Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, and preparation method therefor and use thereof

Abstract

The present invention provides a Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, and a preparation method therefor and a use thereof. The Zn-MOF material uses zinc as a metal center and H2PDBA as a ligand. The chemical molecular formula of the Zn-MOF material is [C34H30N2O4Zn]n, wherein n represents an infinite alternating arrangement of the simplest molecular formula in the internal molecular composition of the material. The present invention further provides a preparation method for the Zn-MOF material. The preparation method comprises adding H2PDBA and an inorganic zinc compound to a first organic mixed solution and placing the mixture in a reaction kettle for a reaction to obtain the Zn-MOF material. The Zn-MOF material of the present invention can realize high-selectivity detection of ATP / ADP in water. In addition, a new fluorescent material is provided for the detection of ATP / ADP, and new ideas are provided for rationally constructing more stable MOFs in terms of structural design.

Description

Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection, preparation method and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of optical sensing and detection, and particularly relates to a Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection, a preparation method and application thereof. BACKGROUND

[0002] Adenosine triphosphate (ATP) plays a very important role in biological energy, metabolism and genetic information transfer. ADP is a compound composed of one molecule of adenosine and two connected phosphate groups. In the body, it is usually the product after ATP hydrolysis loses one phosphate group, i.e. breaks one high-energy phosphate bond and releases energy. Abnormal ATP concentration in the body can cause hypoglycemia and ischemia, triggering a series of diseases such as Parkinson's syndrome and malignant tumors. Therefore, it is of great significance to detect ATP and ADP simultaneously. Researchers have developed methods to detect ATP and ADP, but these methods still have some defects, such as complicated experimental procedures, the need for complex and professional operations, etc. Therefore, it is necessary to develop a simple and effective method to detect ATP and ADP simultaneously. In contrast, fluorescence-based methods have the advantages of high sensitivity, portability and real-time detection. For specific detection of ADP and ADP, it is necessary to avoid the interference of other substances, especially other forms of phosphate such as AMP and phosphate. Therefore, it is challenging to develop a highly selective ADP and ADP detection fluorescent probe. SUMMARY

[0003] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection, a preparation method and application thereof, to solve the problems in the prior art that the ATP / ADP detection sensor causes the signal to be "turned off", has defects such as low selectivity and sensitivity, and cannot well meet the requirements of sensor selectivity and sensitivity in biomolecular detection. The present application provides a Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection, wherein the Zn-MOF material takes zinc as the metal center and H2PDBA as the ligand, and the chemical molecular formula of the Zn-MOF material is: 34 H 30 N2O4Zn] n , n represents the infinite alternating arrangement of the internal molecular composition of the material as the simplest molecular formula; wherein, the structure formula of the H2PDBA is: In some embodiments of the present application, the crystal structure of the Zn-MOF material belongs to the orthorhombic system, and the space group is the orthorhombic space group. 2+ The coordination environment of the Zn-MOF material is composed of one Zn ion, two H2PDBA and two dimethylamine molecules. The second aspect of the present application provides a preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, characterized in that the preparation method comprises adding H2PDBA and an inorganic zinc compound into a first organic mixed solution, and reacting in a reaction kettle to obtain the Zn-MOF material. In some embodiments of the present application, the inorganic zinc compound is selected from one or more of Zn(NO3)2·6H2O, zinc sulfate or zinc acetate. In some embodiments of the present application, the molar ratio of the H2PDBA and the inorganic zinc compound is 1:(1-3). In some embodiments of the present application, the first organic mixed solution is a mixture of a first organic solvent and water. In some embodiments of the present application, the reaction temperature is 130-150℃. In some embodiments of the present application, the reaction time is 24-84h. In some embodiments of the present application, the first organic solvent is selected from one or more of DMF, DMA, DMSO, C2H5OH or CH3OH. In some embodiments of the present application, the volume ratio of the first organic solvent to water is (5-7):1. In some embodiments of the present application, the preparation method of the H2PDBA comprises the following steps: S1, under the condition of inert gas protection, reacting 1,6-dihalopyrene, 4-carboxyphenylboronic acid, alkali salt, organometallic compound and a second organic mixed solution to obtain a first mixture; S2, adding an acid solution into the first mixture obtained in step S1 to obtain the H2PDBA. The third aspect of the present application provides an application of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP as described above, which is used for high-sensitivity and high-selectivity detection of ATP and ADP. The present application has the following beneficial effects: The present application uses H2PDBA to construct a new type of Zn-MOF material with coordination-induced emission effect, and the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP can realize high-selectivity detection of ATP / ADP in water, and provides a new fluorescent material for ATP / ADP detection, and provides a new idea for rationally constructing more stable MOFs from structural design, and the present application effectively overcomes various shortcomings in the prior art and has high industrial utilization value. BRIEF DESCRIPTION OF DRAWINGS

[0004] Figure 1 shows the mass spectrum of the ligand H2PDBA of the present application. Figure 2 shows the hydrogen spectrum of the ligand H2PDBA of the present application. Figure 3 shows the infrared spectrum of the Zn-MOF material of the present application. Figure 4 shows the X-ray single crystal diffraction of the Zn-MOF material of the present application. Figure 5 shows the thermogravimetric curve of the Zn-MOF material of the present application. Figure 6 shows the fluorescence emission spectrum of the Zn-MOF material of the present application in different ions. Figure 7 shows the fluorescence intensity histogram of the Zn-MOF material of the present application in different ions. Figure 8 shows the fluorescence intensity histogram of the Zn-MOF material of the present application in the presence of ATP and different ions. Figure 9 shows the fluorescence intensity histogram of the Zn-MOF material of the present application in the presence of ADP and different ions. Figure 10 shows the fluorescence emission spectrum of the Zn-MOF material of the present application in different concentrations of ATP; wherein (a) shows the fluorescence intensity dot plot of the Zn-MOF material of the present application at 435 nm in different concentrations of ATP. Figure 11 shows the fluorescence emission spectrum of the Zn-MOF material of the present application in different concentrations of ADP; wherein (b) shows the fluorescence intensity dot plot of the Zn-MOF material of the present application at 435 nm in different concentrations of ADP. DETAILED DESCRIPTION

[0005] Other advantages and effects of the present application can be easily understood by those skilled in the art from the above description. The present application can also be implemented or applied in other different specific embodiments, and various modifications or changes can be made to the details of the present application based on different viewpoints and applications without departing from the spirit of the present application. Please refer to Figures 1-11. It should be noted that the drawings provided in the present embodiment only schematically illustrate the basic concept of the present application, and the drawings only show the components related to the present application, not the number, shape and size of the components when actually implemented. The actual implementation of each component may 34 H 30 N2O4Zn] n , n represents the infinite alternating arrangement of the internal molecular composition of the material as the simplest molecular formula; wherein, the structure of the H2PDBA is: The Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the application is constructed from the perspective of framework connection, and the crystal structure of the Zn-MOF material belongs to the orthorhombic system and the orthorhombic space group. The coordination environment of the Zn-MOF material is composed of one Zn 2+ ion, two H2PDBA and two dimethylamine molecules. The Zn 2+ ion adopts a four-coordination mode, wherein two O atoms (O1 and O2) and two N atoms (N1 and N2) are respectively provided by two ligands and two dimethylamine molecules, and a four-coordination tetrahedral cone configuration is presented. The bond distance of Zn-O is in the range of 1.9453(15) to 2.043(2) , and the average bond distance of Zn-N is 2.043(3) . 2+The coordination of ions with another ligand O atom leads to the formation of a one-dimensional structure from the

[0001] direction. Then, the hydrogen bond interaction (N-H···O) between the dimethylamine molecules and H2PDBA extends the one-dimensional structure to a two-dimensional structure. The second aspect of the present application provides a preparation method of a Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, which comprises adding H2PDBA and an inorganic zinc compound into a first organic mixed solution, and placing it in a reaction kettle for reaction to obtain the Zn-MOF material. Specifically, the H2PDBA and the inorganic zinc compound are added into the first organic mixed solution, and placed in a 25 mL reaction kettle for reaction, and after the reactants are cooled to room temperature, a gray crystal, i.e., the Zn-MOF material, is obtained. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the inorganic zinc compound is selected from one or more of Zn(NO3)2·6H2O, zinc sulfate or zinc acetate. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the molar ratio of the H2PDBA and the inorganic zinc compound is 1:(1-3), which can be optionally 1:(1-2) or 1:(2-3), and is preferably 1:2. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the first organic mixed solution is a mixed solution of a first organic solvent and water. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the first organic solvent is selected from one or more of DMF, DMA, DMSO, C2H5OH or CH3OH. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the volume ratio of the first organic solvent to water is (5-7):1, which can be optionally (5-6):1 or (6-7):1, and is preferably 6:1. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the reaction temperature is 130-150°C, which can be optionally 130-140°C or 140-150°C, and is preferably 140°C. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, the reaction time is 24-84h, which can be optionally 24-30h, 30-40h, 40-50h, 50-60h, 60-72h, 72-75h, 72-84h or 75-84h, etc., and is preferably 72h.The application provides a preparation method of Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, and the preparation method of H2PDBA comprises the following steps: S1, under inert gas protection, 1,6-dihalogenated pyrene, 4-carboxyl phenyl boronic acid, alkali salt, organic metal compound and a second organic mixed solution are reacted to obtain a first mixture; and S2, an acid solution is added into the first mixture obtained in the step S1, and reaction is performed to obtain the H2PDBA. In the preparation method of Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, the step S1 is that, under inert gas protection, 1,6-dihalogenated pyrene, 4-carboxyl phenyl boronic acid, alkali salt, organic metal compound and a second organic mixed solution are reacted to obtain a first mixture. Specifically, 1,6-dihalogenated pyrene, 4-carboxyl phenyl boronic acid, alkali salt, organic metal compound and a second organic mixed solution are mixed, stirred uniformly, and reacted under nitrogen protection, and after reaction, the first mixture is collected after being cooled to room temperature. In the step S1, the inert gas is selected from one or both of nitrogen and argon. In the step S1, the 1,6-dihalogenated pyrene is selected from one or both of 1,6-dibromopyrene and 1,6-dichloropyrene. In the step S1, the alkali salt is selected from one or more of K2CO3, sodium carbonate, sodium bicarbonate and potassium bicarbonate. In the step S1, the organic metal compound is Pd(PPh3)4. In the step S1, the second organic mixed solution is a mixed solution of a second organic solvent and water. In the step S1, the molar ratio of the 1,6-dihalogenated pyrene to the 4-carboxyl phenyl boronic acid is 1:(1-3), which can be 1:(1-2) or 1:(2-3), and preferably 1:2. In the step S1, the molar ratio of the 1,6-dihalogenated pyrene to the alkali salt is 1:(9-11), which can be 1:(9-10) or 1:(10-11), and preferably 1:10. In the step S1, the molar ratio of the 1,6-dihalogenated pyrene to the organic metal compound is 1:(0.1-0.5), which can be 1:(0.1-0.2), 1:(0.2-0.4), 1:(0.4-0.5), 1:(0.1-0.3) or 1:(0.1-0.5), etc. In the step S1, the mass-volume ratio of the 1,6-dihalogenated pyrene to the first organic mixed solution is 1g:(70-75)mL, which can be 1g:(70-72)mL, 1g:(72-73)mL, 1g:(72-74)mL, 1g:(74-75)mL or 1g:(72-75)mL, etc., and preferably 1g:72mL. In the step S1, the reaction temperature is 90-110 DEG C, which can be 90-100 DEG C or 100-110 DEG C, and preferably 100 DEG C.In step S1 of the present application, the reaction time is 36-60h, which can be 36-40h, 40-45h, 45-46h, 46-48h, 48-49h, 45-48h, 48-55h or 55-60h, preferably 48h. In step S1 of the present application, the second organic solvent is selected from one or more of DMF, DMA, DMSO, C2H5OH or CH3OH. In step S1 of the present application, the volume ratio of the second organic solvent to water is (5-7):1, which can be (5-6):1 or (6-7):1, preferably 6:1. In the preparation method of the Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP provided by the present application, step S2 is adding an acid solution to the first mixture obtained in step S1 to obtain the H2PDBA. Specifically, an acid solution is added to the first mixture obtained in step S1, and a gray solid powder, i.e., H2PDBA, is obtained by stirring reaction. In step S2 of the present application, the acid solution is selected from one or more of hydrochloric acid aqueous solution, sulfuric acid aqueous solution or nitric acid aqueous solution. In step S2 of the present application, the mass-volume ratio of the 1,6-dihalogenated pyrene to the acid solution is 1g:(80-85)mL, which can be 1g:(80-82)mL, 1g:(82-83)mL, 1g:(83-85)mL or 1g:(80-83)mL, preferably 1g:83mL. In step S2 of the present application, the reaction time is 20-60min, which can be 20-25min, 25-30min, 30-35min, 35-40min, 45-50min, 50-55min or 55-60min, preferably 30min. In step S2 of the present application, the mass fraction of the solute in the acid solution is 8%-12%, which can be 8%-9%, 9%-10%, 10%-11%, 11%-12%, preferably 10%. The third aspect of the present application provides a Zn-MOF material for high-sensitivity and high-selectivity detection of ATP / ADP, which is used for high-sensitivity and high-selectivity detection of ATP and ADP. The recognition mechanism of the Zn-MOF material is that after the Zn-MOF material reacts with ATP or ADP, the interaction between ATP / ADP and the MOF causes the luminescent Zn-MOF framework with ligand-induced luminescence (CIE) effect to collapse in structure and release the ligand H2PDBA, and the fluorescence of the ligand H2PDBA in water is relatively weak, so that the MOF material is quenched and the emission wavelength is red-shifted. In order to make the technical means, creative features and purposes and effects of the present application easy to understand, the present application is specifically described in combination with the embodiments and the drawings. In the following examples, unless otherwise specified, each reaction raw material is a commercially available product. Unless otherwise specified, the purity of each product in each embodiment of the present application is more than 98%.Example 1 Preparation of ligand H2PDBA: 1,6-dibromopyrene (0.36 g, 1.0 mmol), 4-carboxyphenylboronic acid (0.34 g, 2.0 mmol), K2CO3(1.38 g, 10.0 mmol), Pd(PPh3)4(0.12 g, 0.10 mmol), DMF / H2O (v / v = 6 / 1, 24.0 mL) were added into a mixed solution, stirred uniformly, and reacted at 100 °C for 48 h under the protection of nitrogen. After the reaction, the reaction mixture was cooled to room temperature, 10% aqueous HCl solution (30 mL) was added, and the reaction was stirred for 30 min to obtain H2PDBA as a gray solid powder, 0.32 g, yield 72%. M.P.: >300 °C. HRMS calcd. m / z 442.1205 for [M]+, found m / z 465.1098 for [M+Na]+.1H NMR (400 MHz, DMSO-d6) δ 8.35 (d, J = 7.9 Hz, 2H), 8.21 (d, J = 9.4 Hz, 2H), 8.15 (d, J = 9.2 Hz, 2H), 8.09 (d, J = 8.0 Hz, 4H), 8.05 (d, J = 7.9 Hz, 2H), 7.60 (d, J = 7.8 Hz, 4H) (as shown in FIG. 1 and FIG. 2). 34 H 30 N2O4Zn Elemental analysis results: Theoretical value: C, 68.45; H, 5.03; N, 4.70, Actual value: C, 68.37; H, 4.98; N, 4.61. Infrared analysis results: IR (KBr, cm-1): 3424 (m), 3194 (m), 1607 (vs), 1549 (s), 1387 (vs), 1179 (w), 1098 (w), 1052 (w), 844 (s), 786 (s), 716 (w) (as shown in FIG. 3). Example 3 Structural characterization of Zn-MOF 2+ The crystal X-ray diffraction pattern of the Zn-MOF material (as shown in FIG. 4) shows that the Zn-MOF coordinates with Pbcn in an orthogonal space group. The coordination environment is composed of one Zn 2+The ion adopts a tetrahedral coordination, with two O atoms (01 and 02) and two N atoms (N1 and N2) provided by two ligands and two dimethylamine molecules, respectively, assuming a tetrahedral tetragonal pyramidal conformation. The Zn-O bond distances range from 1.9453(15) to 2.043(2) The average Zn-N bond distance is 2.043(3) Zn 2+The coordination of ions with another ligand O atom leads to the formation of a one-dimensional structure from the

[0001] direction. Then, the hydrogen bond interaction (N-H···O) between the dimethylamine molecules and H2PDBA extends the one-dimensional structure to a two-dimensional structure. Example 4 Thermal stability analysis of Zn-MOF: To study the use conditions of Zn-MOF at different temperatures, this example tests the thermogravimetric (TG) curve of Zn-MOF in the range of room temperature to 800℃. An empty crucible is placed in the equipment, weighed, peeled, and the empty crucible is taken out. An appropriate amount of Zn-MOF is weighed from room temperature to 280℃, and the mass loss is 14.93% (the theoretical value is: 14.76%), which can be attributed to the loss of two molecules of coordinated dimethylamine in the Zn-MOF crystal; when the heating temperature exceeds 280℃, the mass loss decreases sharply, and the original framework structure of Zn-MOF collapses (as shown in Figure 5). Example 5 Ion selectivity experiment of Zn-MOF: Determine the optical properties of Zn-MOF in different metal ions: Compound Zn-MOF 0.5mg is dissolved in 3.0mL water to prepare a host solution, different ions are added: 166.67μM, λex: 330nm, and the fluorescence emission spectrum is obtained. The fluorescence intensity at the fluorescence emission peak 435nm is plotted against different ions, and the fluorescence intensity column chart of different ions is obtained, as shown in Figure 7. After adding ATP / ADP, the fluorescence decreases significantly, and after adding other ions, the fluorescence intensity remains basically unchanged. Because the interaction between ATP / ADP and MOF leads to the structural collapse of the luminescent Zn-MOF framework with ligand-induced luminescence (CIE) effect, and the release of the ligand H2PDBA, the ligand H2PDBA has relatively weak fluorescence in water, which causes the fluorescence quenching of the MOF material, and the emission wavelength red shift (as shown in Figure 6). Example 6 Ion competition experiment of Zn-MOF: Determine the optical properties of Zn-MOF in different metal ions: Compound Zn-MOF 0.5mg is dissolved in 3.0mL water to prepare a host solution, ATP 146.67μM and an equal amount of different ions are added, λex: 330nm, and the fluorescence emission spectrum is obtained. The fluorescence intensity at the fluorescence emission peak 435nm is plotted against different ions, and the fluorescence intensity column chart of ATP and different metal ions coexisting is obtained, as shown in Figure 8. When ATP and different ions coexist, they have little effect on the fluorescence intensity.Example 7 Ion competition experiment of Zn-MOF: The optical properties of Zn-MOF in different metal ions were determined: compound Zn-MOF 0.5 mg was dissolved in 3.0 mL of water to prepare a host solution, ADP 166.67 μM and an equal amount of different ions were added, λex: 330 nm, and the fluorescence emission spectrum was obtained. The fluorescence intensity at the fluorescence emission peak 435 nm was plotted against different ions to obtain the fluorescence intensity column chart of ADP and the coexistence of different metal ions, as shown in Figure 9. The coexistence of ADP and different ions has little effect on the fluorescence intensity. Example 8 Continuous titration spectrum of Zn-MOF for detection of different concentrations of ATP: The continuous titration spectrum of compound Zn-MOF for detection of different concentrations of ATP was determined: compound Zn-MOF 0.5 mg was dissolved in 3.0 mL of water to prepare a host solution, and ATP was added, λex: 330 nm, and the fluorescence emission spectrum was obtained. With the increase of ATP concentration, the fluorescence intensity gradually decreased. When the ATP concentration was higher than 130 μM, the solution tended to be saturated, and the fluorescence intensity was almost unchanged. The fluorescence intensity at the fluorescence emission peak 435 nm was plotted against different concentrations of ATP, as shown in Figure 10, to obtain the continuous titration spectrum of compound Zn-MOF for detection of different concentrations of ATP, as shown in Figure 10(a). The detection limit of Zn-MOF for ATP was calculated by the method of 3σ / k to be 0.82 μM. Example 9 Continuous titration spectrum of Zn-MOF for detection of different concentrations of ADP: The continuous titration spectrum of compound Zn-MOF for detection of different concentrations of ADP was determined: compound Zn-MOF 0.5 mg was dissolved in 3.0 mL of water to prepare a host solution, and ADP was added, λex: 330 nm, and the fluorescence emission spectrum was obtained. With the increase of ADP concentration, the fluorescence intensity gradually decreased. When the ADP concentration was higher than 120 μM, the solution tended to be saturated, and the fluorescence intensity was almost unchanged. The fluorescence intensity at the fluorescence emission peak 435 nm was plotted against different concentrations of ADP, as shown in Figure 11, to obtain the continuous titration spectrum of compound Zn-MOF for detection of different concentrations of ADP, as shown in Figure 11(b). The detection limit of Zn-MOF for ADP was calculated by the method of 3σ / k to be 1.7 μM. In combination with the above examples, the Zn-MOF material used for high-sensitivity and high-selectivity detection of ATP / ADP can realize high-selectivity detection of ATP / ADP in water, and provides a new fluorescent material for ATP / ADP detection, and provides a new idea for rationally designing more stable MOFs from the structure. Therefore, the present application effectively overcomes the various shortcomings in the prior art and has high industrial utilization value. The above embodiments are preferred cases of the present application and do not limit the protection scope of the present application.The applicant declares that the Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection and the preparation method and application of the present application are illustrated by the above-mentioned embodiments, but the present application is not limited to the above-mentioned embodiments, that is, it does not mean that the present application must rely on the above-mentioned embodiments to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. all fall within the protection scope and disclosure scope of the present application. The above-mentioned embodiments are preferred cases of the present application, and are not used to limit the protection scope of the present application. However, the present application is not limited to the specific details in the above-mentioned embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept scope of the present application, and these simple modifications all belong to the protection scope of the present application. In addition, it should be noted that each specific technical feature described in the above-mentioned specific embodiments can be combined by any suitable method without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combination methods.

Claims

1. A Zn-MOF material for high sensitivity and high selectivity detection of ATP / ADP, characterized in that, The Zn-MOF material takes zinc as a metal center and takes H2PDBA as a ligand, and a chemical molecular formula of the Zn-MOF material is: [C 34 H 30 N2O4Zn] n n represents infinite alternation of the internal molecular composition of the material to the simplest molecular formula; wherein, a structural formula of the H2PDBA is:

2. The Zn-MOF material for ATP / ADP high-sensitivity, high-selectivity detection according to claim 1, characterized in that, From the perspective of framework connection construction, the crystal structure of the Zn-MOF material belongs to an orthorhombic system, and the space group is an orthorhombic space group.

3. The Zn-MOF material for ATP / ADP high-sensitivity, high-selectivity detection according to claim 1, characterized in that, The coordination environment of the Zn-MOF material consists of one Zn 2+ ion, two H2PDBA and two dimethylamine molecules.

4. A method for preparing Zn-MOF material for high sensitivity and high selectivity detection of ATP / ADP according to any one of claims 1-2, characterized in that, The preparation method comprises the following steps: adding H2PDBA and an inorganic zinc compound into a first organic mixed solution, and reacting in a reaction kettle to obtain the Zn-MOF material.

5. The method for preparing Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection according to claim 4, characterized in that, Any one or more of the following features is included: A1) the inorganic zinc compound is selected from one or more of Zn(NO3)2·6H2O, zinc sulfate or zinc acetate; A2) the molar ratio of the H2PDBA and the inorganic zinc compound is 1:(1-3); A3) the first organic mixed solution is a mixed solution of a first organic solvent and water; A4) the reaction temperature is 130-150 DEG C; A5) the reaction time is 24-84 h.

6. The method for preparing Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection according to claim 5, characterized in that, Any one or more of the following features is included: A31) the first organic solvent is selected from one or more of DMF, DMA, DMSO, C2H5OH or CH3OH; A32) the volume ratio of the first organic solvent to water is (5-7):

1.

7. The method for preparing Zn-MOF material for ATP / ADP high-sensitivity and high-selectivity detection according to claim 5, characterized in that, The preparation method of the H2PDBA comprises the following steps: S1 under the condition of inert gas protection, 1,6-dihalogenated pyrene, 4-carboxyl phenyl boronic acid, alkali salt, organic metal compound and second organic mixed solution are reacted to obtain a first mixture; S2 an acid solution is added into the first mixture obtained in step S1, and reaction is carried out to obtain the H2PDBA.

8. The Zn-MOF material for ATP / ADP high-sensitivity, high-selectivity detection according to claim 7, characterized in that, Any one or more of the following features is included: B1) in step S1, the inert gas is selected from one or both of nitrogen or argon; B2) in step S1, the 1,6-dihalogenated pyrene is selected from one or both of 1,6-dibromopyrene or 1,6-dichloropyrene; B3) in step S1, the alkali salt is selected from one or more of K2CO3, sodium carbonate, sodium bicarbonate or potassium bicarbonate; B4) in step S1, the organic metal compound is Pd(PPh3)4; B5) in step S1, the second organic mixed solution is a mixed solution of a second organic solvent and water; B6) in step S1, the molar ratio of the 1,6-dihalogenated pyrene to the 4-carboxyl phenyl boronic acid is 1:(1-3); B7) in step S1, the molar ratio of the 1,6-dihalogenated pyrene to the alkali salt is 1:(9-11); B8) in step S1, the molar ratio of the 1,6-dihalogenated pyrene to the organic metal compound is 1:(0.1-0.5); B9) in step S1, the mass-volume ratio of the 1,6-dihalogenated pyrene to the first organic mixed solution is 1g:(70-75)mL; B10) in step S1, the reaction temperature is 90-110 DEG C; B11) in step S1, the reaction time is 36-60 h; B12) in step S2, the acid solution is selected from one or more of hydrochloric acid aqueous solution, sulfuric acid aqueous solution or nitric acid aqueous solution; B13) in step S2, the mass-volume ratio of the 1,6-dihalogenated pyrene to the acid solution is 1g:(80-85)mL; B14) in step S2, the reaction time is 20-60 min.

9. The Zn-MOF material for ATP / ADP high-sensitivity, high-selectivity detection according to claim 8, characterized in that, Also included are any one or more of the following features: B51) in step S1, the second organic solvent is selected from one or more of DMF, DMA, DMSO, C2H5OH or CH3OH; B52) in step S1, the volume ratio of the second organic solvent to water is (5-7):1; B121) in step S2, the mass fraction of solute in the acid solution is 8%-12%.

10. Use of Zn-MOF material for ATP / ADP high sensitivity, high selectivity detection according to any one of claims 1 to 9, characterized in that, For high-sensitivity, high-selectivity detection of ATP and ADP.

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