CN115044049A - Metal organic cage based on tetranuclear In cluster and preparation method and application thereof - Google Patents
Metal organic cage based on tetranuclear In cluster and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesis and application of metal organic cages, and discloses a metal organic cage based on a tetranuclear In cluster, a preparation method and application thereof, aiming at the problems of poor stability of the traditional metal organic cage and caused by the poor stability. The metal organic cage is obtained by dissolving indium nitrate and 1,3, 5-tri (4-carboxyphenyl) benzene in a mixed solvent consisting of N, N-dimethylacetamide and water, and carrying out constant-temperature standing reaction. Regulation and control synthesized tetranuclear In cluster metal organic cage { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The cage structure with double interpenetration is a novel and stable material. Can be used as a fluorescent sensor for sensitively identifying antibiotics, has high sensitivity and low detection limit when identifying the antibiotics, and is characterized by a special cageThe window can selectively identify Nitrofurantoin (NFT), and has important practical significance.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of metal organic cages, and particularly relates to a tetranuclear In cluster-based metal organic cage and a preparation method and application thereof.
Background
In recent years, residual antibiotics in the environment have had a serious impact on human health and the ecosystem. Therefore, rapid and accurate detection of antibiotics is imminent. The fluorescence sensing technology developed based on the metal organic cage is easy to operate, low in cost, simple and cheap, and can detect residual antibiotics in the environment.
Metal Organic Cages (MOCs) are coordination compounds composed of metal ions or multidentate organic ligands linked together, and have the characteristics of both an organic linker and metal ions or metal clusters. Due to the diversity of coordination modes of metal ions, the ease of modification of organic ligands, and the adjustability of pore size and pore shape, they have received increasing attention as they exhibit excellent properties in terms of adsorption, separation, catalysis, luminescence, sensing, and the like. However, MOCs materials have poor stability, which limits their use in various fields.
Therefore, the MOCs material which is novel and stable in structure and has excellent performance is regulated and synthesized, and the application of the MOCs material in the field of fluorescence sensing antibiotics is particularly important to develop.
Disclosure of Invention
Aiming at the problems of poor stability of the traditional metal organic cage and caused by the poor stability, the invention provides a metal organic cage based on a tetranuclear In cluster and a preparation method and application thereof. The metal organic cage is formed by high-valence metal indium (III) and a highly symmetrical polycarboxylic acid ligand 1,3, 5-tri (4-carboxyphenyl) benzene (H) 3 BTB) with various pore shapes and pore structures, can be applied to the field of fluorescence sensing antibiotics.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a metal organic cage based on a tetranuclear In cluster, which is characterized In thatMolecular formula C 216 H 132 In 12 O 60 Structural formula { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Wherein the ligand is: 1,3, 5-tris (4-carboxyphenyl) benzene (H) 3 BTB) with cell parameters of
α＝β＝γ＝90°，
Z is 2, and the space group is Im-3.
Further, the structure of the metal organic cage is a double-penetration cage-nested structure.
The invention also provides a preparation method of the metal organic cage based on the tetranuclear In cluster, which comprises the following steps: indium nitrate In (NO) 3 ) 3 And 1,3, 5-tris (4-carboxyphenyl) benzene (H) 3 BTB) is dissolved In a mixed solvent consisting of N, N-Dimethylacetamide (DMA) and water, a constant-temperature standing reaction is carried out, and after the reaction is finished, the reaction is cooled to room temperature to obtain white blocky crystals, namely the tetranuclear In cluster-based metal organic cage.
Further, the indium nitrate is In (NO) 3 ) 3 ·6H 2 O。
Further, the volume ratio of the N, N-dimethylacetamide to the water in the mixed solvent is 4: 1-4.5: 1.5.
further, said In (NO) 3 ) 3 ·6H 2 The molar ratio of O to 1,3, 5-tris (4-carboxyphenyl) benzene is 1: 2-1: 2.5.
further, the amount of the mixed solvent was 5 mL.
Further, the temperature of the constant-temperature standing reaction is 100-120 ℃, and the time is 2-3 days.
The invention also provides application of the metal organic cage based on the tetranuclear In cluster, which can be used as a fluorescent sensor for sensitively identifying antibiotics, In particular to antibiotics such as nitrofurantoin NFT, nitrofurazone NFZ and thiamphenicol THI.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a one-pot hydrothermal method to synthesize a metal organic cage { [ In ] with novel structure and stable cage shape 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The synthetic method is simple, and the synthesized metal organic cage can be used as a sensor for sensitively identifying antibiotics and has important practical significance.
2. The ligand selected by the metal organic cage is 1,3, 5-tri (4-carboxyphenyl) benzene, the ligand has larger molecular size and can construct a large porous framework, and the ligand is coordinated with specific metal ions In to synthesize the metal organic framework material with higher thermal stability and water stability.
3. Sensitivity (Ksv), limit of detection (LOD) and selectivity are important indicators for measuring fluorescent sensing materials. When the metal organic cage is used as a fluorescent sensor for identifying antibiotics, the metal organic cage has high sensitivity (K) sv ) Selectivity and low detection limit. K to Nitrofurantoin (NFT) sv Is 1.47X 10 5 M -1 The detection limit is 12.1 ppm; k to Nitrofurazone (NFZ) sv Is 1.43X 10 5 M -1 The detection limit is 13.8 ppm; k of p-Thiamphenicol (THI) sv Is 4.52 multiplied by 10 3 M -1 The detection limit was 348.6 ppm.
Drawings
FIG. 1 is an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n A diagram of non-basic building blocks.
FIG. 2 is an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The structure diagram of the cage is inserted into each other; in the figure, a is an octahedral inner cage; b is a cubo-octahedral outer cage; c is a three-dimensional structure of the double-layer penetration cage.
FIG. 3 is an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Is shown in the figure.
FIG. 4 isExample { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Fluorescence pattern of Nitrofurantoin (NFT) was sensed.
FIG. 5 shows an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Fluorescence image of Nitrofurazone (NFZ) was sensed.
FIG. 6 shows an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n And (3) sensing a fluorescence map of Thiamphenicol (THI).
FIG. 7 shows an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n A streen-volmer map of Nitrofurantoin (NFT) is sensed.
FIG. 8 is a drawing of an example { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n A steiner-volmer map of Nitrofurazone (NFZ) is sensed.
FIG. 9 is a schematic view of an example { [ In ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n A Steen-Walmer map of Thiamphenicol (THI) is sensed.
FIG. 10 shows an example { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Selectively identify Nitrofurantoin (NFT) patterns.
Detailed Description
The following examples are carried out on the premise of the technical solutions of the present invention, and detailed embodiments and specific operation procedures are given, but the protection scope of the present invention is not limited, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
Preparation of a metal organic cage based on a tetranuclear In cluster:
in (NO) 3 ) 3 ·6H 2 O (0.012g,0.04mmol), and 1,3, 5-tris (4-carboxyphenyl) benzene (0.044g,0.1mmol) were dissolved in 5mL of a solution of N, N-dimethylacetamide and water in a volume ratio of 4.5:1.5 in a mixed solvent, standing at a constant temperature of 120 DEG CAnd (3) placing the mixture for reaction for 48 hours, and cooling the mixture to room temperature after the reaction is finished to obtain white blocky crystals, namely the tetranuclear In cluster-based metal organic cage.
Example 2
Preparation of a metal organic cage based on a tetranuclear In cluster:
in (NO) 3 ) 3 ·6H 2 O (0.015g,0.05mmol) and 1,3, 5-tris (4-carboxyphenyl) benzene (0.055g,0.125mmol) were dissolved in 5mL of a solution of N, N-dimethylacetamide and water in a volume ratio of 4:1 at a constant temperature of 110 ℃ for 60 hours, and cooling to room temperature after the reaction is finished to obtain white blocky crystals, namely the tetranuclear In cluster-based metal organic cage.
Example 3
Preparation of a tetranuclear In cluster-based metal organic cage:
in (NO) 3 ) 3 ·6H 2 O (0.015g,0.05mmol) and 1,3, 5-tris (4-carboxyphenyl) benzene (0.044g,0.1mmol) were dissolved in 5mL of a solution of N, N-dimethylacetamide and water in a volume ratio of 4:1 for 72 hours at a constant temperature, and cooling to room temperature after the reaction is finished to obtain white blocky crystals, namely the tetranuclear In cluster-based metal organic cage.
The obtained metal organic cage has a molecular formula of C 216 H 132 In 12 O 60 The structural formula is { [ In ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Wherein the ligand is: 1,3, 5-tris (4-carboxyphenyl) benzene with unit cell parameters of
α＝β＝γ＝90°，Z＝2，
The space group is Im-3.
(1) Structural analysis of crystals (metal organic cages)
FIG. 1 shows the present embodiment{[In 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n A diagram of non-basic building blocks. As shown In FIG. 1, the asymmetric cell unit of the crystal is composed of two independent In 3+ Ions (In1 and In2), 2/3H 3 BTB ligand and two H 2 O molecular composition; BTB 3- All carboxyl groups of the ligand are deprotonated, BTB 3- Ligand-bridged 6 In 3+ Ion, BTB 3- The carboxyl groups on the ligand all adopt a coordination mode, and all adopt mu 2 -η 1 :η 1 The coordination system of (1). The coordination numbers of both In1 and In2 were 6, and that of In1 and 4 different BTBs 3- The 4 oxygen atoms on the ligand and the two oxygens in the two waters (O3 and O1) coordinate to form an octahedral structure. The 6 oxygens coordinated to In2 come from 5 different BTBs respectively 3- Oxygen on the ligand and one oxygen from a water molecule. In1 and In2 coordinate with oxygen to form a novel tetranuclear cluster [ In ] 4 O 4 (COO) 8 ]。
FIG. 2 shows the present embodiment { [ In { ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The structure of the inter-penetrating cage. 6 four-core clusters [ In ] as shown In FIG. 2(a) 4 O 4 COO) 8 ] 4 Are connected by 8 BTB ligands to form an octahedral cage { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The inner cage of (a); the outer cage is a cubic octahedral cage consisting of 12 In 4 O 4 (COO) 8 ]Clusters and 8 ligands (fig. 2(b)), which in turn propagate to form a double-interspersed cage-cage structure (fig. 2 (c)).
To describe this three-dimensional framework more briefly, its topological structure diagram is shown in fig. 3, which is found to be described as a (3, 8) connected network topology, BTB 3- The ligands are considered to be three-linked-node, tetranuclear [ In ] 4 O 2 (COO) 8 ]A cluster is considered to be an eight-connection node. It has a new topological sign 4 3 } 8 {4 8 .6 4 .8 12 .10 4 } 3 . The analysis shows that the invention synthesizes the metal organic cage with novel and stable structure.
Example 4
1. The invention relates to a metal organic cage { [ In ] 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Application of fluorescent sensor for sensitively recognizing antibiotics
Selecting the most commonly used 3 antibiotics (nitrofurantoin (NFT), Nitrofurazone (NFZ) and Thiamphenicol (THI)), and gradually adding DMF solution (0.001-0.01 μ M) of the antibiotics into the prepared { [ In ] solution at room temperature 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n (0.5mg mL -1 ) Titration experiments were performed in suspension. Record the { [ In ] before and after each titration 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Fluorescence intensity of the suspension.
From the results of FIGS. 4-6, it was found that { [ In ] after addition of 3 antibiotics 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The fluorescence intensity of the suspension drops immediately (recording time is less than 2 seconds), and the quenching effects of 3 antibiotics, namely Nitrofurantoin (NFT), Nitrofurazone (NFZ) and Thiamphenicol (THI) are obvious. Interestingly, it was also found that Nitrofurantoin (NFT) was the most quenching when 5. mu.L of antibiotic was added. Showing that the metal organic cage of the invention { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Can be used as a fluorescent sensor for sensitively identifying antibiotics.
2. Performance evaluation of fluorescent sensor for identifying antibiotics:
(1) sensitivity (K) sv ) Is an important index for measuring the detection of the fluorescence sensing material.
The 3 selected antibiotics for the fluorescence quenching effect of this example were quantitatively explained by fitting experimental data with the Stern-Volmer (SV) equation (I) 0 /I)＝1+K sv [M]In which I 0 And I is { [ In ] before adding antibiotics 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Suspension and after addition of antibiotics { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The fluorescence intensity of the suspension at the maximum emission wavelength; [ M ] A]Is resistant toMolar concentration (M) of biotin molecules; k sv Is SV constant (M) -1 ) The sensitivity of fluorescence quenching is represented.
As can be seen from FIGS. 7-9, { [ In ] at a low concentration range (0.001. mu.M to 0.01. mu.M) 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n The quenching efficiency of the suspension for 3 antibiotics was quantified and was linear with antibiotic concentration. Wherein K of Nitrofurantoin (NFT) is detected sv Is 1.47X 10 5 M -1 B, carrying out the following steps of; k to Nitrofurazone (NFZ) sv Is 1.43X 10 5 M -1 (ii) a K of p-Thiamphenicol (THI) sv Is 4.52 multiplied by 10 3 M -1 . The analysis proves that the metal organic cage based on the tetranuclear In cluster is a sensitive antibiotic fluorescence sensor.
(2) The limit of detection (LOD) is also considered to be a key feature in evaluating the applicability of fluorescent sensors in practical applications.
The detection limit is defined by LOD as 3SD/K sv (SD is the standard deviation of the blank sample, K sv The slope of the calibration curve).
The detection limit of Nitrofurantoin (NFT) is 12.1 ppm; the detection limit of Nitrofurazone (NFZ) is 13.8 ppm; the detection limit for Thiamphenicol (THI) was 348.6 ppm. The metallic organic cage based on the tetranuclear In cluster can be well used for detecting antibiotics.
(3) This example also investigated the selectivity of the tetranuclear In cluster based metal organic cage for the detection of antibiotics.
The NFT was added to both NFZ and THI solutions by titration. From the results of FIG. 10, it can be seen that: the fluorescence intensity of the metallic organic cage based on the tetranuclear In cluster decreases with increasing NFT until quenching, indicating negligible interference of NFZ and THI, demonstrating that the metallic organic cage based on the tetranuclear In cluster is selective for nitrofurantoin NFT. The invention is proved that the metal organic cage based on the tetranuclear In cluster has good selectivity when detecting antibiotics.
Results of comprehensive sensitivity, detection limit and selectivity show that the metal organic cage based on the tetranuclear In cluster is an efficient antibiotic fluorescence sensor.
Claims (9)
1. A metal organic cage based on four-core In cluster is characterized In that: the molecular formula of the metal organic cage is C 216 H 132 In 12 O 60 Structural formula { [ In { [ 6 (O) 3 (BTB) 4 ]·(H 2 O) 3 } n Wherein the ligand is: 1,3, 5-tris (4-carboxyphenyl) benzene with unit cell parameters of
α＝β＝γ＝90°，
Z is 2, and the space group is Im-3.
2. The tetranuclear In cluster-based metal organic cage of claim 1, wherein: the structure of the metal organic cage is a double-layer penetration cage sleeving cage structure.
3. A method for preparing a tetranuclear In cluster based metal organic cage according to any one of claims 1 or 2, characterized In that: dissolving indium nitrate and 1,3, 5-tri (4-carboxyphenyl) benzene into a mixed solvent consisting of N, N-dimethylacetamide and water, standing at constant temperature for reaction, and cooling to room temperature after the reaction is finished to obtain white blocky crystals, namely the tetranuclear In cluster-based metal organic cage.
4. The method for preparing the tetranuclear In cluster-based metal organic cage according to claim 3, wherein the indium nitrate is In (NO) 3 ) 3 ·6H 2 O。
5. The method for preparing a tetranuclear In cluster-based metal organic cage according to claim 3, wherein the method comprises the following steps: the volume ratio of the N, N-dimethylacetamide to the water in the mixed solvent is 4: 1-4.5: 1.5.
6. The method for preparing a metallic organic cage based on a tetranuclear In cluster according to claim 4, wherein the method comprises the following steps: in (NO) In 3 ) 3 ·6H 2 The molar ratio of O to 1,3, 5-tri (4-carboxyphenyl) benzene is 1:2 to 1: 2.5.
7. The method for preparing a tetranuclear In cluster-based metal organic cage according to claim 3, wherein the method comprises the following steps: the dosage of the mixed solvent is 5 mL.
8. The method for preparing a tetranuclear In cluster-based metal organic cage according to claim 3, wherein the method comprises the following steps: the temperature of the constant-temperature standing reaction is 100-120 ℃, and the time is 2-3 days.
9. Use of the tetranuclear In cluster based metal organic cage of claim 1, wherein: can be used as a fluorescent sensor for sensitively identifying antibiotics.
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