Three-dimensional gallium metal-organic frameworks with fluorescence detection function and methods of synthesis and use

Abstract

The present application belongs to the field of chemistry, and particularly relates to a three-dimensional gallium metal organic framework with fluorescence detection function and a synthesis and application method. A gallium metal organic framework compound with fluorescence recognition function has a chemical formula of {[(CH3)2(NH2)Ga(PPTA)]·0.5DMF} n . A preparation method of the gallium metal organic framework chemical substance is as follows: gallium nitrate, 4,4',4'',4'''-(4,4'-(1,4-phenylene)bis(pyridine-6,4,2-triyl))tetraanisic acid (PPTA) and oleic acid are added into a mixed solution of ethanol and N,N-dimethylformamide (DMF), stirred uniformly, and heated at constant temperature to obtain red block crystals, which are the gallium metal organic framework compound with fluorescence recognition function. The gallium metal organic framework compound is applied to detect aminoglycoside antibiotic amikacin. The fluorescence property is derived from ligand luminescence. The gallium metal organic framework material constructed shows different fluorescence properties from the ligand, can have specific fluorescence recognition function for amikacin, and has high sensitivity, anti-interference and recyclability.

Description

Technical Field

[0001] This invention belongs to the field of chemistry, specifically, it relates to a three-dimensional gallium metal-organic framework with fluorescence detection function and its synthesis and application methods. Background Technology

[0002] Amikacin, an aminoglycoside antibiotic, exhibits a lower bacterial resistance rate than most drugs with similar efficacy. Currently, amikacin remains one of the most effective antibiotics for treating major Gram-negative bacteria. However, due to its strong nephrotoxicity and ototoxicity, there is a need to develop accurate and rapid assay methods to measure its concentration in humans or animals. In fact, the lack of a strong ultraviolet-absorbing chromophore, polarity, and non-volatility of aminoglycoside antibiotics like amikacin make direct determination using traditional liquid chromatography, ultraviolet detection, and gas chromatography methods difficult. Therefore, it is essential to prepare a material with specific recognition capabilities for the antibiotic amikacin.

[0003] Among current detection methods, fluorescence methods are widely studied due to their advantages such as short reaction time, simple operation, and high sensitivity.

[0004] In recent years, metal-organic frameworks (MOFs) have attracted widespread attention due to their unique characteristics, such as high porosity, large specific surface area, tunable multifunctional groups, adjustable pore size, and multi-center active sites. Therefore, MOF materials are widely used in various fields, including gas adsorption and separation, thermocatalysis, electrocatalysis, photolysis, drug delivery, and chemical sensing. Particularly in chemical sensing, MOF materials serve as luminescent probes with advantages such as good recyclability, high sensitivity, and ease of operation. To date, MOF materials have been used for the detection of various substances, including cations and anions, pesticides, antibiotics, biomarkers, and explosives. However, no luminescent probe based on MOF materials has yet been developed for the detection of amikacin.

[0005] As a unique gallium metal-organic framework material, its fluorescence properties originate from ligand luminescence. By coordinating gallium with carboxyl groups in the ligand, the constructed gallium metal-organic framework material exhibits fluorescence properties different from those of the ligand. It can have specific fluorescence recognition function for amikacin and has high sensitivity, anti-interference and cyclicity. Summary of the Invention

[0006] This invention discloses a three-dimensional gallium metal-organic framework with fluorescence detection function, as well as its synthesis and application methods.

[0007] The three-dimensional gallium metal-organic framework material with fluorescence detection function of the present invention has the chemical formula {[(CH3)2(NH2)Ga(PPTA)]·0.5DMF} nIts three-dimensional structure diagram is

[0008]

[0009] The aforementioned three-dimensional gallium metal-organic framework material with fluorescence detection function is generated by a solvothermal reaction of 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid (H4PPTA) and gallium nitrate, as shown in the reaction flowchart. Figure 1 As shown.

[0010] This gallium metal-organic framework material with fluorescence recognition function is a two-interpenetrating three-dimensional structure compound based on gallium-carboxylic acid chain building units, containing large one-dimensional channels.

[0011] The method for synthesizing the gallium metal-organic framework material with fluorescence recognition function includes the following steps:

[0012] (1) Gallium nitrate monohydrate, 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid, and oleic acid were added to a mixture of ethanol and N,N-dimethylformamide and stirred until homogeneous. The molar ratio of gallium nitrate monohydrate, 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid, oleic acid, ethanol and N,N-dimethylformamide was (1.8-2.2):(0.9-1.1):(250-300):(1100-1400):(1600-1900);

[0013] (2) Place the mixture obtained in step (1) into a round-bottomed glass bottle with an aluminum cap, seal it and place it in a reaction oven, heat it to 80-110℃ for 48-96 hours to obtain a red blocky crystal product, which is a gallium metal-organic framework material with fluorescence recognition function.

[0014] The method for applying the gallium metal-organic framework material with fluorescence recognition function is used to detect the aminoglycoside antibiotic amikacin.

[0015] The detection of amikacin mainly involves the following steps:

[0016] (1) The gallium metal-organic framework material was ultrasonically dispersed in an aqueous solution, and its fluorescence was tested. The recognition effect of the gallium metal-organic framework material with specific fluorescence recognition function on amikacin was obtained based on the change in fluorescence intensity.

[0017] (2) Add different amounts of amikacin aqueous solution to the aqueous solution of gallium metal-organic framework material with fluorescence recognition function using a pipette and test its fluorescence intensity; fit the obtained data to obtain the quantitative relationship and detection limit of the gallium metal-organic framework material with fluorescence recognition function for the detection of amikacin in aqueous solution.

[0018] (3) Furthermore, amikacin can be identified in aqueous solutions containing some components of blood, such as NaCl, MgCl2, CaCl2, KCl, KHCO3, Zn(NO3)2, creatinine, or glucose.

[0019] Alternatively, amikacin can be identified in aqueous solutions containing other similar antibiotics such as tobramycin, thiamphenicol, norfloxacin, amoxicillin, or lonidazole.

[0020] Alternatively, the procedure in step (2) can be performed to detect amikacin in a diluted human serum solution to obtain the quantitative relationship and detection limit of the gallium metal-organic framework with fluorescence recognition function for the detection of amikacin in the diluted human serum solution.

[0021] This invention has the following advantages:

[0022] 1. Gallium metal-organic framework materials with fluorescence recognition function have a simple and convenient preparation process and mild and environmentally friendly reaction conditions;

[0023] 2. The product has a large yield, high purity, and excellent acid and alkali stability;

[0024] 3. Gallium metal-organic framework materials with specific fluorescence recognition function can quickly and conveniently detect the content of amikacin in aqueous solutions or diluted human serum, with low detection limit, high sensitivity and recyclability. Attached Figure Description

[0025] Figure 1 This is a synthesis reaction route diagram for the three-dimensional gallium metal-organic framework material with fluorescence detection function of the present invention.

[0026] Figure 2 This invention discloses a three-dimensional structure of a gallium metal-organic framework material with fluorescence recognition function.

[0027] Figure 3 a represents the atomic coordination bond length of a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention. Figure 3 b represents a van der Waals stacked three-dimensional structure of a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention.

[0028] Figure 4This invention discloses a single-crystal data simulation of a gallium metal-organic framework material with fluorescence recognition function, and X-ray powder diffraction patterns of the sample, ligand, and metal salt.

[0029] Figure 5 Figure a shows the fluorescence response of a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention to different concentrations of amikacin in aqueous solution. Figure 5 b is a fitting curve of amikacin in aqueous solution for a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention.

[0030] Figure 6 Figure a shows the fluorescence response of a gallium metal-organic framework material with fluorescence recognition function disclosed in Embodiment 1 of this invention to different concentrations of amikacin in diluted human serum. Figure 6 b is a fitting curve of amikacin in diluted human serum solution by a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention.

[0031] Figure 7 This is a fluorescence response diagram of a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention to amikacin in an aqueous solution containing some components of blood.

[0032] Figure 8 This is a fluorescence response diagram of a gallium metal-organic framework material with fluorescence recognition function disclosed in this invention to amikacin in an aqueous solution containing some interfering antibiotics. Detailed implementation method:

[0033] The specific embodiments of the present invention are described in detail below.

[0034] Example 1

[0035] A gallium metal-organic framework material with fluorescence recognition function, its chemical formula is {[(CH3)2(NH4+)2} 2) Ga(PPTA)]·0.5DMF} n Its three-dimensional structure is as follows Figure 2 .

[0036] H4PPTA is 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid, and its structural formula is as follows:

[0037]

[0038] The aforementioned three-dimensional gallium metal-organic framework material with fluorescence detection function is generated by a solvothermal reaction of 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid (H4PPTA) and gallium nitrate, as shown in the reaction flowchart. Figure 1 As shown.

[0039] Furthermore, a gallium metal-organic framework material with fluorescence recognition function is a gallium metal-organic framework compound with fluorescence recognition function, which is a two-fold interpenetrating three-dimensional structure compound based on gallium-carboxylic acid chain building units and contains large one-dimensional channels.

[0040] Structural Description: A gallium metal-organic framework material with fluorescence recognition function, its chemical formula is {[(CH3)2(NH2)Ga(PPTA)]·0.5DMF} n H4PPTA is a 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridine-6,4,2-triyl))tetrabenzoic acid ligand.

[0041] Single-crystal structure analysis of the metal-organic framework (MOF) material with specific fluorescent recognition function revealed that the crystal belongs to the monoclinic C2 / c system. Each independent unit contains only one trivalent gallium atom. In the smallest independent unit, the four-coordinated gallium atom forms a tetrahedral structure with carboxyl oxygen atoms, each belonging to one of four ligand molecules. The bond lengths of each gallium-oxygen bond are approximately the same, and each oxygen atom coordinated with gallium belongs to a hydroxyl oxygen atom within the ligand. Therefore, it can be determined that this MOF material with specific fluorescent recognition function is an anionic framework, where the countercation originates from the dimethylamine cation formed by the decomposition of N,N-dimethylformamide in solution. Each gallium atom is connected to four ligand molecules, and each ligand molecule is in turn coordinated with four gallium atoms, ultimately forming a unique two-fold interpenetrating three-dimensional MOF. Simultaneously, this MOF material with specific fluorescent recognition function exhibits… The crystal has square one-dimensional channels. After removing free solvent molecules from the channels, the porosity of the crystal was calculated to be 70.2%.

[0042] As attached Figure 4 As shown, the X-ray powder diffraction pattern of the sample and the single-crystal simulation pattern are in good agreement, indicating that the synthesized material has high phase purity.

[0043] A method for preparing a gallium metal-organic framework material with fluorescence recognition function includes the following steps:

[0044] (1) Gallium nitrate monohydrate, 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridine-6,4,2-triyl))tetrabenzoic acid, and oleic acid were added to a mixture of ethanol and N,N-dimethylformamide and stirred until homogeneous. The molar ratio of gallium nitrate monohydrate, 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridine-6,4,2-triyl))tetrabenzoic acid, oleic acid, ethanol and N,N-dimethylformamide was (5):(1):(270):(1200):(1850).

[0045] (2) Place the mixture obtained in step (1) into a round-bottomed glass bottle with an aluminum cap, seal it and place it in a reaction oven, heat it to 100°C and continue for 72 hours to obtain a red blocky crystal product, which is a gallium metal-organic framework material with fluorescence recognition function.

[0046] An application of a gallium metal-organic framework material with specific fluorescence recognition for the detection of amikacin.

[0047] The structural formula for Amika Star is as follows:

[0048]

[0049] Detection of amikacin in aqueous solution:

[0050] First, a small amount of gallium metal-organic framework compound with fluorescence recognition function was weighed and dispersed in a certain amount of distilled water. Its emission spectrum was measured, and its maximum emission wavelength was found to be 380 nm. Then, a small amount of amikacin solution of a fixed concentration was added to the aqueous solution of gallium metal-organic framework compound, and its emission spectrum was measured.

[0051] By varying the concentration of amikacin added, the amount was gradually increased using a pipette, and the fluorescence intensity at 380 nm was measured. It was found that the fluorescence intensity gradually decreased with increasing amikacin concentration (see attached figure). Figure 5 As shown in Figure a), the following relationship was calculated: I0 / I = 0.9937 + 0.129C. The relationship between I0 and I conforms to the Stern-Volmer (SV) equation (where Ksv is the quenching constant, C is the analyte concentration, I is the fluorescence intensity after adding amikacin solution, and I0 is the initial fluorescence intensity without adding amikacin solution). A good linear relationship is maintained in the low concentration range (0-7.3 μM), with a correlation coefficient R0. 2 It is 0.9989 (as shown in the attached document) Figure 5 (as shown in b).

[0052] Detection of amikacin in diluted human serum:

[0053] First, human serum was diluted 1000 times. A small amount of gallium metal-organic framework compound with fluorescent recognition function was weighed and dispersed in the diluted human serum solution, and its emission spectrum was measured. Then, a small amount of amikacin solution at a fixed concentration was added to the aqueous solution of the gallium metal-organic framework compound, and its emission spectrum was measured.

[0054] By varying the concentration of amikacin added and gradually increasing it using a pipette, the fluorescence intensity at 380 nm was measured. The results showed that the fluorescence enhancement was similar to the phenomenon observed when amikacin was identified in aqueous solution (see attached image). Figure 6 (As shown in a). The following relationship exists: I0 / I = 0.9944 + 0.111C (where Ksv is the quenching constant, C is the analyte concentration, I is the fluorescence intensity after adding amikacin solution, and I0 is the initial fluorescence intensity without adding amikacin solution). A good linear relationship is maintained in the low concentration range (0-6.8 μM), with a correlation coefficient R0. 2 It is 0.9994 (as shown in the attached document). Figure 6 (as shown in b)

[0055] Blood components (NaCl, MgCl2, CaCl2, KCl, KHCO3, Zn(NO3)2, creatinine, and glucose) at concentrations equal to the quenching concentration of amikacin were added to gallium metal-organic framework compounds containing small amounts of fluorescently recognized components, and their emission spectra were measured. Then, an equal amount of amikacin was added to an aqueous solution of the gallium metal-organic framework compound, and its emission spectrum was measured (see attached figure). Figure 7 (As shown).

[0056] Antibiotics (tobramycin, thiamphenicol, norfloxacin, amoxicillin, and lonidazole) with quenching concentrations equal to that of amikacin were added to gallium metal-organic framework compounds containing small amounts of compounds with fluorescent recognition capabilities, and their emission spectra were measured. Then, an equal amount of amikacin was added to an aqueous solution of the gallium metal-organic framework compound, and its emission spectrum was measured (see attached figure). Figure 8 (As shown).

[0057] Example 2

[0058] A method for preparing a gallium metal-organic framework material with fluorescence recognition function includes the following steps:

[0059] (1) Gallium nitrate monohydrate, 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridine-6,4,2-triyl))tetrabenzoic acid, and oleic acid were added to a mixture of ethanol and N,N-dimethylformamide and stirred until homogeneous. The molar ratio of gallium nitrate monohydrate, 4,4',4”,4”'-(4,4'-(1,4-phenylene)bis(pyridine-6,4,2-triyl))tetrabenzoic acid, oleic acid, ethanol and N,N-dimethylformamide was (5):(1):(225):(1200):(1850).

[0060] (2) Place the mixture obtained in step (1) into a reaction vessel, seal it in a reaction oven, heat it to 80°C for 48 hours, and obtain a red block crystal product, which is a gallium metal-organic framework material with fluorescence recognition function.

Claims

1. A three-dimensional gallium metal-organic framework material with fluorescence recognition function, characterized in that, Its chemical formula is {[(CH3)2(NH2)Ga(PPTA)]·0.5DMF} n The crystal has a space group of C2 / c, which is monoclinic. Each independent unit contains only one trivalent gallium atom. In the smallest independent unit, the four-coordinated gallium atom forms a tetrahedral structure with carboxyl oxygen, where the carboxyl oxygen belongs to four ligand molecules. Each gallium atom is connected to four ligand molecules, and each ligand molecule is coordinated with four gallium atoms, ultimately forming a two-fold interpenetrating three-dimensional metal-organic framework with square one-dimensional channels of 10.8 × 14 Å. Its three-dimensional structure diagram is as follows ； The aforementioned three-dimensional gallium metal-organic framework material with fluorescence recognition function can only be detected through 4,4',4”,4” '-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid (H4PPTA) and gallium nitrate are generated by a solvothermal reaction.

2. A method for synthesizing a gallium metal-organic framework material with fluorescence recognition function as described in claim 1, characterized in that, Includes the following steps: (1) Gallium nitrate monohydrate, 4,4',4'',4'''-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid, and oleic acid were added to a mixture of ethanol and N,N-dimethylformamide and stirred until homogeneous. The molar ratio of gallium nitrate monohydrate, 4,4',4'',4'''-(4,4'-(1,4-phenylene)bis(pyridin-6,4,2-triyl))tetrabenzoic acid, oleic acid, ethanol and N,N-dimethylformamide was (1.8-2.2):(0.9-1.1):(250-300):(1100-1400):(1600-1900). (2) Place the mixture obtained in step (1) into a round-bottomed glass bottle with an aluminum cap, seal it and place it in a reaction oven, heat it to 80-110℃ for 48-96 hours to obtain a red block crystal product, which is a gallium metal-organic framework material with fluorescence recognition function.

3. A method for applying the gallium metal-organic framework material with fluorescence recognition function as described in claim 1, characterized in that, Used to detect the aminoglycoside antibiotic amikacin.

4. The application method of the gallium metal-organic framework material with fluorescence recognition function according to claim 3, characterized in that, The detection of amikacin involves the following steps: (1) The gallium metal-organic framework material was ultrasonically dispersed in an aqueous solution, and its fluorescence was tested. The recognition effect of the gallium metal-organic framework material with specific fluorescence recognition function on amikacin was obtained based on the change in fluorescence intensity. (2) Add different amounts of amikacin aqueous solution to the aqueous solution of gallium metal-organic framework material with fluorescence recognition function using a pipette and test its fluorescence intensity; fit the obtained data to obtain the quantitative relationship and detection limit of the gallium metal-organic framework material with fluorescence recognition function for the detection of amikacin in aqueous solution; (3) Amikacin can be identified in aqueous solutions containing some blood components such as NaCl, MgCl2, CaCl2, KCl, KHCO3, Zn(NO3)2, creatinine or glucose; Alternatively, amikacin can be identified in aqueous solutions containing the antibiotics tobramycin, thiamphenicol, norfloxacin, amoxicillin, or lonidazole. Alternatively, the procedure of step (2) can be performed on a diluted human serum solution to detect amikacin, thereby obtaining the quantitative relationship and detection limit of the gallium metal-organic framework with fluorescence recognition function for the detection of amikacin in the diluted human serum solution.

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