Porous crystal polymer as well as preparation method and application thereof

Abstract

The invention discloses a porous crystal polymer, namely a one-dimensional chiral covalent organic framework (R)-PTCDA-RMP as well as a preparation method and application thereof, and belongs to the technical fields of nano materials, covalent organic frameworks and electrochemical detection. The material is prepared by heating 3, 4, 9, 10-perylene tetracarboxylic dianhydride PTCDA and (R)-(-)-2-methylpiperazine RMP under the catalysis of imidazole, the structure endows the material with adjustable surface charges in an alkaline environment and endows the material with dispersion and anti-aggregation capacities, and an electrochemiluminescence chiral sensor constructed by the material has the advantages of high sensitivity, high sensitivity and high sensitivity. The D / L-penicillamine enantiomer can be simply, quickly and highly specifically recognized and detected.

Description

Technical Field

[0001] The invention relates to a porous crystalline polymer, namely a one-dimensional chiral covalent organic framework (R)-PTCDA-RMP and a preparation method and application thereof, belonging to the technical field of nanomaterials, covalent organic frameworks and electrochemical detection. Background Art

[0002] In the field of analytical chemistry, accurate detection of enantiomers is of great significance due to their unique biological activity and potential impact on the environment. Electrochemiluminescence (ECL) has become a powerful tool for enantiomer detection with its advantages of high sensitivity and low background noise. The core of the progress of ECL enantiomer analysis lies in the research and development of new materials. Only when the materials used selectively produce different interactions with left-handed and right-handed enantiomers and convert these interactions into detectable ECL signals can effective analysis of enantiomers be achieved.

[0003] Cong's team synthesized a macrocyclic compound [Ultrasensitive sensor for L -penicillamine with chirality-induced amplification of benzo[3]uril electrochemiluminescence via supramolecular interactions. Sensors and Actuators B: Chemical . 2022, 362: 131801], the constructed ECL sensor can capture the specific chiral enantiomers of penicillamine and show different ECL intensities through different adsorption effects. Wang et al. developed doped chiral CuO / CoO NFs and used chiral cysteine ​​to electrochemically recognize dopamine (DOPA) enantiomers [Nitrogen-Doped Chiral CuO / CoO Nanofibers: An EnhancedElectrochemiluminescence Sensing Strategy for Detection of 3,4-Dihydroxy-Phenylalanine Enantiomers. Analytical Chemistry . 2021, 93(33): 11470-11478]; the compound has a higher oxidation preference for L-dopamine, a higher electron transfer rate with L-DOPA, and produces a stronger ECL signal. However, the current method is limited in that the two enantiomers show different intensities of ECL signals; this method leads to inaccuracy in the identification and analysis of a pair of enantiomers.

[0004] Covalent organic frameworks (COFs) are a new class of porous, covalently assembled crystalline polymers. COFs have excellent properties such as high surface area, ordered porosity, water resistance, and low toxicity, making them ideal for separations and sensing. Ionic COFs extend this versatility by having ionizable functional groups, allowing for adjustable surface charge; this adjustability is advantageous for chiral recognition because it can adjust the electrostatic environment around the chiral center and enhance the discrimination between enantiomers. In addition, the ability of this material to dynamically adjust the signal response makes ionic COFs a versatile tool for molecular sensing and detection.

[0005] The present invention discloses a one-dimensional chiral COF synthesized by co-condensation of π-conjugated 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and chiral (R)-2-methylpiperazine (RMP); this structure gives the COF an adjustable surface charge in an alkaline environment, thereby regulating its aggregation and dispersion in the detection environment, thereby producing different ECL responses, which is crucial for distinguishing enantiomers.

[0006] The sensor constructed with this chiral COF showed an excellent ability to distinguish the ECL signals of D / L-penicillamine (PA) enantiomers, providing a significant advantage over existing ECL technology.

[0007] The conventional ECL sensor has the same signal response trend for the two enantiomers, with only a change in the amplitude of the signal change, while the sensor of the present invention has a unique bidirectional change in the ECL intensity. Among them, D-PA can significantly enhance the ECL signal, while L-PA significantly reduces the ECL signal. The response to each enantiomer is a breakthrough in ECL sensing analysis and detection, allowing not only effective qualitative identification, but also quantification of chiral molecules based on the degree of change in the ECL signal. This precise chiral identification and quantification capability is expected to greatly improve the accuracy and reliability of the analysis results, opening up a new approach in the field of chiral analysis and molecular diagnostic technology. Summary of the invention

[0008] One of the technical tasks of the present invention is to make up for the deficiencies of the prior art and provide a porous crystalline polymer, namely a one-dimensional chiral covalent organic framework (R)-PTCDA-RMP COF. The COF has an adjustable surface charge in an alkaline environment, thereby giving it dispersion and anti-aggregation properties in a detection environment. The electrochemiluminescence (ECL) chiral sensor constructed from the material has an ECL signal intensity significantly stronger in an alkaline environment than in an acidic environment. The second technical task of the present invention is to provide a method for preparing the (R)-PTCDA-RMP COF, which has low raw material cost, simple preparation process, low reaction energy consumption and has industrial application prospects.

[0009] The third technical task of the present invention is to provide the use of (R)-PTCDA-RMP COF, which is used to construct an electrochemiluminescent ECL material sensor and shows excellent resolution ability to distinguish the ECL signals of D- and L-PA enantiomers.

[0010] To achieve the above purpose, the technical solution adopted by the present invention is as follows: 1. A porous crystalline polymer, wherein the porous crystalline polymer is a one-dimensional chiral covalent organic framework, namely a one-dimensional chiral (R)-PTCDA-RMP COF, wherein the structural formula of (R)-PTCDA-RMP is as follows:

[0011] (R)-PTCDA-RMP is a mesoporous material composed of leaf-shaped nanosheets. The electrochemiluminescence (ECL) chiral sensor constructed with this material has a significantly stronger signal intensity in an alkaline environment than in an acidic environment, especially when D-penicillamine causes an enhancement in its ECL signal, while L-penicillamine causes a quenching of its ECL signal.

[0012] 2. The porous crystalline polymer as described above is prepared as follows: The solvothermal method is adopted for synthesis. First, 1.0-1.5 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and 4.0-4.5 mM of (R)-(-)-2-methylpiperazine RMP are mixed, and 40-60 mM of imidazole catalyst is added; the mixture is heated at 120°C for 12-24 h under stirring; after the reaction is completed, the system is cooled to 70-85°C, filtered, and the obtained solid is washed with deionized water for 3-5 times to remove the unreacted starting material and catalyst, and then vacuum dried at 80°C to remove the solvent and achieve high porosity to obtain a one-dimensional chiral ion (R)-PTCDA-RMP covalent organic framework COF, that is, a porous crystalline polymer (R)-PTCDA-RMPCOF; the preparation reaction formula is as follows:

[0013] 3. Use of the porous crystalline polymer as described above for detecting enantiomers, the steps being as follows: (1) Construction of ECL chiral sensor The platinum carbon electrode GCE with a diameter of 4 mm was finely polished using 0.05 μm α-AlO2 polishing powder; the electrode was then ultrasonically cleaned in ultrapure water and ethanol baths in turn, and then gently dried at room temperature; 6 mg of (R)-PTCDA-RMP and the sample to be tested were accurately weighed and dispersed in N,N-dimethylformamide (DMF) to form a uniform solution with a (R)-PTCDA-RMP concentration of 4 mg / mL; the solution was then ultrasonically treated to ensure that the (R)-PTCDA-RMP and the sample to be tested were uniformly dispersed; subsequently, 8 μL of the well-dispersed solution was carefully coated on the GCE surface and air-dried at room temperature; finally, the electrode was rinsed with ultrapure water to remove any nonspecifically adsorbed substances and air-dried at room temperature to obtain the (R)-PTCDA-RMP / ECL sensor.

[0014] (2) Enantioselective detection Enantioselective detection was carried out in a three-electrode system with (R)-PTCDA-RMP / GCE as the working electrode; a silver chloride electrode as the reference electrode and a platinum wire electrode as the auxiliary electrode; the electrolyte medium consisted of 0.1 M phosphate buffer solution (PBS) adjusted to pH 8.04 and supplemented with 0.1 M potassium persulfate (K2S2O8) as a co-reactant; the ECL detection photomultiplier tube operated at 600 V high voltage, with a potential scanning range from 0 to -1.6 V and a scanning rate of 0.2 mV / s to ensure the consistency and repeatability of the results.

[0015] Using Materials Studio software to simulate the (R)-PTCDA-RMP COF structure, (R)-PTCDA-RMPCOF has two prominent peaks at 11.98° and 24.58°, accompanied by an additional peak at 27.42°; these reflections correspond to the 100, 010, and 012 planes, respectively. Experimental PXRD Figure 1 The difference from this peak is negligible; Scanning electron microscopy (SEM) characterization of the (R)-PTCDA-RMP COF showed that (R)-PTCDA-RMP COF is composed of nanosheets with unique leaf-like contours; these nanosheets have a large specific surface area and a high degree of porosity; the presence of a special microporous framework gives the COF a large number of active sites, which is crucial for improving the sensitivity and selectivity of sensing applications.

[0016] Nitrogen adsorption-desorption tests on (R)-PTCDA-RMP COF showed that the COF exhibited a type III isotherm, which indicates that it is a mesoporous material, and the Brunauer-Emmet-Teller (BET) surface area was measured to be 14.7540±1.8679 m² / g.

[0017] Circular dichroism (CD) spectroscopy confirmed the chiral optical properties of (R)-PTCDA-RMPCOF, with a distinct peak at about 440 nm indicating the intrinsic chirality of the material, which provides evidence of its intrinsic structure for enantioselective interactions and confirms its potential for chiral recognition and sensing applications.

[0018] The (R)-PTCDA-RMP COF was coated on GCE for ECL analysis. The results showed that the ECL signal intensity of (R)-PTCDA-RMP / GCE gradually increased with the increase of pH. The ECL signal intensity in alkaline solution was significantly stronger than that in acidic and neutral environments. Penicillamine (PA) is a metabolite of penicillin, which exhibits different pharmacological activities or toxicities in organisms. D-PA has medical value in the treatment of heavy metal poisoning, Wilson's disease and rheumatoid arthritis, while L-PA can cause adverse reactions such as neuritis, osteomyelitis and olfactory and visual degeneration.

[0019] The results showed that the ECL signal of (R)-PTCDA-RMP / GCE showed different responses to L-PA and D-PA. D-PA enhanced the ECL signal intensity, while L-PA showed a significant quenching effect on the ECL signal intensity.

[0020] The analytical capability of the (R)-PTCDA-RMP / GCE sensor was further investigated. The ECL signal intensity was proportional to the D-PA concentration and inversely proportional to the L-PA concentration. In the range of 50 μM to 1 mM, there was a strong linear correlation between the ECL intensity and the D / L-PA concentration. The linear regression equations for L-PA and D-PA were ECL and L‐PA = -2730.98C (mM) +5888.81 (R2 = 0.9040) and ECL D‐PA = 1780.32C (mM) + 5950.54 (R = 0.9606).

[0021] In order to verify the specificity of the sensor for identifying and detecting penicillamine PA enantiomers, a series of control experiments were carried out on various amino acid enantiomers such as carnitine (Car), methionine (Met), alanine (Ala), serine (Ser), valine (Val), phenylalanine (Phe) and glutamic acid (Glu). The experimental results showed that, except for D / L-PA, the difference between the left-right rotating ECL signals of other enantiomers was very small, confirming the specificity of the sensor in selectively identifying and detecting D / L-PA enantiomers.

[0022] In order to evaluate the actual effect of the established chiral detection sensor, the present invention uses (R)-PTCDA-RMP / GCE to perform ECL detection on mixtures of D-PA and L-PA in different proportions. The total concentration of D-PA and L-PA is maintained at 1 mM. The research results show that the ECL signal is linearly correlated with the proportion of D-PA in the mixture, thereby determining the accurate identification of the PA mixture.

[0023] Beneficial technical effects of the present invention (1) 3,4,9,10-Perylenetetracarboxylic dianhydride (PTCDA) has no chiral sites and cannot identify and detect chiral compounds. In this study, a chiral (R)-PTCDA-RMP COF, a chiral electrochemiluminescent (ECL) material, was synthesized by solvothermal synthesis based on 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and chiral (R)-2-methylpiperazine RMP. This method has low raw material cost, simple preparation process, low reaction energy consumption, and has industrial application prospects.

[0024] (2) The electrochemiluminescence (ECL) chiral sensor (R)-PTCDA-RMP / GCE constructed by the present invention using (R)-PTCDA-RMP COF is used for chiral recognition and detection of D / L-PA enantiomers. D-PA leads to an enhancement of its ECL signal intensity, while L-PA shows a significant quenching effect on the ECL signal intensity, which lays the foundation for accurate recognition and detection.

[0025] (3) The (R)-PTCDA-RMP of the present invention is a one-dimensional COF, and its ECL signal gradually increases with the increase of pH, significantly increases in alkaline environment, and significantly decreases in acidic environment. In alkaline environment, it is a one-dimensional ionic COF material. This obvious sensitivity to pH changes is because the (R)-PTCDA-RMP COF framework contains carboxyl and perylene structural units. This pH-dependent behavior is because under alkaline conditions, the protonation of the basic N in the COF framework is avoided, resulting in the destruction of the conjugated structure with the carbonyl group; and the carboxyl group can be deprotonated, and the negative charge introduced on the COF chain. Both of these effects can lead to an increase in electron density, and due to the electrostatic repulsion between adjacent chains, their aggregation is prevented, which enhances the electron transfer process necessary for ECL. This dispersed state is conducive to maintaining the ECL activity of the perylene unit, thereby allowing effective ECL release; the repulsion between negatively charged chains can also reduce the non-radiative energy transfer pathway, thereby maintaining ECL. signal intensity; in contrast, under neutral conditions, the degree of ionization of the carboxylic acid groups is low and the electrostatic repulsion is weakened. This reduction in repulsion brings the COF chains closer together and interacts through the π-π stacking of perylene, leading to the formation of aggregates. The aggregation of COF chains restricts the molecular motion of perylene, thereby reducing the efficiency of the electron transfer process; in addition, aggregation can promote non-radiative energy transfer and quenching pathways, thereby reducing the ECL signal; this aggregation-induced quenching (AIQ) effect is believed to be the reason for the reduction in ECL signal observed under neutral conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 PXRD spectrum of (R)-PTCDA-RMP (red curve) and simulated standard spectrum (green curve); Figure 2 is the CD spectrum of (R)-PTCDA-RMP; Figure 3 is the effect of pH on the ECL signal intensity of (R)-PTCDA-RMP / GCE; Figure 4 are the ECL spectra of bare GCE, (R)-PTCDA-RMP / GCE, L-PA / (R)-PTCDA-RMP / GCE, and D-PA / (R)-PTCDA-RMP / GCE; Figure 5 Linear relationship between the ECL signal of (R)-PTCDA-RMP COF and the concentrations of L-PA (red line) and D-PA (green line) Figure 6 ECL signals of (R)-PTCDA-RMP / GCE in different enantiomers at 1 mM Figure 7 The linear relationship between the effect of D-PA concentration on the ECL signal (A) and ECL intensity (B) of the mixture of D- and L-PA at different ratios Specific implementation methods

[0027] Example 1 A method for preparing a porous crystalline polymer

[0028] The solvothermal method was used for synthesis. First, 1.0 mM 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and 4.0 mM (R)-(-)-2-methylpiperazine RMP were mixed, and 40 mM imidazole catalyst was added; the mixture was heated at 120 °C for 12 h under stirring; after the reaction, the system was cooled to 70 °C and filtered. The obtained solid was washed with deionized water three times to remove the unreacted starting material and catalyst, and then vacuum dried at 80 °C to remove the solvent and achieve high porosity to obtain a one-dimensional chiral (R)-PTCDA-RMP covalent organic framework COF, that is, a porous crystalline polymer (R)-PTCDA-RMP COF. The preparation reaction formula is as follows: .

[0029] Example 2 A method for preparing a porous crystalline polymer

[0030] The synthesis was carried out by a solvothermal method. First, 1.5 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and 4.5 mM of (R)-(-)-2-methylpiperazine RMP were mixed, and 60 mM of an imidazole catalyst was added; the mixture was heated at 120°C for 24 hours under stirring; after the reaction, the system was cooled to 85°C and filtered, and the obtained solid was washed with deionized water for 5 times to remove unreacted starting materials and catalysts, and then vacuum dried at 80°C to remove the solvent and achieve high porosity to obtain a one-dimensional chiral ion (R)-PTCDA-RMP covalent organic framework COF, i.e., a porous crystalline polymer (R)-PTCDA-RMP COF, and the preparation reaction formula was the same as that in Example 1.

[0031] Example 3 A method for preparing a porous crystalline polymer

[0032] The synthesis was carried out by a solvothermal method. First, 1.3 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and 4.3 mM of (R)-(-)-2-methylpiperazine RMP were blended, and 50 mM of an imidazole catalyst was added; the mixture was heated at 120°C for 13 h under stirring; after the reaction, the system was cooled to 80°C and filtered, and the obtained solid was washed with deionized water for 4 times to remove unreacted starting materials and catalysts, and then vacuum dried at 80°C to remove the solvent and achieve high porosity to obtain a one-dimensional chiral ion (R)-PTCDA-RMP covalent organic framework COF, i.e., a porous crystalline polymer (R)-PTCDA-RMP COF, and the preparation reaction formula was the same as that in Example 1.

[0033] Example 4. Characterization of the structure and performance of the materials obtained in Example 1, Example 2 and Example 3 The (R)-PTCDA-RMP COF structure was simulated using Materials Studio software. The results are shown in the green line in Figure 1. (R)-PTCDA-RMP COF has two prominent peaks at 11.98° and 24.58°, accompanied by an additional peak at 27.42°; these reflections correspond to the 100, 010, and 012 planes, respectively. The experimental PXRD Figure 1 The difference between the main peak of the red line and this peak is negligible.

[0034] Scanning electron microscopy (SEM) characterization of the (R)-PTCDA-RMP COF showed that (R)-PTCDA-RMP COF is composed of nanosheets with unique leaf-like contours; these nanosheets have a large specific surface area and a high degree of porosity; the presence of a special microporous framework gives the COF a large number of active sites, which is crucial for improving the sensitivity and selectivity of sensing applications.

[0035] Nitrogen adsorption-desorption tests on (R)-PTCDA-RMP COF showed that the COF exhibited a type III isotherm, which indicates that it is a mesoporous material, and the Brunauer-Emmet-Teller (BET) surface area was measured to be 14.7540±1.8679 m² / g.

[0036] Depend on Figure 2 The CD spectrum of (R)-PTCDA-RMPCOF shows a distinct peak at about 440 nm, indicating the intrinsic chirality of the material, which provides evidence of its intrinsic structure for enantioselective interactions and confirms its potential for chiral recognition and sensing applications.

[0037] Example 5 Construction of ECL chiral sensor using the porous crystalline polymer prepared in Examples 1-3

[0038] The platinum carbon electrode GCE with a diameter of 4 mm was finely polished using 0.05 μm α-AlO2 polishing powder; the electrode was then ultrasonically cleaned in ultrapure water and ethanol baths in turn, and then gently dried at room temperature; 6 mg of (R)-PTCDA-RMP and the sample to be tested prepared in Example 1, Example 2 or Example 3 were accurately weighed and dispersed in N,N-dimethylformamide DMF to form a uniform solution with a (R)-PTCDA-RMP concentration of 4 mg / mL; the solution was then ultrasonically treated to ensure that the (R)-PTCDA-RMP and the sample to be tested were uniformly dispersed; then, 8 μL of the well-dispersed solution was carefully coated on the GCE surface and air-dried at room temperature; finally, the electrode was rinsed with ultrapure water to remove any nonspecifically adsorbed substances and air-dried at room temperature to obtain a (R)-PTCDA-RMP / ECL sensor.

[0039] Example 6: Application of the ECL chiral sensor constructed in Example 5 for enantioselective detection

[0040] Enantioselective detection was carried out in a three-electrode system, with (R)-PTCDA-RMP / GCE as the working electrode; a silver chloride electrode as the reference electrode and a platinum wire electrode as the auxiliary electrode; the electrolyte medium consisted of 0.1 M phosphate buffer solution (PBS) adjusted to pH 8.04 and supplemented with 0.1 M potassium persulfate (K2S2O8) as a co-reactant; the ECL detection photomultiplier tube operated at 600 V high voltage, with a potential scanning range from 0 to -1.6 V and a scanning rate of 0.2 mV / s to ensure the consistency and repeatability of the results; Depend on Figure 3 It can be seen that the ECL signal intensity of (R)-PTCDA-RMP / GCE gradually increases with the increase of pH, and the ECL signal intensity in alkaline solution is significantly stronger than that in its acidic and neutral environments.

[0041] Penicillamine (PA) is a metabolite of penicillin, which exhibits different pharmacological activities or toxicities in organisms. D-PA has medical value in the treatment of heavy metal poisoning, Wilson's disease and rheumatoid arthritis, while L-PA can cause adverse reactions such as neuritis, osteomyelitis and olfactory and visual degeneration; like Figure 4 As shown, the ECL signal of (R)-PTCDA-RMP / GCE showed different responses to L-PA and D-PA. D-PA led to an enhancement of its ECL signal intensity, while L-PA showed a significant quenching effect on the ECL signal intensity.

[0042] Figure 5 The analytical capability of the (R)-PTCDA-RMP / GCE sensor was further confirmed and evaluated. The ECL signal intensity was proportional to the D-PA concentration and inversely proportional to the L-PA concentration. In the range of 50 μM to 1 mM, there was a strong linear correlation between the ECL intensity and the D / L-PA concentration. The linear regression equations for L-PA and D-PA were ECL and L‐PA = -2730.98C (mM) + 5888.81 (R2 = 0.9040) and ECL D‐PA = 1780.32C (mM) + 5950.54 (R =0.9606).

[0043] In order to verify the specificity of the sensor for the recognition and detection of penicillamine PA enantiomers, a series of control experiments were carried out on various amino acid enantiomers such as carnitine (Car), methionine (Met), alanine (Ala), serine (Ser), valine (Val), phenylalanine (Phe) and glutamic acid (Glu). Figure 6 The experimental results show that, except for D / L-PA, the left-right and right-handed ECL signal differences of other enantiomers are extremely small, confirming the specificity of the sensor in selectively identifying and detecting D / L-PA enantiomers.

[0044] In order to evaluate the actual effect of the established chiral detection sensor, the present invention uses (R)-PTCDA-RMP / GCE to perform ECL detection on mixtures of D-PA and L-PA in different ratios, with the total concentration of D-PA and L-PA maintained at 1 mM. Figure 7 The results showed that the ECL signal was linearly correlated with the ratio of D-PA in the mixture, thus confirming the accurate identification of PA mixtures.

Claims

1. A porous crystalline polymer, characterized in that: The porous crystalline polymer is a one-dimensional chiral covalent organic framework, i.e., a one-dimensional chiral (R)-PTCDA-RMP COF; The (R)-PTCDA-RMP is a mesoporous material composed of nanosheets with leaf-like profiles; the structure belongs to a one-dimensional ionic COF in an alkaline environment, and the negative charge it carries gives it the ability to disperse and resist aggregation; The electrochemiluminescence (ECL) chiral sensor constructed with this material has a significantly stronger ECL signal intensity in an alkaline environment than in an acidic environment. D-penicillamine leads to enhancement of its ECL signal, while L-penicillamine leads to quenching of its ECL signal; The structural formula of the (R)-PTCDA-RMP is as follows: 。 2. The porous crystalline polymer according to claim 1, characterized in that The preparation method is as follows: The solvothermal method is adopted for synthesis. First, 1.0-1.5 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and 4.0-4.5 mM of (R)-(-)-2-methylpiperazine RMP are mixed, and 40-60 mM of imidazole catalyst is added; the mixture is heated at 120 ° C for 12-24 h under stirring; after the reaction is completed, the system is cooled to 70-85 ° C, filtered, and the obtained solid is washed with deionized water for 3-5 times to remove the unreacted starting material and catalyst, and then vacuum dried at 80 ° C to remove the solvent and achieve high porosity to obtain a one-dimensional chiral (R)-PTCDA-RMP covalent organic framework COF, that is, a porous crystalline polymer (R)-PTCDA-RMP COF; the preparation reaction formula is as follows: 。 3. Use of the porous crystalline polymer according to claim 1 for detecting enantiomers.

4. Use of the porous crystalline polymer according to claim 3 for detecting enantiomers, characterized in that: Here are the steps: (1) Construction of ECL chiral sensor The platinum carbon electrode GCE with a diameter of 4 mm was finely polished using 0.05 μm α-AlO2 polishing powder; the electrode was then ultrasonically cleaned in ultrapure water and ethanol baths in turn, and then gently dried at room temperature; Accurately weigh 6 mg of (R)-PTCDA-RMP and the sample to be tested, disperse them in N,N-dimethylformamide (DMF) to form a uniform solution with a (R)-PTCDA-RMP concentration of 4 mg / mL; then ultrasonically treat the solution to ensure that the (R)-PTCDA-RMP and the sample to be tested are uniformly dispersed; Subsequently, 8 μL of the well-dispersed solution was carefully coated on the GCE surface and air-dried at room temperature; finally, the electrode was rinsed with ultrapure water to remove any nonspecifically adsorbed substances and air-dried at room temperature to obtain the (R)-PTCDA-RMP / ECL sensor; (2) Enantioselective detection Enantioselective detection was carried out in a three-electrode system with (R)-PTCDA-RMP / GCE as the working electrode, a silver chloride electrode as the reference electrode, and a platinum wire electrode as the auxiliary electrode; The electrolytic medium consisted of 0.1 M phosphate buffer solution (PBS) adjusted to pH 8.04 and supplemented with 0.1 M potassium persulfate (K2S2O8) as a co-reactant; the ECL detection photomultiplier tube operated at 600 V high voltage, with a potential scanning range from 0 to -1.6 V and a scanning rate of 0.2 mV / s.

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