Preparation method of a perylene-based composite material and its application in electrochemiluminescence detection of glucose

Abstract

Patent of the present invention belongs to the field of electroluminescence, and relates to a preparation method of a perylene-based composite material and its application in electrochemiluminescence detection of glucose. Preparation method comprises the following steps: perylene 3,4,9,10 tetracarboxylic dianhydride PTCDA is mixed with imidazole in DMF, stirring, 1,3,5 tris (4 aminophenyl) benzene TAPB dissolved in DMF is added dropwise, after the addition is completed, the reaction is carried out, cooled to room temperature and methanol is added, the precipitate is collected by filtration, washed with DMF and methanol, and the dried powder is removed. Residual imidazoles are obtained to obtain a deep red powder. The catalyst has ordered porosity, structural stability and a large surface area. The material has good sensitivity, selectivity, stability and reproducibility for electrochemiluminescence detection of Glu, and a new scheme for designing a new electrocatalyst to test Glu is provided.

Description

Technical Field

[0001] The patent of this invention belongs to the field of electroluminescence, and relates to a preparation method of a perylene-based composite material and its application in electrochemiluminescence detection of glucose. Background Art

[0002] Glucose (Glu) is a crucial nutrient for human metabolism. Many chronic diseases, such as cardiovascular disease, hyperglycemia, obesity, and diabetes, are closely related to Glu. Therefore, it is necessary to develop a highly sensitive method for detecting Glu in the human body. Currently, methods for measuring Glu include fluorescence analysis, colorimetry, flow injection analysis, and electrochemiluminescence (ECL). ECL, due to its rapid response, high reliability, and high sensitivity, is one of the most widely used blood glucose detection technologies and holds broad application prospects. Electrochemiluminescence combines the advantages of electrochemistry and spectroscopy, generating light signals electrochemically through the redox reaction of a luminophore. This technique has been widely applied in single-molecule electrochemical reaction imaging, medical diagnostics, environmental monitoring and evaluation, immunoassays, and pharmaceutical analysis. Luminol, with its non-toxicity and high luminescence efficiency, is one of the most classic and common ECL luminescent materials. Excited 3-aminophthalate, the primary emission product of luminol ECL, can be produced using a variety of reactants, including superoxide radicals, hypobromite, or hydrogen peroxide. To date, most conventional luminol-H2O2 ECL systems use H2O2 as a classic co-reactant to generate reactive oxygen species (ROS). ROS react with electrochemically oxidized luminol anions and exhibit significant anodic emission. This invention establishes a new method for detecting Glu using a novel TAPB polymer as an effective co-reactant to induce luminol electroluminescence. Summary of the Invention

[0003] The present invention aims to provide a preparation method of a perylene-based composite material TAPB COF modified electrode with readily available raw materials, simple preparation method, high catalytic efficiency and good selectivity, and its application in electrochemiluminescence detection of Glu.

[0004] The technical solution adopted by the present invention is: a perylene-based composite material, and the preparation method comprises the following steps: mixing perylene-3,4,9,10-tetracarboxylic dianhydride PTCDA and imidazole in DMF, stirring, adding 1,3,5-tris(4-aminophenyl)benzene TAPB dissolved in DMF dropwise, reacting after the dropwise addition is completed, cooling to room temperature and adding methanol, collecting the precipitate by filtration, washing with DMF and methanol, and drying the powder to remove residual imidazole to obtain a deep red powder.

[0005] The above-mentioned perylene-based composite material is stirred at 180°C.

[0006] The above-mentioned perylene-based composite material is reacted at 190° C. for 72 hours.

[0007] The perylene-based composite material has a molar ratio of perylene-3,4,9,10-tetracarboxylic dianhydride to 1,3,5-tris(4-aminophenyl)benzene of 3:2.

[0008] In the above-mentioned perylene-based composite material, the residual imidazole is removed by refluxing methanol at 80°C.

[0009] A perylene-based composite material modified electrode is prepared by dissolving the perylene-based composite material in ethanol, ultrasonically oscillating the perylene-based composite material, and then mixing it with a Nafion ethanol solution and uniformly dispersing it ultrasonically. 5.0 μL of the mixed solution is evenly coated on a treated glassy carbon electrode, and the surface is dried to obtain a perylene-based composite material modified electrode.

[0010] The above-mentioned perylene-based composite modified electrode has a volume ratio of ethanol solution of perylene-based composite material to ethanol solution of Nafion = 1:1, the concentration of the ethanol solution of perylene-based composite material is 1 g / L, and the concentration of the ethanol solution of Nafion is 1%.

[0011] The application of the above-mentioned perylene-based composite material modified electrode in electrochemiluminescence detection of glucose.

[0012] The above application method is as follows: the above-mentioned perylene-based composite material modified electrode is used as the working electrode, the counter electrode is a platinum electrode, the reference electrode is an Ag / AgCl reference electrode, and the electrolyte is 100 mM phosphate buffer, pH = 9 PBS. A constant O2 flow is introduced for 0.5 h before the test. Electrochemical and ECL tests are performed at a scan rate of 50 mV / s under the conditions of a 700 V photomultiplier tube in the voltage range of -1.0 to 0.3 V.

[0013] The beneficial effects of the present invention are:

[0014] 1. This invention utilizes a synthesized catalyst material modified on a glassy carbon electrode for catalytic reaction. The raw materials are readily available, and the synthesis is simple. Prior to ECL measurement, a constant flow of O2 is passed through the electrolyte solution for 0.5 hours to achieve an oxygen-saturated atmosphere, thereby improving the efficiency of the electrocatalytic reaction.

[0015] 2. The catalyst material synthesized in the present invention was used for electrochemiluminescence detection of glucose. By fitting the variation of ECL intensity with Glu concentration, the linear calibration curve with a correlation coefficient of 0.993 and a detection limit of 1.87×10 -5 μM (S / N=3).

[0016] 3. The ECL luminescence intensity of the catalyst material synthesized in the present invention is very stable when continuously scanning 10 cycles of potential in the potential range of -1.2V to 0V in a PBS solution (pH = 9) containing 100mM luminol. The calculated relative standard deviation (RSD) is 3.4%, indicating that the system has good ECL stability and reproducibility. The COF catalyst obtained in the present invention has good application prospects in the field of electrochemiluminescence detection of glucose. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the FT-IR image of the perylene-based composite material TAPB COF modified electrode prepared in Example 1.

[0018] Figure 2 1 is the XRD pattern of TAPB COF powder in the perylene-based composite material TAPB COF modified electrode prepared in Example 1.

[0019] Figure 3 1 is a graph showing the N2 adsorption-desorption test of the perylene-based composite material TAPB COF modified electrode in Example 1 and its corresponding pore size distribution graph.

[0020] Figure 4 This is a comparison chart of the ECL intensity of the perylene-based composite material TAPB COF modified electrode in Example 2 in O2, air and N2 gas.

[0021] Figure 5 This is the stability curve of the luminol electrochemiluminescence system of the perylene-based composite material TAPB COF in Example 2 after 10 scans.

[0022] Figure 6 This is a comparison chart of the ECL intensities of the perylene-based composite material TAPB COF / GCE in Example 2 in Glu solutions of different concentrations.

[0023] Figure 7 is the ΔI and lgC in Example 2 Glu The linear-logarithmic plot of Glu (ΔI=I0-I, where I0 and I are the ECL intensities in the absence and presence of Glu, respectively). DETAILED DESCRIPTION

[0024] Example 1 Preparation of Perylene-based Composite Material TAPB COF Modified Electrode

[0025] (1) The preparation method is as follows:

[0026] 1) Pretreatment of the Glassy Carbon Electrode: Polish a bare glassy carbon electrode to a mirror finish using 3μm Al2O3 powder. Rinse the electrode from the side with distilled water, place it in a bottle of distilled water, and ultrasonicate for 3 minutes. Remove and rinse again with distilled water. Dry the surface with nitrogen. Then, scan the electrode using CV at a scan rate of 0.03V / s in 15mL of 1mmol / L potassium ferricyanide solution. The electrode is considered qualified when the peak potential difference (ΔEp) between the oxidation peak and the reduction peak is 70-80mV, indicating good cleanliness. Rinse again with water, dry with nitrogen, and set aside. If unsatisfactory, re-polish and characterize using CV until a qualified potential difference is achieved.

[0027] 2) Preparation of a perylene-based composite material, TAPB COF: 0.6 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and 20 g of imidazole were mixed in 17 mL of DMF and stirred at 180°C. 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene (TAPB) dissolved in 3 mL of DMF was added dropwise over approximately 20 minutes. The solution was reacted at 190°C for 72 hours. The mixture was then cooled to room temperature and methanol was added. The precipitate was collected by filtration and washed with DMF and methanol. The dried powder was refluxed with methanol at 80°C to remove residual imidazole, yielding a deep red powder.

[0028] 3) Working Electrode Preparation: Dissolve 5.0 mg of TAPB COF powder obtained in step 2) in 5.0 mL of ethanol and sonicate for 1 hour. Then, mix with a 1% Nafion™ ethanol solution at a 1:1 volume ratio and sonicate for 15 minutes to evenly disperse the solution. Apply 5.0 μL of the mixed solution evenly to the treated glassy carbon electrode and allow the surface to dry before use.

[0029] (2) Test results

[0030] Figure 1 The FTIR spectrum of the TAPB COF catalyst powder prepared in Example 1 is shown in Figure 1. The structure of TA-PBCOF was further analyzed and confirmed by infrared spectroscopy. Figure 1 Visible 1698cm -1 、1654cm -1 The asymmetric stretching vibration peak of the carbonyl group in the imide and the peak at 1350 cm -1 The stretching vibration peak of CNC at 3338 cm appears in the infrared absorption curve of TAPB. -1 The -NH2 stretching vibration peak at α-β-D disappeared, indicating that TA-PB COF was successfully prepared. Figure 2The XRD spectrum of the TAPB COF catalyst powder prepared in Example 1 is compared with that of the raw material. In the newly synthesized TA-PB COF catalyst powder, the raw material peak disappears and a (0 0 1) crystal plane appears at 20-30°, proving the formation of a new substance.

[0031] Example 2 Application of perylene-based composite material TAPB COF modified electrode in electrochemiluminescence detection of Glu

[0032] Test method: The prepared TAPB COF-modified glassy carbon electrode was used as the working electrode, the counter electrode was a platinum electrode, the reference electrode was an Ag / AgCl reference electrode, and the electrolyte was 100mM phosphate buffer (PBS, pH=9). A constant O2 flow was introduced for 0.5h before the test. Electrochemical and ECL tests were performed at a scanning speed of 50mV / s in the voltage range of -1.0 to 0.3V and a 700V photomultiplier tube to explore the effect of different concentrations of Glu on the electrochemiluminescence (ECL) intensity.

[0033] The specific surface area of ​​TAPB COF was investigated by nitrogen adsorption test at 77K, such as Figure 3 As shown, TAPB COF exhibits type IV isotherm characteristics, and the BET surface area of ​​TAPT COF is calculated to be 55.04 m 2 ·g -1 ,As can be seen from the inset, the pore size is approximately 20 nm, indicating that the porosity of the material is increased, which is beneficial to the adsorption behavior.

[0034] Example 3 Electrochemiluminescence detection of TAPB COF modified electrode under different atmospheres

[0035] The ECL intensity of TAPB COF modified glassy carbon electrode in O2, air and N2 atmospheres is as follows Figure 4 As shown in the figure, the ECL intensity reaches its highest under O2 saturated conditions. This result proves that O2 is a key species in the electrocatalytic reaction, and its participation in the ORR reaction provides the necessary ROS for the oxidation of luminol, thereby maximizing the ECL signal.

[0036] Stability test such as Figure 5 As shown: First, a PBS solution (pH = 9) containing 100 mM luminol was added to the electrolytic cell, and then the ECL intensity under 10 cycles of potential was continuously scanned in the potential range of -1.2 V to 0 V. The results showed that the ECL intensity was very stable. The relative standard deviation (RSD) was calculated to be 3.4%, indicating that the system has good ECL stability and reproducibility.

[0037] Example 4: Application of Perylene-based Composite Material TAPB COF Modified Electrode in Electrochemiluminescence Detection of Glu

[0038] Depend on Figure 6 , Figure 7 It can be seen that with the change of Glu concentration, the ECL intensity on TA-PB COF / GCE changes, which can be expressed by the equation ΔI = 1045.4logC Glu +4615 describes (ΔI=I0-I, where I0 and I are the ECL intensities in the absence and presence of Glu, respectively). The ECL intensity decreases monotonically with increasing Glu concentration, and the correlation coefficient (R 2 ) was 0.993, indicating a very strong linear correlation between ECL intensity and Glu concentration. In addition, the detection limit of Glu was 1.87×10 -5 μM, which is the lowest concentration measured at a signal-to-noise ratio (S / N) of 3.

[0039] During use, a mixture of TAPB COF powder, ethanol, and Nafion is evenly applied to a pre-treated glassy carbon electrode. Allow the surface to dry before use. Optimizing experimental parameters is crucial for ensuring accuracy and sensitivity in quantitative Glu analysis. Optimization includes, but is not limited to, electrode modification, temperature, pH, and electrolyte selection. Once these parameters are optimized, quantitative analysis performance can be evaluated by testing a series of DA solutions with varying concentrations.

[0040] In summary, the perylene-based composite material TAPB COF modified electrode of the present invention has good sensitivity, selectivity, stability and reproducibility, as well as excellent electrochemiluminescence performance, and has a relatively ideal development prospect in the field of electrochemiluminescence detection of glucose.

Claims

1. Application of a perylene-based composite material modified electrode in electrochemiluminescence detection of glucose, characterized in that: The perylene-based composite material modified electrode is prepared as follows: the perylene-based composite material is dissolved in ethanol, ultrasonically vibrated, and then mixed with a Nafion ethanol solution, ultrasonically dispersed uniformly, and 5.0 μL of the mixed solution is evenly applied to a treated glassy carbon electrode, and the surface is dried to obtain a perylene-based composite material modified electrode. The preparation method of the perylene-based composite material includes the following steps: mixing perylene-3,4,9,10-tetracarboxylic dianhydride PTCDA and imidazole in DMF, stirring, adding 1,3,5-tris(4-aminophenyl)benzene TAPB dissolved in DMF dropwise, reacting after the addition is completed, cooling to room temperature and adding methanol, collecting the precipitate by filtration, washing with DMF and methanol, and drying the powder to remove residual imidazole to obtain a deep red powder.

2. The use according to claim 1, characterized in that The stirring is carried out at 180°C.

3. The use according to claim 1, characterized in that The reaction was carried out at 190°C for 72 h.

4. The use according to claim 1, characterized in that In terms of molar ratio, perylene-3,4,9,10-tetracarboxylic dianhydride:1,3,5-tris(4-aminophenyl)benzene=3:

2.

5. The use according to claim 1, characterized in that The removal of residual imidazole is performed by refluxing methanol at 80°C.

6. The use according to claim 1, characterized in that By volume ratio, the ethanol solution of the perylene-based composite material: the ethanol solution of Nafion is 1:1, the concentration of the ethanol solution of the perylene-based composite material is 1 g / L, and the concentration of the ethanol solution of Nafion is 1%.

7. The use according to claim 1, characterized in that The method is as follows: a perylene-based composite material modified electrode is used as the working electrode, a platinum sheet electrode is used as the counter electrode, an Ag / AgCl reference electrode is used as the reference electrode, and a 100 mM phosphate buffer solution, pH = 9, is used as the electrolyte. A constant O2 flow is introduced for 0.5 h before the test. Electrochemical and ECL tests are performed at a scan rate of 50 mV / s in the voltage range of -1.0~0.3 V and a 700 V photomultiplier tube.

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