants, but also cause poisoning if the human body intakes excessive iron ions. Therefore, it is imminent to be able to efficiently and rapidly detect chromium (VI) ions and iron (III) ions at the same time.
Many advanced techniques such as atomic absorption, colorimetry, chromatography, inductively coupled plasma, spectroscopic analysis, electrochemical methods, etc. have been developed to enable the detection of chromium (VI) and iron (III) ions. Although these methods have the advantages of high sensitivity and accuracy, the technologies generally have the problems of long time consumption, expensive detection equipment, complicated sample pretreatment, requirement of professionals and the like, and the application of the methods is severely limited. Therefore, it is necessary to develop a method for quantitatively detecting chromium (VI) ions and iron (III) ions rapidly and at low cost without performing pretreatment. As an important fluorescent probe material, the molecular fluorescent probe crystalline material generally has good crystallinity, and the structural composition and the spatial configuration of the molecular fluorescent probe crystalline material can be determined by the technologies such as X-ray single crystal and the like, so that the establishment of clear correlation between the structure and the property is facilitated. In addition, the molecular fluorescent probe crystalline material has the advantages of high precision, high sensitivity, short response time, good adaptability and the like, thereby overcoming the defects of the detection method. In addition, few fluorescent probes for identifying chromium (VI) ions and iron (III) ions are reported, especially in water. Therefore, the development of a fluorescent probe capable of identifying chromium (VI) ions and iron (III) ions in a water body with high sensitivity is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a molecular fluorescent probe crystalline material for simultaneously identifying chromium (VI) ions and iron (III) ions with high sensitivity, which has the advantages of simple preparation process and high yield, and has the advantage of identifying the chromium (VI) ions and the iron (III) ions with high sensitivity in a water body, and has great application value in the detection of the chromium (VI) ions and the iron (III) ions in the monitoring of the water body environment.
The invention also aims to provide a preparation method and application of the sub-fluorescent probe crystalline material for simultaneously identifying chromium (VI) ions and iron (III) ions with high sensitivity.
The technical scheme of the invention is that the molecular fluorescent probe crystalline material has a chemical formula of { [ Zn ]2(FDA)2(4-abpt)2(H2O)2]}nOf which FDA2-Is divalent anion of 2, 5-furandicarboxylic acid, 4-abpt is 4-amino-3, 5-di (4-pyridyl) -1,2, 4-triazole, and n is a natural number from 1 to infinity.
More specifically, the molecular fluorescent probe crystalline material belongs to an orthorhombic system, the space group is Aea2, and the unit cell parameters are as follows:
α -90 °, β -90 °, γ -90 °, crystal volume
Z＝8。
More specifically, two Zn exist in the minimum asymmetric structural unit of the molecular fluorescent probe crystalline material2+Ion, two FDAs2-Ligand, two 4-abpt and two waterIn which Zn is2+The ion adopts a coordination mode of six-coordinated octahedron, and is respectively linked with the ions from two FDAs2-Three oxygen atoms in (1), two nitrogen atoms in (4-abpt) and one oxygen atom in water coordinate, and adjacent Zn2+Ion first pass FDA2-The ligand forms a one-dimensional chain structure, and two mutually perpendicular two-dimensional layered structures are formed by the 4-abpt ligand.
The invention also provides a preparation method of the molecular fluorescent probe crystalline material, which comprises the following synthetic steps:
(1) organic ligand H2FDA, 4-abpt and Zn (NO)3)2·6H2Dissolving O in a mixed solvent of N, N-dimethylacetamide and deionized water to obtain a mixed solution;
(2) and (3) placing the mixed solution in a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 90 ℃, taking out a product, separating a solid, and washing the solid for multiple times by using N, N-dimethylacetamide to obtain a colorless blocky crystal.
Further preferably, said H2FDA、4-abpt、Zn(NO3)2·6H2O, N, the molar ratio of N-dimethylacetamide to water is 1:1:1:322.6: 1667.
The molecular fluorescent probe crystalline material is suitable for application in the aspect of detection of chromium (VI) and iron (III) ions in a water body environment, and the detection limit of the molecular fluorescent probe crystalline material is respectively as low as 1.25 × 10-6mol/L(CrO4 2-)、1.42×10-6mol/L(Cr2O7 2-) And 2.17 × 10-6mol/L(Fe3+)。
The molecular fluorescent probe crystalline material has the beneficial effects that (1) the molecular fluorescent probe crystalline material has high selectivity and sensitivity, and simultaneously shows sensitive identification on chromium (VI) ions and iron (III) ions in a water body environment. (2) The molecular fluorescent probe crystalline material is solid powder, is easy to store, has multiple advantages of simple and easy synthesis, no need of pretreatment of a sample, high yield and the like, and has great potential application value in preparation of a fluorescent probe solid device and detection of chromium (VI) and iron (III) ions in water.
Drawings
FIG. 1 is a schematic diagram of a molecular fluorescent probe of the present invention;
FIG. 2 is a two-dimensional structure diagram of a molecular fluorescent probe crystalline material according to the present invention;
FIG. 3 is a powder diffraction pattern of the molecular fluorescent probe crystalline material of the present invention;
FIG. 4 is a fluorescence spectrum of the crystalline material of the molecular fluorescent probe according to the present invention with different anions;
FIG. 5 is a fluorescence spectrum of the molecular fluorescent probe crystalline material of the present invention with different concentrations of dichromate ions,
FIG. 6 is a fluorescence spectrum of the molecular fluorescent probe crystalline material of the present invention with different concentrations of chromate ions.
FIG. 7 is a fluorescence spectrum of the molecular fluorescent probe crystalline material of the present invention for different cationic effects;
FIG. 8 is the fluorescence spectrum of the molecular fluorescent probe crystalline material of the present invention with different concentrations of iron ions.
Detailed Description
The present invention will be described in further detail with reference to examples.
This example provides a molecular fluorescent probe crystalline material for identifying chromium (VI) and iron (III) ions in an aqueous environment, and its chemical formula is: { [ Zn ]2(FDA)2(4-abpt)2(H2O)2]}n,
Of which FDA2-Is 2, 5-furandicarboxylic acid dianion, 4-abpt is 4-amino-3, 5-di (4-pyridyl) -1,2, 4-triazole, and n is a natural number from 1 to infinity;
the material belongs to an orthorhombic system, the space group is Aea2, and the unit cell parameters are as follows:
α -90 °, β -90 °, γ -90 °, crystal volume
Z＝8。
Two Zn exist in the minimum asymmetric structural unit of the material2+Ion, two FDAs2-Ligand, two 4-abpt and two water molecules, wherein Zn2+The ion adopts a coordination mode of six-coordinated octahedron, and is respectively linked with the ions from two FDAs2-Three oxygen atoms in (1), two nitrogen atoms in (4-abpt) and one oxygen atom in water coordinate, and adjacent Zn2+Ion first pass FDA2-The ligand forms a one-dimensional chain structure, and two mutually perpendicular two-dimensional layered structures are formed by the 4-abpt ligand.
The embodiment provides a preparation method of a molecular fluorescent probe crystalline material for identifying chromium (VI) and iron (III) ions in a water environment, which comprises the following synthetic steps:
(1) 1mmol of organic ligand H2FDA, 1mmol 4-abpt and 1mmol Zn (NO)3)2·6H2Dissolving O in a mixed solvent of 3m L N, N-dimethylacetamide and 3m L deionized water to obtain a mixed solution, and (2) placing the mixed solution in a closed hydrothermal reaction kettle, reacting at a constant temperature of 90 ℃ for 72 hours, taking out a product, separating a solid, and washing the solid with N, N-dimethylacetamide for multiple times to obtain a colorless blocky crystal.
The properties of the crystalline material of the molecular fluorescent probe prepared in the example are characterized as follows:
(1) the structure of the molecular fluorescent probe crystalline material of the embodiment is determined as follows:
the crystal structure is determined by Supernova X-ray single crystal diffractometer and Mo-K α ray monochromatized by graphite
Collecting diffraction points in omega-phi scanning mode for incident radiation source, correcting by least square method to obtain unit cell parameters, directly solving difference Fourier electron density diagram by SHE L X L-97 to obtain crystal structure, and obtaining crystal structure by L orentz andand correcting the polarization effect. All H atoms were synthesized by difference Fourier and determined by ideal position calculations. The detailed crystal determination data are shown in table 1.
TABLE 1 crystallography data for molecular fluorescent probes crystalline materials
FIG. 1 is a unit cell diagram of a molecular fluorescent probe crystalline material, from which it can be seen that: two Zn atoms in the smallest asymmetric structural unit2+Ion, two FDAs2-Ligand, two 4-abpt and two water molecules, wherein Zn2+The ion adopts a coordination mode of six-coordinated octahedron, and is respectively linked with the ions from two FDAs2-Three oxygen atoms in (a), two nitrogen atoms in (b) 4-abpt and one oxygen atom in water.
FIG. 2 is a two-dimensional structure diagram of a molecular fluorescent probe crystalline material, from which it can be seen that: the two-dimensional layered structures are almost perpendicular to each other.
(2) Chemical stability test of molecular fluorescent probe crystalline material:
in order to verify whether the structure of the material in the chromium (VI) and iron (III) ion solution is changed, the synthesized material is soaked in the chromium (VI) and iron (III) ion solution and subjected to a powder diffraction test. As shown in fig. 3: the powder diffraction peak of the material soaked in the chromium (VI) and iron (III) ion solution is matched with the simulated powder diffraction peak, which shows that the material can still keep the structure unchanged in the chromium (VI) and iron (III) ion solution.
(3) The fluorescent property of the molecular fluorescent probe crystalline material is characterized in that:
FIG. 4 shows fluorescence spectra of molecular fluorescent probe crystalline materials in different anionic aqueous solutions, showing that: the chromium (VI) ions have obvious quenching effect on the fluorescence intensity of the molecular fluorescent probe crystalline material, and other anions have almost no influence on the fluorescence intensity of the molecular fluorescent probe crystalline material.
FIG. 5 shows the addition of different contents of chromium (VI) ions into the aqueous solution of molecular fluorescent probe crystalline materialIt can be seen from the figure that when dichromate ions are gradually added into the aqueous solution of the molecular fluorescent probe crystalline material, the fluorescence intensity shows a rapid and gradual slow descending trend along with the increase of the amount of the dichromate ions, and the change is obvious, and finally fluorescence quenching occurs, which indicates that the molecular fluorescent probe crystalline material has good fluorescence response to the dichromate ions, can be used as a dichromate ion fluorescent probe, and the detection line is 1.25 × 10-6mol·L-1。
FIG. 6 is a graph showing the change of fluorescence intensity of chromate ions of different contents added into an aqueous solution of a molecular fluorescent probe crystalline material, from which it can be seen that when chromate ions are gradually added into the aqueous solution of the molecular fluorescent probe crystalline material, the fluorescence intensity shows a rapid and then gradually slow down trend along with the increase of the amount of chromate ions, and the change is obvious, and finally fluorescence quenching occurs, which shows that the molecular fluorescent probe crystalline material has a good fluorescence response to chromate ions, can be used as a chromate ion fluorescent probe, and the detection line is 1.42 × 10-6mol/L mol·L-1。
FIG. 7 is a fluorescence spectrum of a molecular fluorescent probe crystalline material in different cation aqueous solutions, and shows that: the iron (III) ions have obvious quenching effect on the fluorescence intensity of the molecular fluorescent probe crystalline material, and other cations have almost no influence on the fluorescence intensity of the molecular fluorescent probe crystalline material.
FIG. 8 is a graph showing the change of the fluorescence intensity of iron (III) ions with different contents dropwise added into an aqueous solution of a molecular fluorescent probe crystalline material, wherein the graph shows that when the iron (III) ions are gradually added into the aqueous solution of the molecular fluorescent probe crystalline material, the fluorescence intensity shows a descending trend of a rapid decrease and a gradual decrease along with the increase of the amount of the iron (III) ions, the change is obvious, and fluorescence quenching is finally carried out, which shows that the molecular fluorescent probe crystalline material has good fluorescence response to the iron (III) ions, can be used as an iron (III) ion fluorescent probe, and the detection line is 2.17 × 10-6mol/L。
Claims (7)
1. A molecular fluorescent probe crystalline material is characterized by a chemical formula { [ Zn ]2(FDA)2(4-abpt)2(H2O)2]}nOf which FDA2-Is divalent anion of 2, 5-furandicarboxylic acid, 4-abpt is 4-amino-3, 5-di (4-pyridyl) -1,2, 4-triazole, and n is a natural number from 1 to infinity.
2. The molecular fluorescent probe crystalline material as claimed in claim 1, wherein the molecular fluorescent probe crystalline material belongs to an orthorhombic system, the space group is Aea2, and the unit cell parameters are:
α -90 °, β -90 °, γ -90 °, crystal volume
Z＝8。
3. The molecular fluorescent probe crystalline material as claimed in claim 1, wherein two Zn exist in the minimum asymmetric structural unit of the molecular fluorescent probe crystalline material2+Ion, two FDAs2-Ligand, two 4-abpt and two water molecules, wherein Zn2+The ion adopts a coordination mode of six-coordinated octahedron, and is respectively linked with the ions from two FDAs2-Three oxygen atoms in (1), two nitrogen atoms in (4-abpt) and one oxygen atom in water coordinate, and adjacent Zn2+Ion first pass FDA2-The ligand forms a one-dimensional chain structure, and two mutually perpendicular two-dimensional layered structures are formed by the 4-abpt ligand.
4. A method for preparing the molecular fluorescent probe crystalline material of claim 1, which is characterized by comprising the following steps:
(1) organic ligand H2FDA, 4-abpt and Zn (NO)3)2 .6H2Dissolving O in a mixed solvent of N, N-dimethylacetamide and deionized water to obtain a mixed solution;
(2) and (3) placing the mixed solution in a closed hydrothermal reaction kettle, reacting at constant temperature, taking out a product, separating the solid, washing the solid for multiple times by using N, N-dimethylacetamide, and obtaining colorless blocky crystals, namely the molecular fluorescent probe crystalline material.
5. The method for preparing the molecular fluorescent probe crystalline material as claimed in claim 4, wherein the H is2FDA、4-abpt、Zn(NO3)2 .6H2O, N, the molar ratio of N-dimethylacetamide to water is 1:1:1:322.6: 1667.
6. The method for preparing the molecular fluorescent probe crystalline material as claimed in claim 4, wherein the reaction temperature is 90 ℃.
7. The molecular fluorescent probe crystalline material of claim 1, for detecting chromium (VI) and iron (III) ions in monitoring of water environment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866989A (en) * | 2017-01-20 | 2017-06-20 | 江南大学 | One kind has selectivity detection Fe3+The preparation method of the luminescent crystal material of ion |
| CN107011367A (en) * | 2017-04-05 | 2017-08-04 | 江南大学 | A kind of preparation for the luminescent crystal material that there is selectivity to detect dichromate ion |
| CN108218900A (en) * | 2017-12-23 | 2018-06-29 | 盐城师范学院 | A kind of preparation and its application of zinc metal complex fluorescent probe |
| CN108299476A (en) * | 2018-02-08 | 2018-07-20 | 昆明学院 | Azacyclo-, Zinc polycarboxylate composition fluorescence probe preparation method and application |
| CN108690059A (en) * | 2018-06-29 | 2018-10-23 | 江南大学 | One kind having selectivity detection Cu(Ⅱ)Luminescent crystal material preparation method and its luminescent crystal material |
-
2020
- 2020-04-26 CN CN202010340533.XA patent/CN111484511B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866989A (en) * | 2017-01-20 | 2017-06-20 | 江南大学 | One kind has selectivity detection Fe3+The preparation method of the luminescent crystal material of ion |
| CN107011367A (en) * | 2017-04-05 | 2017-08-04 | 江南大学 | A kind of preparation for the luminescent crystal material that there is selectivity to detect dichromate ion |
| CN108218900A (en) * | 2017-12-23 | 2018-06-29 | 盐城师范学院 | A kind of preparation and its application of zinc metal complex fluorescent probe |
| CN108299476A (en) * | 2018-02-08 | 2018-07-20 | 昆明学院 | Azacyclo-, Zinc polycarboxylate composition fluorescence probe preparation method and application |
| CN108690059A (en) * | 2018-06-29 | 2018-10-23 | 江南大学 | One kind having selectivity detection Cu(Ⅱ)Luminescent crystal material preparation method and its luminescent crystal material |
Non-Patent Citations (3)
| Title |
|---|
| JINFANG ZHANG等: ""Two luminescent Zn(II)/Cd(II) metal–organic frameworks as rare multifunctional sensors"", 《NEWJ.CHEM.》 * |
| JINFANG ZHANG等: ""Water-Stable Luminescent Zn(II) Metal-Organic Framework as Rare Multifunctional Sensor for Cr(VI) and TNP"", 《CHEMISTRYSELECT》 * |
| MURSEL ARICI等: ""Multifunctional luminescent coordination polymers based on tricarboxylic acid for the detection of 2,4-dinitrophenol and iron(III) and aluminum(III) ions"", 《NEW J. CHEM.》 * |
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