CN113234233B - Europium-based metal-organic framework material with antibiotic fluorescence recognition function and preparation method thereof - Google Patents

Europium-based metal-organic framework material with antibiotic fluorescence recognition function and preparation method thereof Download PDF

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CN113234233B
CN113234233B CN202110607233.8A CN202110607233A CN113234233B CN 113234233 B CN113234233 B CN 113234233B CN 202110607233 A CN202110607233 A CN 202110607233A CN 113234233 B CN113234233 B CN 113234233B
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邹吉勇
李玲
游胜勇
章力
谌开红
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Institute of Applied Chemistry Jiangxi Academy of Sciences
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Abstract

A europium-based metal-organic framework material with antibiotic fluorescence recognition and a preparation method thereof are disclosed, wherein 2,5-furandicarboxylic acid is taken as a ligand, rare earth europium ions are taken as a metal center, and the europium-based metal-organic framework material is synthesized by a solvothermal method. The material prepared by the invention has the advantages of simple preparation method, high purity, good activity, no need of pretreatment on the material, easy implementation, and quick and simple operation, good selectivity, high sensitivity, low detection limit, and recyclability in the aspect of detecting antibiotics, and can be used for detection after being dried at room temperature, so that the material has great potential application value in the preparation of fluorescent probe solid-state devices and the detection of antibiotics.

Description

Europium-based metal-organic framework material with antibiotic fluorescence recognition function and preparation method thereof
Technical Field
The invention relates to a europium-based metal-organic framework material with antibiotic fluorescence recognition and a preparation method thereof, belonging to the technical field of porous molecular crystal materials.
Background
Since 1929, the british scholars alexander fleming discovered penicillin first and applied it clinically, antibiotics as a kind of drugs for the treatment of bacterial infection diseases, has the advantages of broad antibacterial spectrum, definite therapeutic effect, easy use, many varieties, large output, low price, etc., and is widely used for the treatment of bacterial infections in human and animals. However, with the widespread use of antibiotics, the problem of antibiotic abuse is becoming more and more prominent. Antibiotic abuse can cause a range of physical and environmental problems, such as excessive use of antibiotics can cause serious drug resistance in humans and animals, and antibiotic residues are also discharged into the environment through metabolic action, which can cause serious environmental pollution. Therefore, there is a need to develop and develop a method for detecting antibiotics efficiently and rapidly. Methods developed at present for detecting antibiotic pollutants include polarography, supercritical fluid chromatography, high performance liquid chromatography, gas chromatography, spectroscopic analysis, electrochemistry and the like, however, the application of the methods is severely restricted by the problems of time consumption, high cost, complicated pretreatment, requirement of professionals and the like existing in the methods. Therefore, it is necessary to develop a method for quantitatively detecting the antibiotic rapidly at low cost without pretreatment.
The metal-organic framework fluorescent sensing material is considered to be one of the most promising detection methods, and is widely used for identifying harmful substances such as anions, cations, small molecular organic matters and the like, see H. -C.Zh o u et al, chem.Soc.Rev., 2014, 43, 5415-5418 and S. -K.Ghosh et al, chem.Soc.Rev., 2017, 46, 3242-3285. The method allows the presence of an analyte to be detected simply by the change in fluorescence intensity as a function of analyte concentration. Compared with the traditional analysis technology, the fluorescence sensing detection based on the metal-organic framework has the characteristics of high precision, high sensitivity, small size, short response time, good adaptability and the like. In recent years, many reports have been made on the fluorescent response of a metal-organic framework to a single type of antibiotic, for example, zhou et al have reported a metal-organic framework material of terbium and zinc, and the results of fluorescent sensing detection studies show that: the material has good detection performance on nitrofurans such as furazolidone, furacilin, nitrofurantoin and the like in water (see: Z. -H. Z. H.o u and the like, inorg. Chem. 2018, 57, 3833); han et al have reported a sodium and europium metal organic framework material, and the results of fluorescence sensing detection research show that: the material has good selective detection capability on ornidazole and the like in water (see: M. -L. Han et al, J. Mater. Chem. C, 2017, 5, 8469).
The publication number CN110128674 discloses a water-stable rare earth metal organic framework material for fluorescence detection of sulfonamides antibiotics and a preparation method thereof, however, research on simultaneous fluorescence response of multiple antibiotics is still less, and particularly, the simultaneous fluorescence response of the rare earth metal-organic framework to multiple antibiotics is not reported.
Disclosure of Invention
The invention aims to solve the problems and obtain a europium-based metal-organic framework material which has chemical stability and simultaneously responds to nitrofuran antibiotics, nitroimidazole antibiotics and sulfonamide antibiotics in a fluorescence manner.
The technical scheme of the invention is that the europium-based metal-organic framework material with antibiotic fluorescence recognition has a chemical formula as follows: { [ Eu ] 2 (FDA) 3 (H 2 O) 3 (DMF)·DMF·2H 2 O]} n (ii) a In the formula: n is a natural number from 1 to positive infinity; FDA 2- Is obtained by deprotonating 2,5-furandicarboxylic acid; DMF is N, N-dimethylformamide.
The europium-based metal-organic framework material belongs to a monoclinic system, and the space group isP2 1 /nThe unit cell parameters are: a = 10.3176 (3) a, b = 21.0431 (7) a, c = 15.6348 (4) a,α= 90°，ß= 93.844(3) °，γ= 90 °。
the basic structural unit of the europium-based metal-organic framework material contains two kinds of europium ions with coordination environment and 3 deprotonated ligands FDA 2- 3 coordinated water molecules, 1 coordinated DMF molecule and 1 free DMF molecule and 2 free water molecules; euO with europium ion adopting deformed single-cap square antiprism 9 Coordination mode, eu1 ions with ligands from 6 dehydrogenises FDA, respectively 2- 8 oxygen atoms in (a) and oxygen atoms from 1 water are coordinated; eu2 ions with the respective of 4 dehydrogenating ligands from FDA 2- 6 oxygen atoms in the group, 2 oxygen atoms in water and 1 DMF; adjacent europium ions pass through dehydrogenation ligand FDA 2- A three-dimensional network structure is formed spatially.
The europium-based metal-organic framework material can be simplified into a single node of 6,6 connectionpcuTopology with dot symbol {4 12 .6 3 }。
A preparation method of europium-based metal-organic framework material with antibiotic fluorescence recognition comprises the following synthetic steps:
(1) Respectively reacting organic ligands H 2 Dissolving FDA into N, N-dimethylformamide solvent;
(2) Mixing Mn (OAc) 2 . 4H 2 O and Eu (NO) 3 ) 3 . 6H 2 Dissolving O in water;
(3) Mixing the two solutions obtained in the steps (1) and (2), then putting the mixture into a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 90 ℃, taking out a product, and separating a solid;
(4) The solid was washed with N, N-dimethylformamide several times to obtain colorless bulk crystals.
Said H 2 The concentration of the N, N-dimethylformamide solution of FDA is 0.01-1mol/L; the Mn (OAc) 2 . 4H 2 The concentration of the water solution of O is 0.01-1mol/L; the Eu (NO) 3 ) 3 . 6H 2 The concentration of the O aqueous solution is 0.01-1mol/L.
The europium-based metal-organic framework material can stably exist in water, methanol, ethanol, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, acetonitrile, 1,4-dioxane and ethylene glycol solvents.
The europium-based metal-organic framework material has a fluorescence enhancement effect on methanol, N, N-dimethylformamide and N, N-dimethylacetamide.
The europium-based metal-organic framework material can detect nitrofurans antibiotics such as Furazolidone (FZD), nitrofurantoin (NFT) and Nitrofurazone (NFZ), nitroimidazoles antibiotics such as Metronidazole (MND), ornidazole (RND), 1,2-methyl-5-nitroimidazole (DND) and Ornidazole (OND), and sulfonamides antibiotics such as Sulfadiazine (SDZ) and Sulfadimidine (SMZ) through fluorescence change.
The europium-based metal-organic framework material is at a low concentration (0-16 [ mu ] mol. L) -1 ) The fluorescence change curve in the antibiotic DMF solution is in a linear relationship with the antibiotic concentration, and the detection limit is 0.185 mu mol.L -1 ，0.173µmol·L -1 ，0.141µmol·L -1 ，0.346µmol·L -1 ，0.378µmol·L -1 ，0.255µmol·L -1 ，0.323µmol·L -1 ，0.148µmol·L -1 ，0.139µmol·L -1 The europium-based metal-organic framework material can be applied to the field of antibiotic detection fluorescent probes.
The europium-based metal-organic framework material has the beneficial effects that the europium-based metal-organic framework material is different from the existing europium-based framework material and is a new material; the europium-based metal-organic framework material has a linear relation between a fluorescence change curve and the concentration of antibiotics under the condition of a low-concentration DMF solution; different from the prior art, the test conditions are aqueous solutions; in addition, the prior art can only singly recognize the sulfonamide antibiotics through fluorescence, the invention can simultaneously and effectively recognize the three antibiotics, and the detection limit is much lower than that of the prior art.
The material prepared by the invention has the advantages of simple preparation method, high purity, good activity, no need of pretreatment on the material, easy implementation, and quick and simple operation, good selectivity, high sensitivity, low detection limit, and recyclability in the aspect of detecting antibiotics, and can be used for detection after being dried at room temperature, so that the material has great potential application value in the preparation of fluorescent probe solid-state devices and the detection of antibiotics.
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FIG. 1 is a three-dimensional structure diagram of a europium-based metal-organic framework material of the present invention;
FIG. 2 shows fluorescence spectra of europium-based metal-organic frameworks of the present invention in different solvents;
FIG. 3 is a fluorescence spectrum of different concentrations of FZD solutions for europium-based metal-organic frameworks in an example of the present invention;
FIG. 4 is the FZD concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples of the present invention 0 Graph of/I, inset is the FZD concentration versus the fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ FZD)]≤16μmol/L)；
FIG. 5 is a fluorescence spectrum of different concentrations of NFT solutions with europium-based metal-organic frameworks according to an embodiment of the present invention;
FIG. 6 is the fluorescence intensity I of the rare earth metal organic framework material in the NFT concentration vs. example of the invention 0 Graph of/I, inset is the concentration of NFT versus the fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ NFT)]≤16μmol/L)；
FIG. 7 is a fluorescence spectrum of different concentrations of NFZ solutions with europium-based metal-organic frameworks according to an embodiment of the present invention;
FIG. 8 is the fluorescence intensity I of the rare earth metal organic framework material in the example of NFZ concentration vs. the fluorescence intensity of the rare earth metal organic framework material of the present invention 0 Graph of/I, inset is the concentration of NFZ versus the fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ NFZ)]≤16μmol/L)；
FIG. 9 is a fluorescence spectrum of different concentrations of MND solutions with europium-based metal organic framework materials in an example of the present invention;
FIG. 10 shows the fluorescence intensity I of the rare-earth metal organic framework material in an example of MND concentration vs. the invention 0 Graph of MND concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ MND)]≤16μmol/L)；
FIG. 11 is a fluorescent spectrum of different concentrations of RND solutions with europium-based metal-organic frameworks according to an embodiment of the present invention;
FIG. 12 shows the RND concentration versus fluorescence intensity I of the rare earth metal organic framework material in the example of the present invention 0 Graph of RND concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot ([ RND) of/I]≤16μmol/L)；
FIG. 13 is a fluorescence spectrum of different concentrations of DND solutions with europium-based metal-organic frameworks in an example of the present invention;
FIG. 14 shows the fluorescence intensity I of the rare-earth metal organic framework material in the example of DND concentration vs. the invention 0 Graph of DND concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ DND)]≤16μmol/L)；
FIG. 15 is a fluorescence spectrum of europium-based metal-organic framework materials in different concentrations of OND solutions according to an embodiment of the present invention;
FIG. 16 is the OND concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples of the present invention 0 Graph of/I, inset is concentration of OND versus rare earth metal organic framework in the examplesFluorescence intensity of Material I 0 Stern-Volmer Linear plot ([ OND)/I]≤16μmol/L)；
FIG. 17 is a fluorescence spectrum of different concentrations of SDZ with europium-based metal-organic frameworks in an example of the present invention;
FIG. 18 shows the concentration of SDZ versus the fluorescence intensity I of the rare earth metal organic framework material in the example of the present invention 0 Graph of SDZ concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ SDZ)]≤16μmol/L)；
FIG. 19 is a fluorescence spectrum of different concentrations of SMD solutions with europium-based metal-organic frameworks in an example of the present invention;
FIG. 20 shows fluorescence intensity I of rare earth metal organic frameworks in an example of SMD concentration vs. concentration according to the invention 0 Graph of SMD concentration versus fluorescence intensity I of the rare earth metal organic framework material in the examples 0 Stern-Volmer Linear plot of/I ([ SMD]≤16μmol/L)。
Detailed Description
The present embodiment relates to a europium-based metal-organic framework material with antibiotic fluorescence recognition, which has the chemical formula: { [ Eu ] 2 (FDA) 3 (H 2 O) 3 (DMF)·DMF·2H 2 O]} n 。
In the formula: n is a natural number from 1 to positive infinity; FDA 2- Is obtained by deprotonating 2,5-furandicarboxylic acid; DMF is N, N-dimethylformamide.
The europium-based metal-organic framework material belongs to a monoclinic system and has a space group ofP2 1 /nThe unit cell parameters are: a = 10.3176 (3) A, b = 21.0431 (7) A, c = 15.6348 (4) A,α= 90°，ß= 93.844(3) °，γ= 90 °。
the basic structural unit of the europium-based metal-organic framework material contains two kinds of europium ions with coordination environment and 3 deprotonated ligands FDA 2- 3 coordinated water molecules, 1 coordinated DMF molecule and 1 free DMF molecule and 2 free water molecules; euO with europium ion adopting deformed single-cap square antiprism 9 Coordination mode, eu1 ion divisionRespectively from 6 dehydrogenation ligands FDA 2- 8 oxygen atoms in (a) and oxygen atoms from 1 water are coordinated; eu2 ions with the respective of 4 dehydrogenating ligands from FDA 2- 6 oxygen atoms in the group, 2 oxygen atoms in water and 1 DMF; adjacent europium ions pass through dehydrogenation ligand FDA 2- A three-dimensional network structure is formed in space.
The europium-based metal-organic framework material can be simplified into a single node of 6,6 connectionpcuTopology, dot symbol of {4 } 12 .6 3 }。
The preparation method of the europium-based metal-organic framework material with antibiotic fluorescence recognition of the embodiment comprises the following synthesis steps:
(1) 31.2 mg of H 2 FDA was dissolved in 3mL of N, N-dimethylformamide solvent.
(2) 24.5mg of Mn (OAc) 2 . 4H 2 O and 44.6mgEu (NO 3) 3 . 6H 2 O was dissolved in 3mL of water.
(3) Mixing the two solutions in the steps 1 and 2, then putting the mixture into a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 90 ℃, taking out a product, and separating a solid.
(4) The solid was washed 3 times with N, N-dimethylformamide and water to give colorless bulk crystals with a yield of 65% calculated on the basis of europium metal.
The properties of the europium-based metal-organic framework material with antibiotic fluorescence recognition prepared in the example are characterized as follows:
(1) The structure of europium-based metal-organic framework material with antibiotic fluorescence recognition of this example was determined:
the crystal structure is measured by using a Supernova type X-ray single crystal diffractometer, using Mo-K alpha rays (lambda = 0.71073A) subjected to graphite monochromatization as an incident radiation source, collecting diffraction points in an omega-phi scanning mode, correcting by a least square method to obtain unit cell parameters, directly solving a crystal structure from a difference Fourier electron density diagram by using an SHELXL-97 method, and correcting by Lorentz and a polarization effect. All H atoms were synthesized by difference Fourier and determined by ideal position calculations. The exact number of solvent molecules was determined by thermogravimetric and elemental analysis tests, and the detailed crystal determination data is shown in table 1.
Figure DEST_PATH_IMAGE001
FIG. 1 is a three-dimensional structural diagram of the europium-based metal-organic framework material of this example, wherein n is a natural number from 1 to positive infinity, indicating that the material is a polymer.
(2) The fluorescence property of the europium-based metal-organic framework material of the embodiment is characterized:
FIG. 2 shows fluorescence spectra of europium-based metal-organic frameworks in different solvents according to the present invention. The figure shows that: the europium-based metal-organic framework material has a fluorescence enhancement effect in methanol, N, N-dimethylformamide and N, N-dimethylacetamide. And other solvents have little influence on the fluorescence intensity of the europium-based metal-organic framework material.
FIG. 3 is a fluorescence spectrum of different concentrations of FZD solutions for europium-based metal-organic frameworks in the examples of the present invention. As can be seen from the figure: when the FZD is gradually added into the DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the FZD shows a descending trend along with the increase of the amount of the FZD, the change is obvious, and finally fluorescence quenching occurs, which indicates that the europium-based metal-organic framework material has good fluorescence response to the FZD and can be used as an FZD fluorescent probe.
FIG. 4 shows FZD concentration versus fluorescence intensity I of europium-based metal-organic framework materials in examples of the present invention 0 Plot of/I, inset is FZD concentration versus fluorescence intensity I of europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot of/I ([ FZD)]Less than or equal to 16 mu mol/L). As can be seen from the figure: at lower FZD concentration (0-16 mu mol/L), the europium-based metal-organic framework material has fluorescence intensity I 0 the/I and the FZD concentration are in a linear relation, and the detection limit is 0.185 mu mol L -1 When the concentration of FZD is higher, the fluorescence intensity I of the europium-based metal-organic framework material 0 the/I shows a slow-first and fast-second trend along with the concentration of the FZD and does not show a linear relation any more.
FIG. 5 is a fluorescence spectrum of different concentrations of NFT solutions with europium-based metal-organic frameworks according to an embodiment of the present invention. As can be seen from the figure: when NFT is gradually added into DMF solution of europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the amount of the NFT, the change is obvious, and the fluorescence quenching finally occurs, so that the europium-based metal-organic framework material has good fluorescence response to the NFT and can be used as an NFT fluorescent probe.
FIG. 6 shows the NFT concentration versus fluorescence intensity I of europium-based metal-organic frameworks in examples of the present invention 0 Graph of/I inset is the NFT concentration versus the europium-based metal-organic framework material fluorescence intensity I in the examples 0 Stern-Volmer Linear plot of/I ([ NFT)]Less than or equal to 16 mu mol/L). As can be seen from the figure: when the NFT concentration is lower (0-16 mu mol/L), the europium-based metal-organic framework material has the fluorescence intensity I 0 the/I and the NFT concentration are in a linear relation, and the detection limit is 0.173 mu mol.L -1 Europium-based metal-organic framework material fluorescence intensity I at higher NFT concentration 0 the/I shows a slow-first and fast-second trend with NFT concentration, no longer in a linear relationship.
FIG. 7 shows the fluorescence spectra of different concentrations of NFZ solutions with europium-based metal-organic frameworks according to the example of the present invention. As can be seen from the figure: when the NFZ is gradually added into the DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the amount of the NFZ, the change is obvious, and finally fluorescence quenching occurs, which shows that the europium-based metal-organic framework material has good fluorescence response to the NFZ and can be used as an NFZ fluorescent probe.
FIG. 8 shows the NFZ concentration versus fluorescence intensity I of europium-based metal-organic frameworks in examples of the present invention 0 Graph of/I inset is the NFZ concentration versus the fluorescence intensity I of the europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot of/I ([ NFZ)]Less than or equal to 16 mu mol/L). As can be seen from the figure: at a lower NFZ concentration (0-16. Mu. Mol/L), the europium-based metal-organic framework material has a fluorescence intensity I 0 the/I and the NFZ concentration are in a linear relation, and the detection limit is 0.141 mu mol.L -1 At higher NFZ concentrations, europium-based metal-ionsFluorescence intensity of machine frame material I 0 the/I shows a slow-first and fast-second trend with the NFZ concentration, no longer in a linear relationship.
FIG. 9 shows the fluorescence spectra of different concentrations of MND solutions with europium-based metal-organic framework materials in the present example. As can be seen from the figure: when MND is gradually added into a DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the quantity of the MND, the change is obvious, and finally fluorescence quenching occurs, so that the europium-based metal-organic framework material has good fluorescence response to the MND and can be used as a MND fluorescent probe.
FIG. 10 shows the fluorescence intensity I of europium-based metal-organic framework materials in the MND concentration versus example of the invention 0 Plot of/I, inset is MND concentration versus fluorescence intensity I of europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot of/I ([ MND)]Less than or equal to 16 mu mol/L). As can be seen from the figure: at low MND concentration (0-16 mu mol/L), the europium-based metal-organic framework material has fluorescence intensity I 0 the/I and the MND concentration are in a linear relation, and the detection limit is 0.346 mu mol.L -1 Europium-based metal-organic framework materials have fluorescence intensity I at higher MND concentrations 0 the/I shows a slow-first-then-fast trend with MND concentration and no longer shows a linear relationship.
FIG. 11 shows the fluorescence spectra of different concentrations of RND solutions with europium-based metal-organic framework materials in the examples of the present invention. As can be seen from the figure: when the RND is gradually added into the DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the quantity of the RND, the change is obvious, and finally fluorescence quenching occurs, which shows that the europium-based metal-organic framework material has good fluorescence response to the RND and can be used as an RND fluorescent probe.
FIG. 12 shows the RND concentration versus fluorescence intensity I of europium-based metal-organic framework materials in examples of the present invention 0 Graph of/I with inset graph of RND concentration versus fluorescence intensity I of europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot ([ RND) of/I]Less than or equal to 16 mu mol/L). As can be seen from the figure: at lower RND concentrations (0-16. Mu. Mol/L), europium-based metal-organic framework materials are fluorescentLight intensity I 0 the/I and the RND concentration are in a linear relation, and the detection limit is 0.378 mu mol.L -1 Europium-based metal-organic framework material fluorescence intensity I at higher RND concentration 0 the/I shows a slow-first and fast-second trend with RND concentration, no longer linear.
FIG. 13 shows the fluorescence spectra of different concentrations of DND solutions with europium-based metal-organic frameworks in the examples of the present invention. As can be seen from the figure: when DND is gradually added into the DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the amount of DND, the change is obvious, and finally fluorescence quenching occurs, which shows that the europium-based metal-organic framework material has good fluorescence response to DND and can be used as a DND fluorescent probe.
FIG. 14 shows the fluorescence intensity I of europium-based metal-organic framework materials in examples of DND concentration according to the invention 0 Plot of the DND concentration versus the fluorescence intensity I of the europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot of/I ([ DND)]Less than or equal to 16 mu mol/L). As can be seen from the figure: at lower DND concentrations (0-16. Mu. Mol/L), the europium-based metal-organic framework materials have a fluorescence intensity I 0 The concentration of the DND is in a linear relation, and the detection limit is 0.255 mu mol.L -1 Europium-based metal-organic framework material fluorescence intensity I at higher DND concentration 0 the/I shows a slow-first followed by fast trend with DND concentration, no longer linear.
FIG. 15 shows the fluorescence spectra of europium-based metal-organic frameworks in different concentrations of OND solutions according to the example of the present invention. As can be seen from the figure: when OND is gradually added into a DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the OND shows a descending trend along with the increase of the amount of the OND, the change is obvious, and fluorescence quenching is finally generated, so that the europium-based metal-organic framework material has good fluorescence response to the OND and can be used as an OND fluorescent probe.
FIG. 16 shows the OND concentration versus fluorescence intensity I of europium-based metal-organic framework materials in examples of the present invention 0 Plot of the OND concentration versus the fluorescence intensity I of the europium-based metal-organic framework materials in the examples 0 St of/Iern-Volmer Linear plot ([ OND)]Less than or equal to 16 mu mol/L). As can be seen from the figure: when the OND concentration is lower (0-16 mu mol/L), the europium-based metal-organic framework material has the fluorescence intensity I 0 the/I and the OND concentration are in a linear relation, and the detection limit is 0.323 mu mol.L -1 Europium-based metal-organic framework material fluorescence intensity I at higher OND concentration 0 the/I shows a slow-first and fast-second trend with the OND concentration and no longer shows a linear relationship.
FIG. 17 shows the fluorescence spectra of different concentrations of SDZ solutions for europium-based metal-organic framework materials in examples of the present invention. As can be seen from the figure: when SDZ is gradually added into a DMF solution of the europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the amount of the SDZ, the change is obvious, and finally fluorescence quenching occurs, which shows that the europium-based metal-organic framework material has good fluorescence response to the SDZ and can be used as an SDZ fluorescent probe.
FIG. 18 shows the SDZ concentration versus fluorescence intensity I of europium-based metal-organic framework materials in examples of the present invention 0 Graph of/I inset shows SDZ concentration versus fluorescence intensity I of europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot of/I ([ SDZ)]Less than or equal to 16 mu mol/L). As can be seen from the figure: at low SDZ concentrations (0-16. Mu. Mol/L), europium-based metal-organic framework materials have fluorescence intensity I 0 the/I and the SDZ concentration are in a linear relation, and the detection limit is 0.148 mu mol.L -1 The europium-based metal-organic framework material has a fluorescence intensity I at a higher SDZ concentration 0 the/I shows a slow-first and fast-second trend with the SDZ concentration and no longer shows a linear relationship.
FIG. 19 is a fluorescence spectrum of different concentrations of SMZ solutions with europium-based metal-organic frameworks in an example of the present invention. As can be seen from the figure: when SMZ is gradually added into a DMF (dimethyl formamide) solution of the europium-based metal-organic framework material, the fluorescence intensity of the europium-based metal-organic framework material shows a descending trend along with the increase of the amount of the SMZ, the change is obvious, and fluorescence quenching finally occurs, so that the europium-based metal-organic framework material has good fluorescence response to the SMZ and can be used as an SMZ fluorescent probe.
FIG. 20 shows the fluorescence of europium-based metal-organic framework materials in the SMZ concentration vs. examples of the inventionLight intensity I 0 Plot of the SMZ concentration versus the fluorescence intensity I of the europium-based metal-organic framework materials in the examples 0 Stern-Volmer Linear plot of/I ([ SMZ)]Less than or equal to 16 mu mol/L). As can be seen from the figure: at low SMZ concentration (0-16 mu mol/L), the europium-based metal-organic framework material has fluorescence intensity I 0 the/I and the SMZ concentration are in a linear relation, and the detection limit is 0.139 mu mol.L -1 The europium-based metal-organic framework material has fluorescence intensity I at higher SMZ concentration 0 the/I shows a slow-first and fast-second trend with SMZ concentration and no longer shows a linear relationship.

Claims (7)

1. A europium-based metal-organic framework material with antibiotic fluorescence recognition is characterized in that: the europium-based metal-organic framework material has the chemical formula: { [ Eu ] Eu 2 (FDA) 3 (H 2 O) 3 (DMF)·DMF·2H 2 O]} n ；
In the formula: n is a natural number from 1 to positive infinity; FDA 2- Is obtained by deprotonating 2,5-furandicarboxylic acid; DMF is N, N-dimethylformamide;
the europium-based metal-organic framework material belongs to a monoclinic system, and the space group isP2 1 /nThe unit cell parameters are: a = 10.3176 (3) a, b = 21.0431 (7) a, c = 15.6348 (4) a,α= 90°，ß= 93.844(3) °，γ= 90 °；
the basic structural unit of the europium-based metal-organic framework material contains two kinds of europium ions with coordination environment and 3 deprotonated ligands FDA 2- 3 coordinated water molecules, 1 coordinated DMF molecule and 1 free DMF molecule and 2 free water molecules; euO with europium ion adopting deformed single-cap square antiprism 9 Coordination mode, eu1 ions with ligands from 6 dehydrogenises FDA, respectively 2- 8 oxygen atoms in (a) and oxygen atoms from 1 water are coordinated; eu2 ions with the respective of 4 dehydrogenating ligands from FDA 2- 6 oxygen atoms in the group, 2 oxygen atoms in water and 1 DMF; adjacent europium ions pass through dehydrogenation ligand FDA 2- Forming a three-dimensional network structure in space;
the europium-based metal-organic framework material can be simplified to be a single node of 6,6 connectionpcuTopology with dot symbol {4 12 .6 3 }。
2. The europium-based metal-organic framework material with antibiotic fluorescence recognition function of claim 1, wherein the europium-based metal-organic framework material is stable in water, methanol, ethanol, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, acetonitrile, 1,4-dioxane and ethylene glycol solvents; the europium-based metal-organic framework material generates a fluorescence enhancement effect in methanol, N, N-dimethylformamide and N, N-dimethylacetamide.
3. The europium-based metal-organic framework material with antibiotic fluorescence recognition function of claim 1, wherein the europium-based metal-organic framework material is used for detecting nitrofuran antibiotics of furazolidone, nitrofurantoin and nitrofurazone, nitroimidazole antibiotics of metronidazole, ornidazole, 1,2-methyl-5-nitroimidazole and ornidazole by fluorescence change.
4. The europium-based metal-organic framework material with antibiotic fluorescence recognition function of claim 3, wherein the fluorescence change curve of the europium-based metal-organic framework material in a low-concentration antibiotic DMF solution is in a linear relationship with the antibiotic concentration, and the detection limit of the europium-based metal-organic framework material is 0.185 μmol-L -1 ，0.173µmol·L -1 ，0.141µmol·L -1 ，0.346µmol·L -1 ，0.378µmol·L -1 ，0.255µmol·L -1 ，0.323µmol·L -1 (ii) a The europium-based metal-organic framework material can be applied to the field of antibiotic detection fluorescent probes.
5. The europium-based metal-organic framework material with antibiotic fluorescence recognition function of claim 4, wherein the low concentration is 0-16 μmol-L -1 。
6. Method for the preparation of a europium-based metal-organic framework material with antibiotic fluorescence recognition according to one of claims 1 to 5, comprising the following synthetic steps:
(1) Respectively reacting organic ligands H 2 Dissolving FDA into N, N-dimethylformamide solvent;
(2) Mixing Mn (OAc) 2 . 4H 2 O and Eu (NO) 3 ) 3 . 6H 2 Dissolving O in water;
(3) Mixing the two solutions obtained in the steps (1) and (2), then putting the mixture into a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 90 ℃, taking out a product, and separating a solid;
(4) And washing the solid for multiple times by using N, N-dimethylformamide to obtain the colorless blocky crystal europium-based metal-organic framework material with antibiotic fluorescence recognition.
7. The method for preparing the europium-based metal-organic framework material with antibiotic fluorescent recognition function as claimed in claim 6, wherein H is 2 The concentration of the N, N-dimethylformamide solution of FDA is 0.01-1mol/L; the Mn (OAc) 2 . 4H 2 The concentration of the water solution of O is 0.01-1mol/L; the Eu (NO) 3 ) 3 . 6H 2 The concentration of the O aqueous solution is 0.01-1mol/L.
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