(R)-BNDE-PyTTA-COF polymer as well as preparation method and application thereof
The (R)-BNDE-PyTTA-COF polymer prepared by solvothermal method was used as a fluorescent probe, which solved the shortcomings of covalent organic framework materials in the enantioselective recognition of chiral organic molecules and achieved efficient and stable fluorescent probe detection.
Patent Information
- Application Number
- CN202511313559.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-15
- Publication Date
- 2025-12-12
AI Technical Summary
Existing technologies have limited applications of covalent organic framework materials in the enantioselective recognition of chiral organic molecules, and the sensitivity and selectivity of fluorescent probe methods for the detection of trace analytes need to be improved.
(R)-BNDE-PyTTA-COF polymer containing imine bonds was synthesized by a solvothermal method. The imine condensation reaction catalyzed by acetic acid was used to prepare (R)-BNDE-PyTTA-COF polymer with high crystallinity and stability, which was then used as a fluorescent probe for enantioselective recognition of chiral organic molecules.
An enantioselective fluorescence enhancement ratio of 3.2 was achieved, with a greater fluorescence response to (R)-α-phenylethylamine than to (S)-α-phenylethylamine. Furthermore, the polymer maintained good crystallinity and stability after five cycles, thus improving the reusability and detection efficiency of the fluorescent probe.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of porous organic polymer materials, and particularly relates to a (R)-BNDE-PyTTA-COF polymer and a preparation method and application thereof. BACKGROUND
[0002] The information disclosed in the background of the present application is only intended to increase the understanding of the overall background of the present application and should not necessarily be regarded as acknowledging or implicitly suggesting that this information constitutes prior art known to those of ordinary skill in the art.
[0003] Covalent organic framework materials (COFs) are a class of crystalline porous organic polymer materials, which have highly ordered structure, adjustable pore channel, and high porosity, low density and excellent stability. Due to the strong designability of the synthesis unit and the connection mode, the function of COFs materials can be precisely controlled at the molecular level, thus showing broad application potential in the field of fluorescence sensing, especially in the enantioselective recognition of chiral organic molecules.
[0004] The fluorescence probe method is an analysis technology based on the change of fluorescence signal to realize the detection of target substances. The basic principle is that the probe molecule and the analyte have specific interaction (such as chemical reaction), which causes measurable changes in fluorescence properties (such as intensity, emission wavelength or lifetime, etc.), thereby realizing the qualitative and quantitative analysis of target substances. This method has the significant advantages of high selectivity and high sensitivity: the probe can be designed to recognize sites according to the structure of the target substance, which can effectively distinguish target molecules and reduce interference even in complex matrix; at the same time, this method can still produce a significant response to trace analytes, and reliable detection can be realized at very low concentrations, so it has wide application in important fields such as environmental monitoring, biological sensing and chiral recognition. However, there are few reports on the application of covalent organic framework materials to enantioselective recognition of chiral organic molecules. SUMMARY
[0005] Therefore, the present application provides a (R)-BNDE-PyTTA-COF polymer and a preparation method and application thereof.
[0006] In order to achieve the above purpose, the present application is realized by the following technical scheme: In a first aspect, the present application provides a (R)-BNDE-PyTTA-COF polymer, wherein the (R)-BNDE-PyTTA-COF polymer takes a structure represented by formula (I) as a structural repeat unit.
[0007] Formula (I).
[0008] The (R)-BNDE-PyTTA-COF polymer is an imine bond-containing COF polymer.
[0009] In a second aspect, the present application provides a preparation method of the (R)-BNDE-PyTTA-COF polymer of the first aspect, comprising: The ligand (R)-BINOLDE-DA and 1,3,6,8-(4-aminophenyl)pyrene (PyTTA) are dispersed in an organic solvent, and a solvent thermal reaction is carried out after adding a catalyst to obtain the (R)-BNDE-PyTTA-COF polymer.
[0010] Further, the catalyst is acetic acid. The acetic acid has a better catalytic effect on the imine condensation reaction than other catalysts.
[0011] Further, the organic solvent is a mixed solution of mesitylene and ethanol, and the volume ratio of mesitylene to ethanol is (2.8-3.2):(0.8-1.2), preferably 3:1.
[0012] Further, the molar ratio of (R)-BINOLDE-DA to 1,3,6,8-(4-aminophenyl)pyrene (PyTTA) is (1.8-2.2):(0.8-1.2), preferably 2:1.
[0013] Further, the temperature of the solvent thermal reaction is 130-140 ℃, preferably 120 ℃, and the time of the solvent thermal reaction is 96-144 h, preferably 120 h. Under this temperature and time, the reaction can be better carried out.
[0014] Further, after adding the catalyst, ultrasonic treatment is carried out for 10-30 min. The ultrasonic treatment can make the components better mixed and uniform.
[0015] In a third aspect, the present application provides an application of the (R)-BNDE-PyTTA-COF polymer of the first aspect or the (R)-BNDE-PyTTA-COF polymer prepared by the preparation method of the second aspect as a fluorescent probe.
[0016] Further, the application is an application in enantioselective recognition of chiral organic molecules.
[0017] Further, the application includes enantioselective recognition of (R)-α-phenethylamine and (S)-α-phenethylamine. The (R)-BNDE-PyTTA-COF is used for enantioselective recognition of α-phenethylamine, and the fluorescent response of the (R)-BNDE-PyTTA-COF to (R)-α-phenethylamine is greater than that to (S)-α-phenethylamine.
[0018] In a fourth aspect, the present application provides a method for enantioselective recognition of alpha-phenethylamine, comprising the following steps: The (R)-alpha-phenethylamine or (S)-alpha-phenethylamine and the (R)-BNDE-PyTTA-COF polymer described above are dissolved in an organic solvent, and the reaction is carried out at room temperature to obtain the product.
[0019] Further, the organic solvent is acetonitrile, mesitylene, dimethyl sulfoxide, acetone, o-dichlorobenzene, dichloromethane, chloroform, isopropanol, tetrahydrofuran, ethanol, methanol, and preferably acetonitrile.
[0020] Further, the reaction is carried out for 12-24 hours, and preferably for 24 hours.
[0021] Further, the molar ratio of (R)-alpha-phenethylamine or (S)-alpha-phenethylamine to (R)-BNDE-PyTTA-COF polymer is 100-500:1, and preferably 100-300:1.
[0022] Compared with the prior art, the present application has the following beneficial effects: In the present application, (R)-BINOLDE-DA is used as a new monomer and 1,3,6,8-tetra(4-formylphenyl)pyrene (TFPPY) is used to synthesize a high-stability polymer (R)-BNDE-PyTTA-COF with a urea-like active site by a solvothermal method. The (R)-BNDE-PyTTA-COF has higher crystallinity and stability, and the thermal stability reaches 200°C. As a fluorescent probe, the (R)-BNDE-PyTTA-COF has an enantioselective fluorescence enhancement ratio ef of 3.2 in the enantioselective recognition of alpha-phenethylamine, can be recycled for five times, and still retains good crystallinity. BRIEF DESCRIPTION OF DRAWINGS
[0023] The drawings accompanying the specification of the present application serve to provide a further understanding of the present application, and the illustrative embodiments of the present application and their descriptions serve to explain the present application, and do not constitute an improper limitation on the present application.
[0024] Figure 1 A scanning electron microscope image of the (R)-BNDE-PyTTA-COF polymer prepared in Example 1; Figure 2 A thermogravimetric diagram of the (R)-BNDE-PyTTA-COF polymer prepared in Example 1; Figure 3 A PXRD diagram of the (R)-BNDE-PyTTA-COF polymer prepared in Example 1; Figure 4 An infrared diagram of the (R)-BNDE-PyTTA-COF polymer prepared in Example 1; Figure 5 N2adsorption plot of (R)-BNDE-PyTTA-COF polymer prepared for Example 1; Figure 6 I value plot of (R)-BNDE-PyTTA-COF polymer prepared for Experimental Example 1 after 5 cycles as a fluorescent probe. R / I S DETAILED DESCRIPTION
[0025] It should be noted that the following detailed description is merely exemplary and is intended to provide further description of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
[0026] The technical solutions of the present application will be further described below in combination with specific examples.
[0027] Example 1 Preparation of (R)-BNDE-PyTTA-COF polymer: The ligand (R)-BINOLDE-DA (6.0 mg, 0.00970 mmol) and PyTTA (2.8 mg, 0.00494 mmol) were added to a test tube, and mesitylene / ethanol (volume ratio 3:1, 2.00 mL) and HAc (6 M, 200 μL) were added to the test tube, which was ultrasonicated for 20 min and sealed. The reaction was carried out at 120°C for five days. After being washed with DMF, ethanol and dichloromethane for five times respectively, the yellow-green solid 5 mg was obtained by vacuum drying, and the yield was 59.5%.
[0028] The (R)-BNDE-PyTTA-COF polymer prepared in this example was characterized. Figure 1 The transmission electron microscopy plot of (R)-BNDE-PyTTA-COF polymer. Figure 2 The thermogravimetric plot of (R)-BNDE-PyTTA-COF polymer. Figure 3 The PXRD plot of (R)-BNDE-PyTTA-COF polymer. Figure 4 The infrared spectrogram of (R)-BNDE-PyTTA-COF polymer. Figure 5 The N2adsorption plot of (R)-BNDE-PyTTA-COF polymer. From Figure 1 , Figure 3 and Figure 5 It can be seen from the above that the (R)-BNDE-PyTTA-COF polymer prepared in this example has a porous structure. From Figure 2 it can be seen that the (R)-BNDE-PyTTA-COF polymer has high thermal stability. From Figure 4 The molecular structure and chemical bonds of the (R)-BNDE-PyTTA-COF polymer can be seen.
[0029] Example 2 (R)-BNDE-PyTTA-COF polymer prepared in Example 1 as a fluorescent probe for enantioselective recognition of α-phenethylamine (R)-α-phenethylamine (8 x 10 -3 mmol) and (R)-BNDE-PyTTA-COF (4 x 10 -5 mmol) was dissolved in acetonitrile (4 mL), left for 24 h, shaken uniformly, and its fluorescence emission spectrum was measured at room temperature with an excitation wavelength of 390 nm and an emission wavelength of 480 nm, and the fluorescence emission intensity I R at a wavelength of 480 nm was recorded.
[0030] The above (R)-α-phenethylamine (8 x 10 -3 mmol) was replaced with (S)-α-phenethylamine (8 x 10 -3 mmol), and the above operation was repeated, and its fluorescence emission spectrum was measured, and the fluorescence emission intensity I S at a wavelength of 480 nm was recorded, and I R / I S was calculated. After the reaction was completed, the COF was separated by centrifugation.
[0031] The reaction was tracked by TLC, and after the reaction was completed, the fluorescent probe was recovered by centrifugation and directly used in the next cycle of reaction. According to the above conditions, the fluorescent probe was used for five cycles, and I R / I S was calculated. Figure 5 The I R / I S value graph of the fluorescent probe after 5 cycles is shown in Figure Figure 6 It can be seen that after 5 cycles of the fluorescent probe, the (R)-BNDE-PyTTA-COF polymer framework did not change. As can be seen from Table 1, the yield of the product remained basically unchanged, and after five cycles, only a slight downward trend was shown, which reflects the excellent stability of the catalyst, which can be reused for more than five times, can significantly improve the utilization rate of the catalyst, and reduce the production cost.
[0032] Table 1 Catalytic effect of PA-COF polymer in multiple cycle reactions
[0033] As the fluorescent probe, the (R)-BNDE-PyTTA-COF polymer provided by the application has an enantioselective fluorescence enhancement ratio of 3.2 in the enantioselective recognition of alpha-phenylethylamine. Meanwhile, the (R)-BNDE-PyTTA-COF polymer still has good crystallinity after five cycles of reaction, and therefore it can be proved that the (R)-BNDE-PyTTA-COF polymer provided by the application has high and stable catalytic performance and can be recycled for multiple times.
[0034] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A (R)-BNDE-PyTTA-COF polymer, characterized in that, The (R)-BNDE-PyTTA-COF polymer uses the structure shown in formula (Ⅰ) as the repeating unit. Equation (Ⅰ).
2. The method for preparing the (R)-BNDE-PyTTA-COF polymer as described in claim 1, characterized in that, Includes the following steps: The ligand (R)-BINOLDE-DA and 1,3,6,8-(4-aminophenyl)pyrene (PyTTA) were dispersed in an organic solvent, and a catalyst was added before a solvothermal reaction was carried out to obtain the (R)-BNDE-PyTTA-COF polymer.
3. The preparation method according to claim 2, characterized in that, The organic solvent is a mixed solution of mesitylene and ethanol, wherein the volume ratio of mesitylene to ethanol is (2.8~3.2):(0.8~1.2), preferably 3:1; or, the catalyst is acetic acid.
4. The preparation method according to claim 2, characterized in that, The molar ratio of (R)-BINOLDE-DA to 1,3,6,8-(4-aminophenyl)pyrene (PyTTA) is (1.8~2.2):(0.8~1.2), preferably 2:
1.
5. The preparation method according to claim 2, characterized in that, After adding the catalyst, the mixture is subjected to ultrasonic treatment for 10-30 minutes.
6. The preparation method according to claim 2, characterized in that, The temperature of the solvothermal reaction is 130~140 ℃, preferably 120 ℃; or the time of the solvothermal reaction is 96~144 h, preferably 120 h.
7. The application of the (R)-BNDE-PyTTA-COF polymer as described in claim 1 as a fluorescent probe, preferably, in the enantioselective recognition of chiral organic molecules.
8. The application as described in claim 7, characterized in that, The applications include enantioselective recognition of (R)-α-phenylethylamine and (S)-α-phenylethylamine.
9. A method for enantioselective recognition of α-phenylethylamine, characterized in that, Includes the following steps: The (R)-α-phenylethylamine or (S)-α-phenylethylamine and the (R)-BNDE-PyTTA-COF polymer of claim 1 are dissolved in an organic solvent and reacted at room temperature to obtain the product.
10. The method as described in claim 9, characterized in that, The organic solvent is acetonitrile, mesitylene, dimethyl sulfoxide, acetone, o-dichlorobenzene, dichloromethane, chloroform, isopropanol, tetrahydrofuran, ethanol, or methanol, preferably acetonitrile; or, the reaction time is 12-24 h, preferably 24 h; or, the molar ratio of (R)-α-phenylethylamine or (S)-α-phenylethylamine to (R)-BNDE-PyTTA-COF polymer is 100-500:1; preferably 100-300:1.