Hydrogen bond organic framework material, preparation method and application of hydrogen bond organic framework material in dopamine detection

Abstract

The invention provides a hydrogen bond organic framework material, a preparation method and application of the hydrogen bond organic framework material in dopamine detection, the preparation method of the hydrogen bond organic framework material comprises the following steps: S1, dissolving 1, 3, 5-tri (4-carboxyphenyl) benzene in an organic solvent to obtain an organic solution; and S2, dropwise adding an alcohol solvent into the organic solution to react to obtain turbid liquid, and drying to obtain the hydrogen bond organic framework material. The hydrogen bond organic framework material HOF-BTB prepared by the invention is a porous material, has two-dimensional (2D) pi-pi stacked hexagonal lamellas and complex eight interpenetration, generates a one-dimensional channel in the framework, and is simple in preparation process, mild in synthesis condition, low in cost, good in biocompatibility and low in cytotoxicity; and due to rigid organic construction molecules, the compound shows excellent fluorescence performance. The HOF-BTB material has high selectivity due to differential recognition of binding sites, and can be effectively applied to detection of dopamine.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen-bonded organic framework materials, and in particular to a hydrogen-bonded organic framework material, a preparation method and application thereof in dopamine detection. Background Art

[0002] Dopamine is an important hormone and neurotransmitter in the catecholamine and phenylethylamine classes. It plays many regulatory roles in the human brain and controls many physiological functions, such as motivation, emotion, endocrine regulation, and movement. Many diseases, such as Parkinson's disease, schizophrenia, and anorexia, are associated with abnormal DA levels. To study the biological functions of DA during life, establishing methods to test DA has always been one of the hot topics in the analytical field.

[0003] So far, the methods for detecting DA include high performance liquid chromatography, mass spectrometry, spectrophotometry and electrochemical methods, etc. All of the above methods have disadvantages. For example, chromatography and mass spectrometry methods rely on expensive equipment and specific sample pretreatment procedures; spectrophotometry has relatively low sensitivity, and electrochemical methods usually produce similar oxidation potentials due to the interference of ascorbic acid, so the application of the above methods is greatly limited. Fluorescence analysis methods have become a better alternative method for detecting DA due to their outstanding features such as low cost, simple operation, high sensitivity, strong practicality, and good selectivity. Moreover, most fluorescence methods have the advantage of directly detecting DA in complex biological matrices without separation procedures. Currently, some fluorescent probes, such as organic dyes and single-arm carbon nanotubes, are being developed as selective and sensitive methods for directly detecting neurotransmitter DA. However, organic dye fluorescent probes are inevitably subject to certain limitations due to toxicity and complex synthesis steps. Therefore, it is of great significance to develop a fluorescent sensor for detecting DA with a simple preparation process, mild synthesis conditions, low cost, good biocompatibility, and low cytotoxicity. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art and to provide a hydrogen-bonded organic framework material, a preparation method and an application thereof in dopamine detection.

[0005] The technical solution adopted by the present invention is as follows: The first aspect of the present invention provides a method for preparing a hydrogen-bonded organic framework material, comprising the following steps: S1. dissolving 1,3,5-tris(4-carboxyphenyl)benzene in an organic solvent to obtain an organic solution; S2. dropping an alcohol solvent into the above organic solution to react and obtain a suspension, and drying the suspension to obtain a hydrogen-bonded organic framework material.

[0006] Preferably, in step S1, the organic solvent includes at least one of DMF, N,N-dimethylacetamide and dimethyl sulfoxide.

[0007] Preferably, in step S2, the alcohol solvent includes at least one of methanol and ethanol.

[0008] Preferably, the ratio of 1,3,5-tris(4-carboxyphenyl)benzene to methanol is (60-100) mg:1 mL.

[0009] The second aspect of the present invention provides an application of a hydrogen-bonded organic framework material prepared by the preparation method described above in dopamine detection.

[0010] Preferably, the method comprises the following steps: (A) Detection of dopamine content in standard solution: The hydrogen-bonded organic framework material prepared by the above preparation method is dispersed in deionized water to obtain a HOF-BTB suspension. Under the excitation of excitation light, the fluorescence spectrum of the HOF-BTB suspension after adding dopamine standard solution samples of different concentrations is measured, and a standard working straight line is established based on the relationship between the concentration of the standard solution sample and the fluorescence spectrum I0 / I; wherein I0 represents the original fluorescence of the HOF-BTB suspension itself, and I represents the fluorescence emitted after adding dopamine of different concentrations; (B) Detection of dopamine content in samples: Detect the fluorescence spectrum of the sample solution and calculate the dopamine content in the sample solution based on the obtained standard working straight line.

[0011] Preferably, in step (A), the concentration of the HOF-BTB suspension is 0.1-0.3 g / L.

[0012] Preferably, in step (A), the wavelength of the excitation light is 312 nm.

[0013] The beneficial effects of the present invention are as follows: (1) The hydrogen-bonded organic framework material HOF-BTB prepared by the present invention is a porous material having two-dimensional (2D) π-π stacked hexagonal sheets and complex eight-fold interpenetration, producing one-dimensional channels in the framework; the preparation process is simple, the synthesis conditions are mild, the cost is low, the biocompatibility is good, and the cytotoxicity is low.

[0014] (2) The rigid organic structural molecules enable it to exhibit excellent fluorescence properties. The porosity and large specific surface area of ​​the HOF-BTB material facilitate full contact with the analyte and promote interaction with the guest molecules, thereby improving detection sensitivity. The differential recognition of binding sites makes it highly selective and can be effectively applied to the concentration detection of dopamine. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, without paying creative labor, other drawings obtained based on these drawings still belong to the scope of the present invention.

[0016] Figure 1 is the structural formula of 1,3,5-tris(4-carboxyphenyl)benzene; Figure 2 is the X-ray diffraction pattern of the HOF-BTB powder prepared in Example 1; Figure 3 is the SEM image of the HOF-BTB powder prepared in Example 1; Figure 4 The HOF-BTB powder prepared in Example 1 was dispersed in a concentration of 2.28×10 -3 Excitation and emission spectra of M in suspension; Figure 5 PL spectra of HOF-BTB with different dopamine concentrations added; Figure 6 The Stern-Volmer fitting diagram of dopamine and the linear fitting curve at low concentration; Figure 7 It is the fitting curve diagram of HOF-BTB emission intensity under different dopamine (DA) concentrations; Figure 8 PL spectra of HOF-BTB with different concentrations of organic molecules (cysteine, phenylalanine, glutamate, and urea) added; Fig. 9 PL spectra of HOF-BTB with different concentrations of organic molecules (glucose, tryptophan and aspartic acid) added. DETAILED DESCRIPTION

[0017] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings.

[0018] Example 1 This embodiment provides a HOF-BTB material, and the preparation method thereof comprises the following steps: Weigh 200 mg of white powder 1,3,5-tri(4-carboxyphenyl)benzene and add it to a beaker containing 0.5 mL of DMF solution. Transfer the beaker to an ultrasonic machine. After ultrasonic treatment for several minutes, the powder completely dissolves in the DMF solution to obtain a light yellow transparent solution. Use a pipette to drop 2.5 mL of methanol into the light yellow transparent solution obtained above, mix well, and then ultrasonicate for several minutes to obtain a white suspension. Finally, place it in a 60°C oven overnight to obtain yellow crystals, which are washed with methanol several times and air-dried to finally obtain the HOF-BTB material.

[0019] The morphology of the HOF-BTB material prepared in Example 1 was characterized, and the following results were obtained: The powder X-ray diffraction (PXRD) patterns of the HOF-BTB samples were collected by X-ray diffractometer (D8 PHASER) with Cu Kα = 1.54056 Å and a scan rate of 5 ° / min, scanning range is 5 - 50 ° . 1,3,5-Tris(4-carboxyphenyl)benzene H3BTB has a hexagonal (6,3) honeycomb structure motif, connected by carboxylic acid dimers to form hexagonal sheets. The synthesized HOF-BTB has two-dimensional (2D) π-π stacked hexagonal sheets and complex eight-fold interpenetration, resulting in one-dimensional channels in the framework. The synthesized HOF-BTB was analyzed by PXRD analysis, as shown in Figure 2 As shown, the diffraction peaks of the synthesized HOF-BTB were consistent with the simulated peaks characterized by powder X-ray diffraction (PXRD), which well demonstrated the crystalline phase purity of the prepared sample.

[0020] The size and morphology of the HOF-BTB sample were obtained by field emission scanning electron microscopy (FE-SEM), where the setting parameters (acceleration voltage) were 10 kV. The shape and size were further studied by scanning electron microscopy (SEM), such as Figure 3 As shown, the HOF-BTB sample exhibits a block-like morphology with a size of approximately 50 μm.

[0021] The fluorescence performance of the HOF-BTB material prepared in Example 1 was tested, and the following results were obtained: The fluorescence emission of HOF-BTB can be attributed to the emission of organic building molecules, and HOF-BTB exhibits stronger emission due to tighter interactions of the rigid framework, which restricts the intramolecular motion. HOF-BTB dispersed in deionized water has a strong emission peak at 397nm when excited at the optimal excitation wavelength of 312nm.

[0022] Example 2 This embodiment provides an application of a hydrogen-bonded organic framework material in dopamine detection, comprising the following steps: (A) Detection of dopamine content in standard solution: 10 mg of the HOF-BTB material prepared in Example 1 was dispersed in 50 mL of deionized water. After ultrasonic treatment for 15 minutes, a uniformly dispersed HOF-BTB suspension was obtained. 2 mL of the uniformly dispersed HOF-BTB suspension was taken and transferred to a quartz cuvette. Various analytes were then gradually added to the cuvette for fluorescence sensing experiments.

[0023] Under 312nm excitation, the fluorescence spectra of the HOF-BTB suspension after adding different concentrations of dopamine samples were measured, and a standard working straight line was established based on the relationship between the concentration of the dopamine sample and the fluorescence spectrum I0 / I; where I0 represents the original fluorescence of the HOF-BTB suspension itself, and I represents the fluorescence emitted after adding different concentrations of dopamine; (B) Detection of dopamine content in samples: Detect the fluorescence spectrum of the sample solution and calculate the dopamine content in the sample solution based on the obtained standard working straight line.

[0024] Based on the fluorescence titration method, different concentrations of dopamine were gradually added to the suspension of HOF-BTB, and the emission spectra were shown in Figure 2. Figure 5 As shown in the figure, the luminescence intensity is gradually quenched with the increase of dopamine concentration. The quenching efficiency of dopamine can be quantitatively explained by the Stern-Volmer equation I0 / I=1+KSV[Q]. Where I0 is the fluorescence intensity of the HOF-BTB suspension, I is the fluorescence intensity after adding dopamine, and [Q] is the concentration of dopamine (DA). It is worth noting that the HOF-BTB solution has a linear relationship with dopamine in the low concentration range. When the dopamine concentration is 0.56mM, the quenching efficiency reaches 92.6%.

[0025] HOF-BTB has high selectivity and sensitivity in detecting dopamine in water samples.

[0026] The sensing performance of HOF-BTB for different organic molecules was investigated. When a small amount of dopamine was added, the PL emission of HOF-BTB was significantly quenched ( Figure 5 ), while the addition of other organic molecules, such as cysteine, phenylalanine, glutamic acid, urea, glucose, tryptophan and aspartic acid, showed no significant change in the PL emission of HOF-BTB ( Figure 8 , 9 ). The fluorescence intensity of HOF-BTB solution is linearly related to the amount of dopamine added in the low concentration range. This relationship can be explained by the Stern-Volmer equation. The calculated quenching coefficient Ksv is about 2.01×10 4 M -1, the detection limit was 32.95 μM ( Figure 6 , 7 ).

[0027] The above disclosure is only the preferred embodiment of the present invention, which certainly cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention are still within the scope of the present invention.

Claims

1. A method for preparing a hydrogen-bonded organic framework material, characterized in that: The steps include: S1. dissolving 1,3,5-tris(4-carboxyphenyl)benzene in an organic solvent to obtain an organic solution; S2. dropping an alcohol solvent into the above organic solution to react and obtain a suspension, and drying the suspension to obtain a hydrogen-bonded organic framework material.

2. The method for preparing a hydrogen-bonded organic framework material according to claim 1, characterized in that: In step S1, the organic solvent includes at least one of DMF, N,N-dimethylacetamide, and dimethyl sulfoxide.

3. The method for preparing a hydrogen-bonded organic framework material according to claim 1, characterized in that: In step S2, the alcohol solvent includes at least one of methanol and ethanol.

4. The method for preparing a hydrogen-bonded organic framework material according to claim 3, characterized in that: The ratio of the 1,3,5-tris(4-carboxyphenyl)benzene to methanol is (60-100) mg:1 mL.

5. Application of the hydrogen-bonded organic framework material prepared by the preparation method according to any one of claims 1 to 4 in dopamine detection.

6. The use according to claim 5, characterized in that The steps include: (A) Detection of dopamine content in a standard solution: The hydrogen-bonded organic framework material prepared by any one of the preparation methods of claims 1 to 4 is dispersed in deionized water to obtain a HOF-BTB suspension. Under the excitation of excitation light, the fluorescence spectrum of the HOF-BTB suspension after adding dopamine standard solution samples of different concentrations is measured, and a standard working straight line is established based on the relationship between the concentration of the standard solution sample and the fluorescence spectrum I0 / I; wherein I0 represents the original fluorescence of the HOF-BTB suspension itself, and I represents the fluorescence emitted after adding dopamine of different concentrations; (B) Detection of dopamine content in samples: Detect the fluorescence spectrum of the sample solution and calculate the dopamine content in the sample solution based on the obtained standard working straight line.

7. The use according to claim 6, characterized in that: In step (A), the concentration of the HOF-BTB suspension is 0.1-0.3 g / L.

8. The use according to claim 6, characterized in that: In step (A), the wavelength of the excitation light is 312 nm.

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