CN112940265B - Zirconium metal organic framework material based on eight-head carboxylic acid ligand, preparation method thereof and sensing detection application thereof - Google Patents
Zirconium metal organic framework material based on eight-head carboxylic acid ligand, preparation method thereof and sensing detection application thereof Download PDFInfo
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Abstract
Based on eight carboxylic acidsA zirconium metal organic framework material, a preparation method thereof and a sensing detection application belong to the technical field of crystalline materials. Chemical formula is [ Zr ]6O4(OH)8(H2O)4(TCTA)]，H8TCTA is the organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid. The synthesis of the metal-organic framework is carried out under a closed condition, and 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H)8TCTA) and zirconyl chloride (ZrOCl)2·8H2O) in a mixed solution of N, N-Dimethylformamide (DMF) and benzoic acid, and obtaining a crystal of the metal organic framework material through a solvothermal reaction; the metal organic framework material shows the detection capability on tumor markers.
Description
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, which is characterized by a zirconium metal-organic framework material, a preparation method and a sensing detection application study thereof.
Background
Metal-Organic Frameworks (MOFs) are constructed by inorganic Metal ions and Organic ligands through coordination bonds, are novel Organic-inorganic hybrid materials, and have the characteristics of large specific surface area, high porosity, adjustable porosity, easiness in functionalization and the like.
MOFs can be combined with various guest molecules by means of encapsulation, covalent bond connection of molecules with specific functions and the like, so that a novel composite material for specific purposes is designed. Due to the inherent biodegradability and biocompatibility of the MOFs, the MOFs have greater advantages compared with inorganic nano materials. Among the numerous MOFs, the Zr (IV) -MOFs have good chemical stability and the characteristics of low toxicity and high biocompatibility, and lay a foundation for potential biomedical applications.
Disclosure of Invention
The invention aims to provide a zirconium metal organic framework material based on eight-head carboxylic acid ligands, a preparation method and application thereof.
The invention relates to a zirconium metal-organic framework material based on eight-head carboxylic acid ligand, which is characterized in that the chemical molecular formula is [ Zr ]6O4(OH)8(H2O)4(TCTA)]，H8TCTA is an octameric carboxylic acid organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid.
From the angle of frame connection construction, the crystal structure of the metal-organic frame belongs to a tetragonal system, the space group is P4/mm, and the unit cell parameters are as follows:
α＝β＝γ＝90°。
in the metal-organic framework, the asymmetric unit of the crystal comprises 1 TCTA8-Ligand, 6 zirconium (Zr) atoms and 16O atoms. Each Zr is coordinated by a double-inverse quadrangular pyramid and two O atoms from different ligands, four mu3-O/OH atoms and two O atoms from the water in the reaction system; six Zr and eight μ3The oxygen atoms in the form of-O/OH, eight oxygen atoms from water and eight carboxyl oxygen atoms from different ligands are joined to form a secondary building block Zr of zirconium hexanuclear6O4(OH)8(H2O)4(COO)8I.e. Zr6O8And (4) clustering.
In the metal-organic framework, the Zr-O bond has a length of
Within the range; TCTA8-Four carbazoles in the ligand are vertical to the central benzene ring, and the included angle between two carboxyl groups on the carbazoles is 90 degrees; each TCTA8-Ligand and eight Zr6O8Cluster linked, each Zr6O8Cluster and TCTA equivalent from eight crystals8-And connecting the ligands to form a three-dimensional framework structure with one-dimensional diamond and square pore channels.
From a topological point of view, each pair of TCTAs8-The ligands can all be regarded as 8-linked nodes, while eight coordinated Zr6O8Clusters are regarded as 8-connected vertices, and these two types of building blocks are alternately connected to form a (8,8) -connected bcu network.
Eight-head carboxylic acid ligand characterized in thatThe organic ligand is 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H)8TCTA), structural formula shown below:
the ligand comprises four carbazole groups, each carbazole group is provided with two carboxyl groups, and the included angle is 90 degrees; four carbazoles in the ligand are respectively positioned at 2,3,5 and 6 positions of a benzene ring, and two carboxyl groups positioned at para positions are arranged on a middle benzene ring.
The novel synthesis method of the eight-head carboxylic acid ligand comprises the following two steps:
suzuki coupling: firstly, adding 3, 6-dibromo-9H-carbazole and p-methoxycarbonyl phenylboronic acid into ethylene glycol dimethyl ether and water, adding potassium carbonate and tetrakis (triphenylphosphine) palladium, heating to 60-100 ℃ to react under the protection of sealing and inert gas to obtain dimethyl 4,4' - (9H-carbazole-3, 6-diyl) dibenzoate;
nucleophilic substitution: dispersing dimethyl 4,4'- (9H-carbazole-3, 6-diyl) dibenzoate in tetrahydrofuran solution, adding sodium hydride, adding 2,3,5, 6-tetrafluoroterephthalonitrile, and reacting at room temperature to obtain octamethyl 4,4' - ((3, 6-terephthalonitrile-1, 2,4, 5-diyl) tetra (9H-carbazole-9, 3, 6-triyl)) octabenzoate;
deprotection: heating, refluxing and deprotecting octamethyl 4,4' ((3, 6-terephthalonitrile-1, 2,4, 5-tetra-yl) tetra (9H-carbazole-9, 3, 6-tri-yl)) octabenzoate and sodium hydroxide in a mixed solution of tetrahydrofuran/methanol/water (preferably in a volume ratio of 1:1:1) to obtain 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H, 3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid8TCTA)。
The synthesis method of the metal-organic framework material comprises the following steps:
organic ligand, 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid (H) under sealed condition8TCTA) and zirconyl chloride (ZrOCl)2·8H2O) in a mixed solution of N, N-Dimethylformamide (DMF) and benzoic acid, to obtain crystals of the metal-organic framework via a solvothermal reaction.
Further preferred is the organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl)Yl) -9H-carbazol-9-yl terephthalic acid (H)8TCTA) and zirconyl chloride in the molar ratio of 1 to 10, wherein each 0.05mmol of zirconyl chloride corresponds to 1 to 10mL of DMF and 0.1 to 2g of benzoic acid, the temperature of the thermal reaction is 100 to 150 ℃, and the reaction time is 8 to 72 hours.
Is used for preparing a fluorescent probe and detecting tumor markers miRNA-21 and MUC-1.
The organic ligand synthesized by the invention belongs to a novel eight-head carboxylic acid ligand. The metal-organic framework has good stability and fluorescence, so that the MOF has potential application in the aspect of simultaneously detecting double tumor markers in living cells.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of an eight-head carboxylic acid ligand for the synthesis of the metal-organic framework.
FIG. 2 is a diagram of a secondary building block of the metal-organic framework; (a) zr6O4(OH)8(H2O)4(COOH)8A metal cluster, (b) an organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid.
Fig. 3 is a schematic three-dimensional structure of the metal-organic framework.
FIG. 4 is a fluorescence quenching curve diagram of the metal-organic framework material for detecting tumor markers with different concentrations. (a) miRNA-21, (b) MUC-1.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
adding 3, 6-dibromo-9H-carbazole (20.0mmol), p-methoxycarbonylphenylboronic acid (48.0 mmol), ethylene glycol dimethyl ether (150mL) and water (30mL) into a 250mL round-bottom flask under the protection of nitrogen, adding a magneton, stirring, and then adding K2CO3(60.0mmol) and Pd (PPh)3)4(1.0mmol) and the reaction was stirred at 80 ℃ for 48 h. After completion of the reaction, the solvent of the reaction system was spin-dried, and the residue was dispersed in acetone (200mL), followed by suction filtration and washing with water (100 mL. times.4) and acetone (100 mL. times.2) in this orderAfter drying, off-white solid dimethyl 4,4' - (9H-carbazole-3, 6-diyl) dibenzoate was obtained (yield 81%).
Example 2:
the off-white solid obtained in the previous step was dispersed in a tetrahydrofuran solution (150mL), and sodium hydride (28.0mmol) was added thereto at room temperature, followed by stirring for 1 hour, followed by addition of 2,3,5, 6-tetrafluoroterephthalonitrile (6.0mmol) and reaction for 24 hours at room temperature. After the reaction, water was added to quench, followed by suction filtration and washing with water (100 mL. times.4) and acetone (100 mL. times.2) in this order to obtain octamethyl 4,4' ((3, 6-terephthalonitrile-1, 2,4, 5-tetrayl) tetrakis (9H-carbazole-9, 3, 6-triyl)) octabenzoate as a red solid (yield: 71%).
Example 3
Heating and refluxing the red octamethyl 4,4' - ((3, 6-terephthalonitrile-1, 2,4, 5-tetrayl) tetra (9H-carbazole-9, 3, 6-triyl)) octabenzoate and sodium hydroxide (50.0mmol) in a solution of tetrahydrofuran (80mL), methanol (80mL) and water (80mL), adjusting the pH to 3 by using a 2M hydrochloric acid solution after the reaction is finished, performing suction filtration and drying to obtain a yellow solid 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H-9-yl) as a yellow solid8TCTA), (yield 71%).1H NMR (DMSO-d6，400MHz)δ8.56(s，8H)，8.11(d，J＝8.4Hz，8H)，8.02(d，J＝ 8.4Hz，16H)，7.88(d，J＝8.4Hz，16H)，7.77(d，J＝8.4Hz，8H)。
Example 4
Weighing ligand H8TCTA (0.06mmoL) and ZrOCl2·8H2O (0.30mmoL) was put into a 20mL glass vial, and 12mL of DMF solution and 2g of benzoic acid were added, and then the vial was put into an ultrasonic device and subjected to ultrasonic treatment at room temperature for 5 minutes. After sealing, the vial was placed in a 110 ℃ oven for reaction for 36 hours. After the reaction is finished, the drying oven is closed, after the reaction is cooled to room temperature, the obtained product is filtered to collect solid particles, and DMF and H are sequentially used for the obtained product2Washed with O and EtOH (5 mL. times.3), and observed under a microscope to give golden color block-like crystals (Zr)6O4(OH)8(H2O)4(TCTA)), (yield-Rate: 61% based on H8TCTA ligand).
The test results of the products obtained in the above examples are the same, and specifically the following are given:
(1) determination of crystal structure:
the powder with proper size is selected, and data are collected by using a PANalytical X' Pert PRO high-resolution powder diffractometer at 273K. Data collection Using Cu-Ka monochromated by graphite monochromator
A target ray. Data absorption correction was done using SCALE3 absack software. The crystal structure was resolved by direct methods using the program SHELXTL-97. Firstly, determining all non-hydrogen atom coordinates by using a difference function method and a least square method, obtaining the hydrogen atom position by using a theoretical hydrogenation method, and then refining the crystal structure by using SHELXTL-97. The structure is shown in fig. 2 to 4. The crystallographic data are shown in table 1.
TABLE 1 crystallography data for metal organic framework materials
The eight head carboxylic acid ligand synthesis scheme of FIG. 1 shows: firstly, adding 3, 6-dibromo-9H-carbazole and p-methoxycarbonyl phenylboronic acid into ethylene glycol dimethyl ether and water, adding potassium carbonate and tetrakis (triphenylphosphine) palladium, sealing, vacuumizing, protecting by inert gas, and heating to react to obtain dimethyl 4,4' - (9H-carbazole-3, 6-diyl) dibenzoate; then, dispersing dimethyl 4,4'- (9H-carbazole-3, 6-diyl) dibenzoate in tetrahydrofuran solution, adding sodium hydride, then adding 2,3,5, 6-tetrafluoroterephthalonitrile, and reacting at room temperature to obtain octamethyl 4,4' - ((3, 6-terephthalonitrile-1, 2,4, 5-diyl) tetra (9H-carbazole-9, 3, 6-triyl)) octabenzoate; finally, octamethyl 4,4',4Heating reflux and deprotection of octabenzoate (3, 6-terephthalonitrile-1, 2,4, 5-tetra-yl) tetra (9H-carbazole-9, 3, 6-triyl)) and sodium hydroxide in tetrahydrofuran/methanol/water solution to obtain 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H, 3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid8TCTA)。
The block diagram of fig. 2 shows: the inorganic node contained in the frame structure is cubic Zr6O4(OH)8(H2O)4(COOH)8Metal cluster, organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid.
The block diagram of fig. 3 shows: a three-dimensional stacking diagram in the metal-organic framework.
(2) Detection of tumor markers
FIG. 4 is a fluorescence quenching curve of the material of the invention for detecting tumor markers with different concentrations, wherein the tumor markers are miRNA-21 and MUC-1, and it can be seen that the material can detect the tumor markers with different concentrations. FIG. 4 is a fluorescence quenching curve diagram of the material of the invention for detecting tumor marker miRNA-21(a-n, 0.2-80nM) at different concentrations in FIG. 4 (a) and MUC-1(a-j, 0-800nM) in FIG. 4 (b). The detection process was performed in phosphate buffer, with a concentration of 0.01M of the material.
Claims (7)
1. A metal-organic framework material of zirconium based on eight-head carboxylic acid ligands, characterized in that the chemical formula is [ Zr ]6O4(OH)8(H2O)4(TCTA)]，H8TCTA is octameric carboxylic acid organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid;
from the angle of frame connection construction, the crystal structure of the metal-organic frame belongs to a tetragonal system, the space group is P4/mmm, and the unit cell parameters are as follows:
α＝β＝γ＝90°；
in the metal-organic framework, the asymmetric unit of the crystal comprises 1 TCTA8-Ligand, 6Zirconium (Zr) atoms and 16O atoms; each Zr is coordinated by a double-inverse quadrangular pyramid and two O atoms from different ligands, four mu3-O/OH atoms and two O atoms from the water in the reaction system; six Zr and eight μ3The oxygen atoms in the form of-O/OH, eight oxygen atoms from water and eight carboxyl oxygen atoms from different ligands are joined to form a secondary building block Zr of zirconium hexanuclear6O4(OH)8(H2O)4(COO)8I.e. Zr6O8Clustering;
in the metal-organic framework, the Zr-O bond has a length of
Within the range; TCTA8-Four carbazoles in the ligand are vertical to the central benzene ring, and the included angle between two carboxyl groups on the carbazoles is 90 degrees; each TCTA8-Ligand and eight Zr6O8Cluster linked, each Zr6O8Cluster and TCTA equivalent from eight crystals8-Ligand connection is carried out to form a three-dimensional frame structure with one-dimensional diamond and square pore channels;
from a topological point of view, each pair of TCTAs8-The ligands can all be regarded as 8-linked nodes, while eight coordinated Zr6O8Clusters are regarded as 8-connected vertices, and these two types of building blocks are alternately connected to form an 8, 8-connected bcu network.
2. The metal-organic framework material of zirconium based on octa-carboxylic acid ligands according to claim 1, characterized in that octa-carboxylic acid organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid (H8TCTA), structural formula shown below:
the ligand comprises four carbazole groups, each carbazole group is provided with two carboxyl groups, and the included angle is 90 degrees; four carbazoles in the ligand are respectively positioned at 2,3,5 and 6 positions of a benzene ring, and two carboxyl groups positioned at para positions are arranged on a middle benzene ring.
3. The metal-organic framework material of zirconium based on octa-carboxylic acid ligands according to claim 1, characterized in that the synthesis method of octa-carboxylic acid organic ligands comprises the following two steps:
suzuki coupling: firstly, adding 3, 6-dibromo-9H-carbazole and p-methoxycarbonyl phenylboronic acid into ethylene glycol dimethyl ether and water, adding potassium carbonate and tetrakis (triphenylphosphine) palladium, heating to 60-100 ℃ to react under the protection of sealing and inert gas to obtain dimethyl 4,4' - (9H-carbazole-3, 6-diyl) dibenzoate;
nucleophilic substitution: dispersing dimethyl 4,4'- (9H-carbazole-3, 6-diyl) dibenzoate in tetrahydrofuran solution, adding sodium hydride, adding 2,3,5, 6-tetrafluoroterephthalonitrile, and reacting at room temperature to obtain octamethyl 4,4' - ((3, 6-terephthalonitrile-1, 2,4, 5-diyl) tetra (9H-carbazole-9, 3, 6-triyl)) octabenzoate;
deprotection: heating, refluxing and deprotecting octamethyl 4,4' ((3, 6-terephthalonitrile-1, 2,4, 5-tetra-yl) tetra (9H-carbazole-9, 3, 6-tri-yl)) octabenzoate and sodium hydroxide in a tetrahydrofuran/methanol/water mixed solution to obtain 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H-carbazole-9-yl) terephthalic acid8TCTA)；
4. The method for synthesizing an eight-head carboxylic acid ligand-based zirconium metal-organic framework material according to claim 1, comprising the steps of:
organic ligand, 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid H under sealed condition8TCTA and zirconyl chloride ZrOCl2·8H2O in N, N-dimethylThe crystals of the metal-organic framework are obtained via a solvothermal reaction in a mixed solution of formamide (DMF) and benzoic acid.
5. The process as claimed in claim 4, wherein the organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid H8The molar ratio of TCTA to zirconyl chloride is 1 (1-10), each 0.05mmol of zirconyl chloride corresponds to 1-10 mL of DMF and 0.1-2 g of benzoic acid, the temperature of the thermal reaction is 100-150 ℃, and the reaction time is 8-72 hours.
6. Use of the zirconium metal-organic framework material based on eight-head carboxylic acid ligands according to claim 1 for the preparation of fluorescent probes.
7. Use according to claim 6 for the detection of the tumour markers miRNA-21 and MUC-1.
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