A porous crystalline polymer and a preparation method and application thereof

Abstract

The application discloses a kind of porous crystal polymer, namely one-dimensional chiral covalent organic framework (R) -PCTCA-RMP and its preparation method and application, belong to nanomaterial, covalent organic framework and electrochemical detection technical field.It is specifically to heat 3,4,9,10-pyrene tetracarboxylic dianhydride PTCDA and (R) -(−) -2-methylpiperazine RMP under the catalysis of imidazole, and the structure gives its adjustable surface charge in alkaline environment, gives it dispersion and anti-aggregation ability, and the electrochemiluminescence chiral sensor constructed from the material can simply, quickly, high specificity identify and detect D / L-penicillamine enantiomer.

Description

TECHNICAL FIELD

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

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

[0003] Cong's team synthesized a macrocyclic compound by encapsulating L-cysteine hydrochloride in a benzene [3] urea cavity [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 specific chiral enantiomers of penicillamine and exhibit 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 Enhanced Electrochemiluminescence Sensing Strategy for Detection of 3,4-Dihydroxy-Phenylalanine Enantiomers. Analytical Chemistry . 2021, 93(33): 11470-11478]; this compound has a high oxidative preference for L-dopamine and a high electron transfer rate with L-DOPA, resulting in a strong ECL signal. However, the current method has the limitation of showing different intensities of ECL signals for both enantiomers; this method leads to inaccuracies in the recognition and analysis of a pair of enantiomers.

[0004] Covalent organic frameworks (COFs) are a new class of porous, crystalline polymers assembled through covalent bonds. COFs have excellent properties such as high surface area, ordered porosity, water resistance, and low toxicity, making them ideal for separation and sensing. Ionic COFs allow for tunable surface charge by having functional groups that can ionize, expanding this versatility; this tunability is advantageous for chiral recognition as it can tune the electrostatic environment around the chiral center, enhancing the differentiation between enantiomers. Additionally, the ability of this material to dynamically tune 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 confers tunable surface charge on the COF in basic environments, allowing it to adjust its aggregation and dispersion in the detection environment, thus producing different ECL responses, which is crucial for differentiating enantiomers.

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

[0007] Traditional ECL sensors show consistent signal response trends for both enantiomers, with only changes in the magnitude of signal changes, while the sensor of the present invention has a unique bidirectional change in ECL intensity as its response characteristic. Specifically, D-PA significantly enhances the ECL signal, while L-PA significantly reduces the ECL signal. The response to each enantiomer is a breakthrough in ECL analytical and detection, not only allowing effective qualitative recognition, but also quantification of chiral molecules based on the degree of ECL signal change. This precise chiral discrimination and quantification capability is expected to greatly improve the accuracy and reliability of the analysis results, opening up a new method in the field of chiral analysis and molecular diagnostic technology. SUMMARY

[0008] One of the technical tasks of the present application is to make up for the deficiency of the prior art, provide a porous crystalline polymer, namely one-dimensional chiral covalent organic framework (R)-PTCDA-RMP COF, which has adjustable surface charge in alkaline environment, thereby endowing it with dispersion and anti-aggregation in the detection environment, and an electrochemiluminescence (ECL) chiral sensor constructed from the material, which has significantly stronger ECL signal intensity in alkaline environment than in acidic environment.

[0009] The second technical task of the present application is to provide a preparation method of the (R)-PTCDA-RMP COF, which has low cost of raw materials, simple preparation process, low reaction energy consumption, and industrial application prospect.

[0010] The third technical task of the present application is to provide the use of the (R)-PTCDA-RMP COF, which is used to construct an electrochemiluminescence (ECL) material sensor, and shows excellent resolution ability of ECL signal in distinguishing D- and L- PA enantiomers.

[0011] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0012] 1. A porous crystalline polymer, which is one-dimensional chiral covalent organic framework, namely one-dimensional chiral (R)-PTCDA-RMP COF, the structure of (R)-PTCDA-RMP is as follows:

[0013]

[0014] (R)-PTCDA-RMP is a mesoporous material composed of leaf-shaped nanosheets; an electrochemiluminescence (ECL) chiral sensor constructed from the material has significantly stronger ECL signal intensity in alkaline environment than in acidic environment, and especially, D-penicillamine leads to the enhancement of ECL signal, while L-penicillamine leads to the quenching of ECL signal.

[0015] 2. The porous crystalline polymer as described above, the preparation method is as follows:

[0016] Synthesis by solvothermal method, 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 blended, 40-60 mM of imidazole catalyst is added; the mixture is heated at 120℃ for 12-24 h under stirring; after the reaction is completed, the system is cooled to 70-85℃, filtered, the obtained solid is washed with deionized water for 3-5 times to remove unreacted starting materials and catalyst, and continuously dried at 80℃ under vacuum to remove solvent and achieve high porosity, to obtain one-dimensional chiral ion (R)-PTCDA-RMP covalent organic framework COF, i.e. porous crystalline polymer (R)-PTCDA-RMP COF; the preparation reaction formula is as follows:

[0017]

[0018] 3. Use of the porous crystalline polymer as described above for detecting enantiomers, the steps are as follows:

[0019] (1) Construction of ECL chiral sensor

[0020] The 4 mm diameter platinum carbon electrode GCE is finely polished with 0.05 μm α-AlO2 polishing powder; then the electrode is ultrasonically washed in ultrapure water and ethanol bath in turn, and then dried at room temperature;

[0021] Accurately weigh 6 mg of (R)-PTCDA-RMP and the sample to be tested, disperse in N,N-dimethylformamide DMF to form a uniform solution with (R)-PTCDA-RMP concentration of 4 mg / mL; then the solution is ultrasonically treated to ensure uniform dispersion of (R)-PTCDA-RMP and the sample to be tested; then, 8 μL of the well-dispersed solution is carefully coated on the surface of the GCE, and dried at room temperature; finally, the electrode is washed with ultrapure water to remove any non-specifically adsorbed substances, and dried at room temperature to obtain (R)-PTCDA-RMP / ECL sensor.

[0022] (2) Enantioselective detection

[0023] The enantioselective detection is carried out in a three-electrode system, the working electrode is (R)-PTCDA-RMP / GCE; the silver chloride electrode is used as the reference electrode, and the platinum wire electrode is used as the auxiliary electrode; the electrolyte medium is composed of 0.1 M phosphate buffer solution PBS solution, adjusted to pH 8.04, and supplemented with 0.1 M potassium persulfate K2S2O8 as a co-reactant; the ECL detection photomultiplier tube works at a high voltage of 600 V, the potential scanning range is from 0 to-1.6 V, and the scanning rate is 0.2 mV / s, to ensure consistency and repeatability of the results.

[0024] The simulation of (R)-PTCDA-RMP COF structure by Materials Studio software showed that (R)-PTCDA-RMP COF had two prominent peaks at 11.98° and 24.58° with an additional peak at 27.42°; these reflections corresponded to 100, 010 and 012 planes, respectively, and the experimental PXRD pattern of (R)-PTCDA-RMP COF was consistent with the simulated PXRD pattern. Figure 1 The difference between the two peaks was negligible;

[0025] The morphology of (R)-PTCDA-RMP COF was characterized by scanning electron microscopy (SEM), which showed that (R)-PTCDA-RMP COF was composed of nanosheets with unique leaf-like profiles; these nanosheets had a large specific surface area and high porosity; the presence of a special microporous framework provided a large number of active sites for the COF, which was crucial for improving the sensitivity and selectivity of sensing applications.

[0026] Nitrogen adsorption-desorption tests of (R)-PTCDA-RMP COF showed that the COF exhibited type III isotherms, indicating that it was a mesoporous material, and the measured brunauer-emmet-teller (BET) surface area was 14.7540±1.8679 m² / g.

[0027] Circular dichroism (CD) spectroscopy confirmed the chiral optical properties of (R)-PTCDA-RMP COF, and the obvious peak at about 440 nm indicated the inherent chirality of the material, which provided evidence for the enantioselective interaction of its internal structure and confirmed its potential for chiral recognition and sensing applications.

[0028] ECL analysis of (R)-PTCDA-RMP COF coated GCE showed that the ECL signal intensity of (R)-PTCDA-RMP / GCE gradually increased with increasing pH, and the ECL signal intensity in alkaline solution was significantly stronger than that in acidic and neutral environments,

[0029] Penicillamine (PA) is a metabolite of penicillin and exhibits different pharmacological activities or toxicities in living 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 visual degradation.

[0030] The research shows that the ECL signal of (R)-PTCDA-RMP / GCE shows obvious different response to L-PA and D-PA, and D-PA causes the ECL signal intensity to enhance, and L-PA shows obvious quenching effect on the ECL signal intensity.

[0031] The analysis ability of the (R)-PTCDA-RMP / GCE sensor is further researched, and the ECL signal intensity is proportional to the D-PA concentration and inversely proportional to the L-PA concentration; in the range of 50 mu M to 1 mM, there is a strong linear correlation between the ECL intensity and the D / L-PA concentration, and the linear regression equations of L-PA and D-PA are ECL L‐PA = -2730.98C (mM) +5888.81(R2 = 0.9040)and ECL D‐PA = 1780.32C (mM) + 5950.54(R = 0.9606).

[0032] In order to verify the specificity of the sensor in recognizing and detecting the penicillamine PA enantiomers, the present application carries out a series of control experiments on carnitine (Car), methionine (Met), alanine (Ala), serine (Ser), valine (Val), phenylalanine (Phe) and glutamic acid (Glu) and other amino acid enantiomers, and the experimental results show that, in addition to D / L-PA, the left and right ECL signals of other enantiomers are extremely small, which confirms the specificity of the sensor in selectively recognizing and detecting D / L-PA enantiomers.

[0033] In order to evaluate the actual effect of the established chiral detection sensor, the present application uses (R)-PTCDA-RMP / GCE to detect the ECL of the mixture of D-PA and L-PA in different proportions, and the total concentration of D-PA and L-PA is kept as 1 mM, and the research results show that the ECL signal is linearly related to the proportion of D-PA in the mixture, so as to determine the accurate recognition of the PA mixture.

[0034] The beneficial technical effects of the present application

[0035] (1) 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) has no chiral site and cannot recognize and detect chiral compounds, and the present research simply synthesizes a chiral electrochemiluminescence (ECL) material (R)-PTCDA-RMP COF based on 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and chiral (R)-2-methylpiperazine (RMP) through a solvothermal synthesis method; the method has low raw material cost, simple preparation process and low reaction energy consumption, and has industrial application prospect.

[0036] (2) The electrochemiluminescence (ECL) chiral sensor (R)-PTCDA-RMP / GCE constructed by the (R)-PTCDA-RMP COF is used for chiral recognition and detection of D / L-PA enantiomers, D-PA causes the ECL signal intensity to increase, and L-PA shows an obvious quenching effect on the ECL signal intensity, which lays a foundation for accurate recognition and detection.

[0037] (3) The (R)-PTCDA-RMP of the application belongs to a one-dimensional COF, and the ECL signal gradually increases with the increase of pH, is significantly enhanced in an alkaline environment, and is significantly reduced in an acidic environment; the one-dimensional ion COF material in the alkaline environment; the obvious sensitivity to pH change is because the (R)-PTCDA-RMP COF framework contains carboxyl and perylene structural units; the pH-dependent behavior is because under alkaline conditions, the protonation of basic N in the COF framework is avoided, which causes the destruction of the conjugated structure with the carbonyl group; and the carboxyl group can realize deprotonation, introducing negative charges on the COF chain, both of which can cause the increase of electron density, and due to the electrostatic repulsion between adjacent chains, the aggregation is prevented, which enhances the electron transfer process necessary for ECL, and this dispersed state is beneficial to maintain the ECL activity of the perylene unit, thereby allowing effective ECL release; the repulsion between the negatively charged chains can also reduce the non-radiative energy transfer pathway, thereby maintaining the ECL signal intensity; in contrast, under neutral conditions, the degree of ionization of the carboxyl group is low, and the electrostatic repulsion is weakened; the reduction of this repulsion makes the COF chains closer, and through the π-π stacking interaction of perylene, the formation of aggregates is caused, and the aggregation of the COF chain will limit 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 considered to be the reason for the reduction of the ECL signal observed under neutral conditions. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 PXRD spectrum of (R)-PTCDA-RMP (red curve) and simulated standard spectrum (green curve);

[0039] Figure 2 Circular dichroism spectrum of (R)-PTCDA-RMP;

[0040] Figure 3 Effect of pH on the ECL signal intensity of (R)-PTCDA-RMP / GCE;

[0041] Figure 4ECL spectra of bare GCE, (R)-PTCDA-RMP / GCE, L-PA / (R)-PTCDA-RMP / GCE and D-PA / (R)-PTCDA-RMP / GCE

[0042] Figure 5 Linear relationship of ECL signal of (R)-PTCDA-RMP COF with L-PA (red line) and D-PA (green line) concentration

[0043] Figure 6 ECL signal of (R)-PTCDA-RMP / GCE in 1 mM different enantiomers

[0044] Figure 7 Linear relationship of ECL signal (A) and ECL intensity (B) of D-PA concentration on different ratios of D- and L-PA mixture Detailed implementation method

[0045] Example 1: A method for preparing a porous crystal polymer

[0046] Using a solvothermal method, first, 1.0 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA is blended with 4.0 mM of (R)-(-)-2-methylpiperazine RMP, and 40 mM of imidazole catalyst is added; the mixture is heated at 120°C for 12 h under stirring; after the reaction is completed, the system is cooled to 70°C, filtered, and the obtained solid is washed with deionized water for 3 times to remove unreacted starting materials and catalysts, and then continuously dried at 80°C under vacuum to remove the solvent and achieve high porosity, thereby obtaining a one-dimensional chiral (R)-PTCDA-RMP covalent organic framework COF, i.e., a porous crystal polymer (R)-PTCDA-RMP COF. The preparation reaction formula is as follows:

[0047] .

[0048] Example 2: A method for preparing a porous crystal polymer

[0049] Synthesis by 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, 60 mM of imidazole catalyst was added; the mixture was heated at 120 °C for 24 h under stirring; after the reaction was completed, the system was cooled to 85 °C, filtered, the obtained solid was washed with deionized water for 5 times to remove the unreacted starting materials and catalyst, and vacuum dried at 80 °C to remove the solvent and achieve high porosity, to obtain one-dimensional chiral ionic (R)-PTCDA-RMP covalent organic framework COF, i.e. porous crystalline polymer (R)-PTCDA-RMP COF, the preparation reaction formula is the same as that of Example 1.

[0050] Example 3. A method for preparing a porous crystalline polymer

[0051] Synthesis by solvothermal method, first, 1.3 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA and 4.3 mM of (R)-(-)-2-methylpiperazine RMP were mixed, 50 mM of imidazole catalyst was added; the mixture was heated at 120 °C for 13 h under stirring; after the reaction was completed, the system was cooled to 80 °C, filtered, the obtained solid was washed with deionized water for 4 times to remove the unreacted starting materials and catalyst, and vacuum dried at 80 °C to remove the solvent and achieve high porosity, to obtain one-dimensional chiral ionic (R)-PTCDA-RMP covalent organic framework COF, i.e. porous crystalline polymer (R)-PTCDA-RMP COF, the preparation reaction formula is the same as that of Example 1.

[0052] Example 4. Structural and performance characterization of the materials prepared in Example 1, Example 2 and Example 3

[0053] The structure of (R)-PTCDA-RMP COF was simulated by using Materials Studio software, and the results are shown by the green line in FIG. 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, and the experimental PXRD Figure 1 The difference between the main peak of the red line and this peak is negligible.

[0054] The morphology characterization of (R)-PTCDA-RMP COF by scanning electron microscopy SEM shows that (R)-PTCDA-RMP COF is composed of nanosheets with unique leaf-like profiles; these nanosheets have a large specific surface area and high porosity; the presence of special microporous framework makes COF have a large number of active sites, which is crucial for improving the sensitivity and selectivity of sensing applications.

[0055] Nitrogen adsorption-desorption tests of (R)-PTCDA-RMP COF showed that the COF exhibited type III isotherm, which indicated that it was a mesoporous material, and the measured brunauer-emmet-teller (BET) surface area was 14.7540±1.8679 m² / g.

[0056] From Figure 2 Circular dichroism CD spectra of (R)-PTCDA-RMP COF showed that the obvious peak at about 440 nm indicated the inherent chirality of the material, which provided evidence for the enantioselective interaction of its internal structure, and confirmed its potential for chiral recognition and sensing applications.

[0057] Example 5 Construction of ECL chiral sensor with porous crystal polymers prepared in Examples 1-3

[0058] A platinum carbon electrode GCE with a diameter of 4 mm was finely polished with 0.05 μm α-AlO2 polishing powder; then the electrode was ultrasonically washed in an ultrapure water and ethanol bath, and then gently dried at room temperature;

[0059] Accurately weigh 6 mg of (R)-PTCDA-RMP prepared in Example 1, Example 2 or Example 3 and the sample to be tested, and disperse them in N,N-dimethylformamide DMF to form a uniform solution with a (R)-PTCDA-RMP concentration of 4 mg / mL; then the solution was ultrasonically treated to ensure uniform dispersion of (R)-PTCDA-RMP and the sample to be tested; then, 8 μL of the well-dispersed solution was carefully coated on the surface of the GCE, and air-dried at room temperature; finally, the electrode was rinsed with ultrapure water to remove any non-specifically adsorbed substances, and air-dried at room temperature to obtain a (R)-PTCDA-RMP / ECL sensor.

[0060] Example 6 Use of the ECL chiral sensor constructed in Example 5 for enantioselective detection

[0061] 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 solution, adjusted to pH 8.04, and supplemented with 0.1 M potassium persulfate K2S2O8 as a co-reactant; the ECL detection photomultiplier tube worked at a high voltage of 600 V, the potential scan range was from 0 to-1.6 V, and the scan rate was 0.2 mV / s to ensure consistency and repeatability of the results.

[0062] From Figure 3It 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 the alkaline solution is obviously stronger than that in the acidic and neutral environment.

[0063] Penicillamine (PA) is a metabolite of penicillin, which shows different pharmacological activities or toxicities in organisms. D-PA has medical value in treating heavy metal poisoning, Wilson's disease and rheumatoid arthritis, while L-PA can cause adverse reactions such as neuritis, osteomyelitis and olfactory vision degradation;

[0064] As shown in Figure 4 The ECL signal of (R)-PTCDA-RMP / GCE shows obvious different responses to L-PA and D-PA, D-PA leads to the increase of ECL signal intensity, while L-PA shows obvious quenching effect on ECL signal intensity.

[0065] Figure 5 The analysis ability of (R)-PTCDA-RMP / GCE sensor is further verified and evaluated, and the ECL signal intensity is proportional to the concentration of D-PA and inversely proportional to the concentration of L-PA; within the range of 50 μM ~ 1 mM, there is a strong linear correlation between ECL intensity and D / L-PA concentration, and the linear regression equations of L-PA and D-PA are ECL L‐PA = -2730.98C (mM) + 5888.81 (R2 = 0.9040) and ECL D‐PA = 1780.32C (mM) + 5950.54(R =0.9606)。

[0066] In order to verify the specificity of the sensor in recognizing and detecting the enantiomers of penicillamine PA, the present application carries out a series of control experiments on the enantiomers of carnitine (Car), methionine (Met), alanine (Ala), serine (Ser), valine (Val), phenylalanine (Phe) and glutamic acid (Glu), Figure 6 The experimental results show that the difference between the left and right ECL signals of other enantiomers is very small except D / L-PA, which confirms the specificity of the sensor in selectively recognizing and detecting the enantiomers of D / L-PA.

[0067] In order to evaluate the actual effect of the established chiral detection sensor, the present application uses (R)-PTCDA-RMP / GCE to detect the ECL of the mixture of D-PA and L-PA in different proportions, and the total concentration of D-PA and L-PA is kept at 1 mM, Figure 7The results show that the ECL signal is linearly related to the ratio of D-PA in the mixture, thus determining the accurate identification of PA mixture.

Claims

1. A porous crystalline polymer, characterized by, The porous crystal polymer is a one-dimensional chiral covalent organic framework, namely a one-dimensional chiral (R)-PTCDA-RMP COF; The (R)-PTCDA-RMP is a mesoporous material composed of leaf-shaped nanosheets; the structure belongs to a one-dimensional ionic COF in an alkaline environment, carries a negative charge, and endows it with dispersion and anti-aggregation ability; The electrochemiluminescence (ECL) chiral sensor constructed from the material has a significantly stronger ECL signal intensity in an alkaline environment than in an acidic environment; D-penicillamine causes the ECL signal to be enhanced, while L-penicillamine causes the ECL signal to be quenched; the (R)-PTCDA-RMP has the following structure: 。 2. The porous crystalline polymer of claim 1, wherein, The preparation method is as follows: The one-dimensional chiral (R)-PTCDA-RMP covalent organic framework COF, namely the porous crystal polymer (R)-PTCDA-RMP COF, is synthesized by a solvothermal method, first, 1.0-1.5 mM of 3,4,9,10-perylenetetracarboxylic dianhydride PTCDA is blended with 4.0-4.5 mM of (R)-(-)-2-methylpiperazine RMP, and 40-60 mM of an imidazole catalyst is added; the mixture is heated at 120 DEG C for 12-24 h under stirring; after the reaction is completed, the system is cooled to 70-85 DEG C, filtered, and the obtained solid is washed with deionized water for 3-5 times to remove unreacted starting materials and the catalyst, and then continuously dried at 80 DEG C under vacuum to remove the solvent and achieve high porosity; the one-dimensional chiral (R)-PTCDA-RMP covalent organic framework COF, namely the porous crystal polymer (R)-PTCDA-RMP COF, is obtained; the preparation reaction formula is as follows: 。 3. Use of the porous crystal polymer according to claim 1 for detecting D / L-penicillamine enantiomers.

4. Use of the porous crystalline polymer according to claim 3 for the detection of the D / L- penicillamine enantiomer, characterized in that, The steps are as follows: (1) Construction of an ECL chiral sensor A platinum carbon electrode GCE with a diameter of 4 mm is finely polished with 0.05 μm α-Al2O3 polishing powder; then the electrode is ultrasonically washed in an ultrapure water bath and an ethanol bath in turn, and then is gently dried at room temperature; 6 mg of (R)-PTCDA-RMP and a sample to be detected are accurately weighed, and are dispersed in N, N-dimethylformamide DMF to form a uniform solution with a (R)-PTCDA-RMP concentration of 4 mg / mL; then the solution is ultrasonically treated to ensure that the (R)-PTCDA-RMP and the sample to be detected are uniformly dispersed; Subsequently, 8 μL of the well-dispersed solution is carefully coated on the surface of the GCE, and is air-dried at room temperature; finally, the electrode is washed with ultrapure water to remove any non-specifically adsorbed substances, and is air-dried at room temperature to obtain a (R)-PTCDA-RMP / ECL sensor; (2) Enantioselective detection Enantioselective detection is carried out in a three-electrode system, and the working electrode is (R)-PTCDA-RMP / GCE; a silver chloride electrode is used as a reference electrode, and a platinum wire electrode is used as an auxiliary electrode; The electrolyte medium consists of 0.1 M phosphate buffer solution PBS solution, adjusted to pH 8.04, and supplemented with 0.1 M potassium persulfate K2S2O8 as a co-reactant; the ECL detection photomultiplier tube works at a high voltage of 600 V, the potential scanning range is from 0 to-1.6 V, and the scanning rate is 0.2 mV / s.

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