CN113461957A - Three-dimensional rare earth terbium compound and synthesis method and application thereof - Google Patents
Three-dimensional rare earth terbium compound and synthesis method and application thereof Download PDFInfo
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- CN113461957A CN113461957A CN202110610172.0A CN202110610172A CN113461957A CN 113461957 A CN113461957 A CN 113461957A CN 202110610172 A CN202110610172 A CN 202110610172A CN 113461957 A CN113461957 A CN 113461957A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 18
- -1 rare earth terbium compound Chemical class 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000003115 biocidal effect Effects 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000003242 anti bacterial agent Substances 0.000 claims description 20
- 229940088710 antibiotic agent Drugs 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 9
- 229960000282 metronidazole Drugs 0.000 claims description 5
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 5
- KPQZUUQMTUIKBP-UHFFFAOYSA-N 1-(2-methyl-5-nitro-1-imidazolyl)-2-propanol Chemical compound CC(O)CN1C(C)=NC=C1[N+]([O-])=O KPQZUUQMTUIKBP-UHFFFAOYSA-N 0.000 claims description 4
- IPWKIXLWTCNBKN-UHFFFAOYSA-N Madelen Chemical compound CC1=NC=C([N+]([O-])=O)N1CC(O)CCl IPWKIXLWTCNBKN-UHFFFAOYSA-N 0.000 claims description 4
- 229940123317 Sulfonamide antibiotic Drugs 0.000 claims description 4
- 239000004098 Tetracycline Substances 0.000 claims description 4
- HJLSLZFTEKNLFI-UHFFFAOYSA-N Tinidazole Chemical compound CCS(=O)(=O)CCN1C(C)=NC=C1[N+]([O-])=O HJLSLZFTEKNLFI-UHFFFAOYSA-N 0.000 claims description 4
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 claims description 4
- 229960005091 chloramphenicol Drugs 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- IAIWVQXQOWNYOU-FPYGCLRLSA-N nitrofural Chemical compound NC(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 IAIWVQXQOWNYOU-FPYGCLRLSA-N 0.000 claims description 4
- NXFQHRVNIOXGAQ-YCRREMRBSA-N nitrofurantoin Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)NC(=O)C1 NXFQHRVNIOXGAQ-YCRREMRBSA-N 0.000 claims description 4
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- 229960004076 secnidazole Drugs 0.000 claims description 4
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 4
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- 230000002194 synthesizing effect Effects 0.000 claims description 4
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 4
- 229960002180 tetracycline Drugs 0.000 claims description 4
- 229930101283 tetracycline Natural products 0.000 claims description 4
- 235000019364 tetracycline Nutrition 0.000 claims description 4
- OTVAEFIXJLOWRX-NXEZZACHSA-N thiamphenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CO)NC(=O)C(Cl)Cl)C=C1 OTVAEFIXJLOWRX-NXEZZACHSA-N 0.000 claims description 4
- 229960003053 thiamphenicol Drugs 0.000 claims description 4
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- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
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- 229960001907 nitrofurazone Drugs 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- JQBILSNVGUAPMM-UHFFFAOYSA-K terbium(3+);triacetate Chemical compound [Tb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JQBILSNVGUAPMM-UHFFFAOYSA-K 0.000 claims description 3
- UFPWIQQSPQSOKM-UHFFFAOYSA-H terbium(3+);trisulfate Chemical compound [Tb+3].[Tb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UFPWIQQSPQSOKM-UHFFFAOYSA-H 0.000 claims description 3
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 3
- 150000003522 tetracyclines Chemical class 0.000 claims description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007850 fluorescent dye Substances 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 229960002135 sulfadimidine Drugs 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 4
- 150000003502 terbium compounds Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
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- 239000011540 sensing material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 229940125904 compound 1 Drugs 0.000 description 27
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- RRSNDVCODIMOFX-MPKOGUQCSA-N Fc1c(Cl)cccc1[C@H]1[C@@H](NC2(CCCCC2)[C@@]11C(=O)Nc2cc(Cl)ccc12)C(=O)Nc1ccc(cc1)C(=O)NCCCCCc1cccc2C(=O)N(Cc12)C1CCC(=O)NC1=O Chemical compound Fc1c(Cl)cccc1[C@H]1[C@@H](NC2(CCCCC2)[C@@]11C(=O)Nc2cc(Cl)ccc12)C(=O)Nc1ccc(cc1)C(=O)NCCCCCc1cccc2C(=O)N(Cc12)C1CCC(=O)NC1=O RRSNDVCODIMOFX-MPKOGUQCSA-N 0.000 description 1
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- FBOUIAKEJMZPQG-BLXFFLACSA-N diniconazole-M Chemical compound C1=NC=NN1/C([C@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-BLXFFLACSA-N 0.000 description 1
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- 229960000349 nitrofural Drugs 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention relates to the technical field of fluorescent sensing materials, in particular to a three-dimensional rare earth terbium compound and a synthesis method and application thereof, wherein the method comprises the steps of mixing 5- (4' -carboxyphenoxy) isophthalic acid with a terbium source in the presence of a water-containing solvent to obtain a mixed solution, adjusting the pH value of the mixed solution to 5-7, and then carrying out hydrothermal reaction to obtain the three-dimensional rare earth terbium compound; the terbium compound synthesized by the method provided by the invention has excellent water stability, and further research finds that the terbium compound has a three-dimensional pore channel structure, and an active site is arranged in a pore channel, so that the fluorescent probe antibiotic sulfadimidine with high sensitivity and high selectivity can be obtained.
Description
Technical Field
The invention relates to the technical field of fluorescent sensing materials, in particular to a three-dimensional rare earth terbium compound and a synthesis method and application thereof.
Background
Antibiotics have been widely used in feed additives for poultry and aquaculture to prevent and intervene in bacterial infections, however, abuse of these antibiotics has caused serious environmental problems by inducing the spread of antibiotic resistance. Therefore, the relevant departments have recognized the seriousness of the problem and started to strictly forbid the use of antibiotics, but unfortunately, the existence of antibiotics is still found in many agricultural products and drinking water, and these antibiotics can be introduced into human bodies through food chains and cause many abnormal diseases, and therefore, the development of a material having superior performance and capable of rapidly detecting antibiotics in food or water safely and efficiently is urgently required.
Among various materials, metal-organic frameworks (MOFs) are attractive in the fields of material science and chemistry due to their wide application, and in particular, lanthanide-based MOFs (Ln-MOFs) have been explored as highly sensitive luminescent solid materials, which are monitored and analyzed by shifts and intensity changes of the luminescence spectrum, and exhibit various outstanding advantages such as high color purity, visibility to the naked eye, long luminescence lifetime, etc., compared to other similar materials. To date, few Ln-MOFs materials have detected some antibiotics in aqueous solutions, but the stability of the existing Ln-MOFs materials is still insufficient, and the selectivity and sensitivity for detecting specific antibiotics under complex detection environments are poor, so that the design and preparation of stable Ln-MOFs have long-term and profound significance for high-selectivity and high-sensitivity luminescence sensing of antibiotics in aqueous solutions.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for synthesizing a three-dimensional rare earth terbium compound, and the three-dimensional rare earth terbium compound synthesized based on the method has excellent water stability.
In order to achieve the above object, one aspect of the present invention provides a method for synthesizing a three-dimensional rare earth terbium compound, the method comprising: in the presence of an aqueous solvent, 5- (4' -carboxyphenoxy) isophthalic acid and a terbium source are mixed to obtain a mixed solution, the pH value of the mixed solution is adjusted to 5-7, and then hydrothermal reaction is carried out to obtain the three-dimensional rare earth terbium compound.
Preferably, the molar ratio of the 5- (4' -carboxyphenoxy) isophthalic acid to the terbium source is 1: 2-4.
Preferably, the conditions of the hydrothermal reaction at least satisfy: the temperature is 140 ℃ and 220 ℃, and the time is 48-96 h.
Preferably, the conditions of the hydrothermal reaction at least satisfy: the temperature is 160-200 ℃ and the time is 60-84 h.
Preferably, the method further comprises: and cooling the material obtained by the hydrothermal reaction to room temperature at the speed of 3-8 ℃/h.
Preferably, the terbium source is selected from at least one of terbium nitrate, terbium sulfate, terbium chloride and terbium acetate.
The invention provides a three-dimensional rare earth terbium compound synthesized by the method.
The third aspect of the invention provides an application of the three-dimensional rare earth terbium compound in detecting antibiotics. The antibiotic is at least one of tetracycline, thiamphenicol, secnidazole, tinidazole, metronidazole, ornidazole, nitrofurantoin, nitrofural, chloramphenicol, sulfamethoxazole and sulfonamide antibiotics; and further preferably a sulfonamide antibiotic.
Compared with the prior art, the terbium compound synthesized by the method provided by the invention has excellent water stability, and further research finds that the terbium compound has a three-dimensional pore channel structure, and an active site is arranged in a pore channel, so that the fluorescent probe antibiotic sulfadimidine has high sensitivity and high selectivity.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 shows [ Tb (L) (H) synthesized according to example 1 of the present invention2O)2]n·3H2Tb center geometric coordination diagram in O;
in FIG. 2，(a)[Tb(L)(H2O)2]n·3H2In O to L3-A linking mode; (b) a one-dimensional rod-like structure of the Tb chain; (c) a tunnel map of the three-dimensional network; (d) a topological map of compound 1;
figure 3 shows a graph of TGA of compound 1 synthesized according to example 1 of the present invention;
FIG. 4 (a) effect of fluorescence intensity of 5g/L Compound 1 dispersed in an aqueous solution containing 0.04mM antibiotic; (b) emission spectra for 5g/L of Compound 1 dispersed in SMZ water at different concentrations; (c) effect of different concentrations of SMZ on the fluorescence intensity of compound 1; (d) effect of other antibiotics on compound 1 fluorescent probe SMZ;
FIG. 5 shows the concentration of C in a low concentration antibiotic aqueous solution0/C-A plot of concentration versus antibiotic concentration;
figure 6 shows PXRD for compound 1 under different conditions.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the specific embodiments.
The invention provides a method for synthesizing a three-dimensional rare earth terbium compound, which comprises the following steps: in the presence of an aqueous solvent, 5- (4' -carboxyphenoxy) isophthalic acid and a terbium source are mixed to obtain a mixed solution, the pH value of the mixed solution is adjusted to 5-7, and then hydrothermal reaction is carried out to obtain the three-dimensional rare earth terbium compound.
The inventors of the present application found that by incorporating a flexible bridging ligand, 5- (4' -carboxyphenoxy) isophthalic acid (H)3L) is further assembled with Tb (III) ions by a hydrothermal synthesis method, and the synthesized metal complex has excellent water stability and shows high sensitivity and high selectivity to antibiotics, especially sulfonamide antibiotics.
According to the present invention, as the method for adjusting the pH value, a method well known to those skilled in the art can be selected, and in the present invention, the pH value is adjusted to be within a limited range by adding an alkaline solution to the mixed solution, specifically, the alkaline solution can be selected from sodium hydroxide solution, and more specifically, the concentration of the sodium hydroxide solution is 0.5 mol/L.
According to the present invention, the molar ratio of the 5- (4 '-carboxyphenoxy) isophthalic acid to the terbium source can be selected in a wide range, and preferably, the molar ratio of the 5- (4' -carboxyphenoxy) isophthalic acid to the terbium source is 1: 2-4.
According to the present invention, the conditions of the hydrothermal reaction can be selected within a wide range, and preferably, the conditions of the hydrothermal reaction at least satisfy: the temperature is 140 ℃ and 220 ℃, and the time is 48-96 h.
Further preferably, the temperature is 160-.
According to the invention, the method also comprises the step of cooling the material obtained by the hydrothermal reaction to room temperature at the speed of 3-8 ℃/h.
In the present invention, the terbium source is at least one selected from terbium nitrate, terbium sulfate, terbium chloride and terbium acetate, and terbium nitrate is more preferable.
The following specific examples are provided to illustrate the synthesis method of the three-dimensional rare earth terbium compound of the present invention.
With respect to the laboratory instruments and drugs used in the following examples, all reagents used for synthesis and detection were obtained from commercial sources and used without further extensive processing and purification.
The powder X-ray diffractometer adopts a Bruk advanced X-ray diffractometer, Cu-Ka radiation (lambda is 1.5418 mu), a scanning voltage of 50kV, a scanning speed of 6 DEG/min, a step size of 0.02 DEG and a power of 20 mA. Fourier transform infrared spectra (FT-IR) of the two MOFs as KBr discs were recorded using a Nicolet Impact750FTIR over the range of 400-4000 cm-1. Thermogravimetric analysis (TGA) was performed under a nitrogen atmosphere, heating from room temperature to 900 ℃ at a rate of 10 ℃/min.
The experimental apparatus and experimental drug are shown in tables 1 and 2 below, respectively.
TABLE 1 types of laboratory instruments and production sites
TABLE 2 purity of experimental drugs and their manufacturing plant
Example 1
H is to be3Mixture of L (0.15mmol, 0.045g), Tb (NO)3)3·6H2O (0.40mmol, 0.174g) was added to distilled water (10mL) and the solution was diluted with 0.5mol L-1The pH was adjusted to 6.0 with aqueous sodium hydroxide, the aqueous solution was placed in a stainless steel teflon-lined container (25mL), heated to 180 ℃ for 72 hours, and then cooled to room temperature at 5 ℃/h.
To obtain [ Tb (L) (H) with a yield of 63%2O)2]n·3H2O colorless bulk crystals.
IR (Infrared) (cm)-1)：3211(v)、1601(v)、1530(v)、1388(m)、1273(v)、1182(m)、1067(v)；976(v)、879(v)、789(m)、725(m)。
Example 2
H is to be3Mixture of L (0.15mmol, 0.045g), Tb (NO)3)3·6H2O (0.40mmol, 0.174g) was added to distilled water (10mL) and the solution was diluted with 0.5mol L-1The pH was adjusted to 4.0 with aqueous sodium hydroxide, the aqueous solution was placed in a stainless steel teflon-lined container (25mL), heated to 180 ℃ for 72 hours, and then cooled to room temperature at 5 ℃/h. No crystals were obtained.
Example 3
H is to be3Mixture of L (0.15mmol, 0.045g), Tb (NO)3)3·6H2O (0.40mmol, 0.174g) was added to distilled water (10mL) and the solution was diluted with 0.5mol L-1Adjusting pH to 8.0 with sodium hydroxide water solution, placing the water solution in polytetrafluoroethyleneEthylene-lined stainless steel vessel (25mL), heated to 180 ℃ for 72 hours, and then cooled to room temperature at a rate of 5 ℃/h. No crystals were obtained.
Based on the above specific examples, it can be seen that crystals could not be obtained when the pH of the mixed solution was adjusted to a value outside the range of 5-7, and that [ Tb (L) (H) (example 1) was obtained in a yield of 63% when the pH was adjusted to 6.02O)2]n·3H2O is colorless bulk crystal, and for convenience of subsequent description, the product is defined as compound 1.
Crystallographic data for Compound 1
Single crystal x-ray diffraction data for both MOFs were collected on a Bruker smart APEX diffractometer equipped with graphitic monochromatic MOF radiation (λ -0.71073 a). The structure is solved by direct method (SHLEXS-2014) using a method based on F2(Shelxl-2014) was refined by a full matrix least squares method. Some of the hydrogen atoms were generated geometrically and isotropically refined using a riding model. The crystallographic data for compound 1 are shown in table 3.
TABLE 3 crystallographic data for Compound 1
*R＝∑(Fo–Fc)/∑(Fo)，**wR2＝{∑[w(Fo 2–Fc 2)2]/∑(Fo 2)2}1/2.
Structural description of compound 1:
compound [ Tb (L) (H)2O)2]n·3H2O in an asymmetric unit, with a completely deprotonated L3-Chaining structures, 1 Tb3+Ions, two coordinated waters and three free water molecules. Each Tb3+Consists of two water molecules and fourThe oxygen atom of the bridged bidentate carboxylate and the oxygen atoms of the two chelated bidentate carboxylates with six Tb3+The coordination of atoms constitutes a coordination environment diagram as shown in FIG. 1. The observed binding pattern of the carboxylic acid ligand for compound 1 is shown in fig. 2a, with a dihedral angle between the two phenyl rings of 62.1 °. Tb in Compound 13+The ligand adopts a (k)1-k1-μ2)-(k1-k1-μ2)-((k1-k1-μ1)-μ5Coordinate mode to connect 5 Tb3+Ions. Adjacent Tb3+The ions are linked by two carboxylate-O atoms in two different ligands forming a one-dimensional chain, Tb.56 and Tb
(FIG. 2 b). The metal chain is composed of Tb3+Connected to form a three-dimensional frame (fig. 2 c). Mixing L with3-Ligand as 3 connecting node, binuclear Tb unit as 5 connecting node, compound 1 overall structure is a three-dimensional 5-connected bnn topological framework (figure 2 d). So far, only a few examples of bnn topologies have been observed in Ln-MoFs.
Performance testing of compound 1:
the thermal stability of complex 1 was analyzed using Thermogravimetry (TG). The sample was heated at a rate of 10 ℃/min under a nitrogen atmosphere at 30-800 ℃ (fig. 3). For compound 1, the TG curve shows two major weight loss processes. The first weight loss occurred between 30-162 c, corresponding to the loss of three crystalline water molecules from compound 1. Upon further heating of compound 1, the framework of compound 1 began to collapse at 250 ℃, corresponding to decomposition of the organic ligand in compound 1.
To study [ Tb (L) (H)2O)2]n·3H2O (1) fluorescence sensing properties for antibiotics in aqueous media. The inventors added an aqueous solution containing 0.04mM of each antibiotic to 5g/L of a well-dispersed 1 aqueous suspension. The experiment selects 12 common antibiotics including Tetracycline (TCY), Thiamphenicol (THI), Secnidazole (SIZ), Tinidazole (TDZ), Diniconazole (DTZ), Metronidazole (MDZ), Ornidazole (ODZ) and nitrofurantoin (TM) (nitrofurazone (MDZ))NFT), Nitrofurazone (NZF), Chloramphenicol (CAP), Sulfamethoxazole (SMT), and Sulfadimidine (SMZ). The experimental results show that the antibiotic Sulfadimidine (SMZ) exhibits a significant fluorescence quenching to the sensor (fig. 4 a).
To further investigate the sensitivity of compound 1 to Sulfadimidine (SMZ) sensing, the inventors performed a quantitative titration experiment (fig. 4 b). When the SMZ concentration increased from 0 to 600ppm, the emission intensity of the compound 1 solution dropped significantly, indicating that the fluorescence intensity is inversely proportional to the antibiotic concentration. The fluorescence quenching efficiency can be quantitatively expressed by the Stern-Volmer (SV) equation C0/C1 + KSV x [ C ]. The limit of detection of SMZ by compound 1 was calculated based on the KSV value according to the formula 3 σ/KSV, where σ is the standard deviation of three replicate luminescence measurements (fig. 5). Stern-Volmer (SV) analysis further showed that there was a near linear relationship between quenching efficiency and SMZ antibiotic usage, with both static and dynamic mechanisms present during quenching (FIG. 4 d). Monitoring at 545nm, from SMZ to LOD as low as 1.43 ppm. Furthermore, the inventors investigated the effect of controlling the range of 0.1 to 0.4mm on the quenching effect when the amount of addition was 200ppm, and as a result, it was shown that the quenching efficiency can be improved by a high concentration (FIG. 4 c).
According to table 4, the sensitivity of this work is far superior to most of the reported SMZ fluorescent probes. The excellent sensitivity to SMZ indicates that compound 1 has a high quenching efficiency for sulfonamides, but a poor quenching efficiency for other classes of antibiotics. In addition, the inventors further investigated the ability of sulfonamides to detect selection in the presence of other antibiotics (fig. 4 d). In a control experiment, a 0.04mm aqueous solution of each antibiotic was first added to the aqueous suspension of compound 1. The SMZ solution was then added drop by drop. In the presence of other excess antibiotics, the luminescence intensity of compound 1 slightly changed. When the SMZ is introduced into a mixed solution of the compound 1 and other antibiotics, the fluorescence intensity is remarkably quenched, and the experiment proves that the compound 1 has high quenching selectivity on the SMZ. After fluorescent probe PXRD of the sample and compound 1 almost perfectly matched (fig. 6), indicating that compound 1 has no structural change after fluorescent probe SMZ. Thus, the compound [ Tb (L) (H)2O)2]n·3H2O (1) can be used as a fluorescent probe antibiotic Sulfadimidine (SMZ) with high sensitivity and high selectivity.
TABLE 4 comparison of Compound 1 with other Tb (III) -MOFs for antibiotic fluorescent probes
The foregoing shows and describes the general principles, essential features, and inventive features of this invention. 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 (9)
1. A method for synthesizing a three-dimensional rare earth terbium compound is characterized by comprising the following steps: in the presence of an aqueous solvent, 5- (4' -carboxyphenoxy) isophthalic acid and a terbium source are mixed to obtain a mixed solution, the pH value of the mixed solution is adjusted to 5-7, and then hydrothermal reaction is carried out to obtain the three-dimensional rare earth terbium compound.
2. The method of claim 1, wherein the molar ratio of the 5- (4' -carboxyphenoxy) isophthalic acid to the terbium source is 1: 2-4.
3. The method according to claim 1, wherein the conditions of the hydrothermal reaction at least satisfy: the temperature is 140 ℃ and 220 ℃, and the time is 48-96 h.
4. The method according to claim 1, wherein the conditions of the hydrothermal reaction at least satisfy: the temperature is 160-200 ℃ and the time is 60-84 h.
5. The method of any of claims 1-4, wherein the method further comprises: and cooling the material obtained by the hydrothermal reaction to room temperature at the speed of 3-8 ℃/h.
6. The method of any one of claims 1-5, wherein said terbium source is selected from at least one of terbium nitrate, terbium sulfate, terbium chloride, terbium acetate.
7. A three-dimensional rare earth terbium compound synthesized by the method of any one of claims 1 to 6.
8. Use of the three-dimensional rare earth terbium compound of claim 1 or claim 7 for the detection of antibiotics.
9. The use according to claim 8, wherein the antibiotic is selected from at least one of tetracycline, thiamphenicol, secnidazole, tinidazole, metronidazole, ornidazole, nitrofurantoin, nitrofurazone, chloramphenicol, sulfamethoxazole and sulfonamide antibiotics; preference is given to sulphonamide antibiotics.
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