CN110982046A - Tetraphenyl ethylene-based conjugated microporous polymer aggregation-induced electrochemical luminescence sensor and preparation method and application thereof - Google Patents
Tetraphenyl ethylene-based conjugated microporous polymer aggregation-induced electrochemical luminescence sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an electrochemiluminescence sensor induced by aggregation of a tetraphenyl ethylene-based conjugated microporous polymer, and a preparation method and application thereof. The present invention studies the advantages of ECL mechanism combining luminescence and electrochemical technology using three TPE-CMP (i.e., TPE-CMP-1, TPE-CMP-2 and TPE-CMP-3), prepares tris (4-ethynylphenyl) amine (TEPA), 4,4' -diacetylene biphenyl (DEBP) and 2,4,6 tris (4-ethynylphenyl) -1,3, 5-triazine (TEPT) by using different coupling agents, respectively, and further used to construct ECL sensors for detecting dopamine. Experiments prove that the electrochemical luminescence sensor has extremely high sensitivity to dopamine, can be used for analyzing biological samples, and therefore has good practical application value.
Description
Technical Field
The invention belongs to the technical field of electrochemical luminescence detection, and particularly relates to a tetraphenyl ethylene-based conjugated microporous polymer aggregation-induced electrochemical luminescence sensor, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Tetraphenylethylene (TPE) -based Conjugated Microporous Polymer (CMP) materials have attracted increasing attention, a class of porous organic materials and have high flexibility in the molecular design of conjugated backbones and microporous structures. Due to its large surface area and microporous nature, CMP can be used as a porous material for gas adsorption, chemical sensing, catalysis, and light trapping. Recently, a series of AIE active Electrochemiluminescence (ECL) emitters with optical signal enhancement in the aggregated state have been reported. Aggregation Induced Emission (AIE) is an improved luminescence produced by molecules in an aggregated state due to intramolecular vibration, rotation and restricted motion. AIE has found widespread use in the fields of bioprobes, photodynamic therapy, tissue imaging, and organic light emitting diodes. Tetraphenylethylene can produce aggregation-induced emission, and the introduction of pores in solid AIE materials can promote diffusion of sensing targets into the materials, thereby improving assay performance. A variety of TPE-based AIE active materials are reported to be useful for the detection of small molecules, proteins and also for photodynamic therapy.
Electrochemiluminescence (ECL) is an optical emission process of electrochemical excitation caused by energy relaxation of an excited species. ECL exhibits a relatively low detection background and allows control of the reaction in time and space and is widely used in bioanalysis as well as in theranostics. Ru (bpy)3 2+Luminol, quantum dot, is three widely used ECL emitters. However, no work has reported the use of tetraphenylethylene-covalent microporous polymers (TPE-CMP) as ECL emitters.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an aggregation-induced electrochemical luminescence sensor based on a tetraphenyl ethylene conjugated microporous polymer, and a preparation method and application thereof. The present invention uses three TPE-CMP (i.e., TPE-CMP-1, TPE-CMP-2 and TPE-CMP-3) to study the advantages of ECL mechanism combining luminescence and electrochemical technology, and further used to construct an electrochemiluminescence sensor (ECL) sensor for detecting dopamine. Experiments prove that the electrochemical luminescence sensor has extremely high sensitivity to dopamine, can be used for analyzing the dopamine in a biological sample, and therefore has good practical application value.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a tetraphenyl vinyl conjugated microporous polymer having a structure represented by any one of the following formulas (I) to (III):
the conjugated microporous polymer has an aggregation-induced emission (AIE) effect.
The second aspect of the invention provides a preparation method of the conjugated microporous polymer, wherein the preparation method comprises the step of carrying out Sonogashira-Hagihara coupling reaction on aromatic alkynyl benzene and 1,1,2, 2-tetra (4-bromophenyl) ethylene (TBTPE) serving as raw materials to obtain the conjugated microporous polymer.
Wherein the molar ratio of the aromatic alkynyl benzene to the 1,1,2, 2-tetra (4-bromophenyl) ethylene is 1: 0.1-1, preferably 1: 0.75;
the aromatic alkynyl benzenes include, but are not limited to, tris (4-ethynylphenyl) amine (TEPA), 4,4' diacetylene biphenyl (DEBP), and 2,4,6 tris (4-ethynylphenyl) -1,3, 5-triazine (TEPT).
Further, when the conjugated microporous polymer is a compound represented by formula (I), the preparation method comprises:
mixing TBTPE and TEPA in an organic solvent, adding a catalyst under the protection of inert atmosphere, refluxing at high temperature, and purifying to obtain the catalyst.
Further, when the conjugated microporous polymer is a compound represented by formula (II), the preparation method thereof comprises:
mixing TBTPE and DEBP in an organic solvent, adding a catalyst under the protection of inert atmosphere, refluxing at high temperature, and purifying to obtain the catalyst.
Further, when the conjugated microporous polymer is a compound represented by formula (III), the preparation method thereof comprises:
mixing TBTPE and TEPT in an organic solvent, adding a catalyst under the protection of inert atmosphere, refluxing at high temperature, and purifying to obtain the catalyst.
Wherein the organic solvent is a mixed solution of anhydrous triethylamine and N, N '-dimethylformamide, and the volume ratio of the anhydrous triethylamine to the N, N' -dimethylformamide is 1: 1-5, preferably 1: 2;
the high-temperature reflux condition is specifically as follows: refluxing at 90-100 deg.C for 60-80 hr, preferably 100 deg.C for 72 hr.
The catalyst is CuI and CuI/Pd (PPh)3)4Any one or more of them.
The purification involved filtering the product, washing with methanol to obtain a yellow precipitate, and further purification by soxhlet extraction.
In a third aspect of the present invention, there is provided the use of the above conjugated microporous polymer in an electrochemiluminescence sensor.
In a fourth aspect of the invention, there is provided an electrochemiluminescence sensor comprising the above conjugated microporous polymer.
Further, the electrochemical luminescence sensor includes: an electrode, and the above-mentioned conjugated microporous polymer supported on the electrode; further, the electrode is a Glassy Carbon (GCE) electrode.
In a fifth aspect of the present invention, there is provided the use of the above-mentioned conjugated microporous polymer and/or the above-mentioned conjugated microporous polymer for detecting dopamine in an environment or a biological sample.
The biological sample comprises serum.
In a sixth aspect of the present invention, there is provided a method for detecting dopamine, the method comprising: and immersing the electrochemical luminescence sensor into a sample to be detected, and performing electrochemical luminescence detection by using a three-electrode system.
Further, in the above-mentioned case,during detection, a co-reactant is added into the reaction system, and the co-reactant is tri-n-propylamine (TPrA). Tri-n-propylamine as co-reactant can be oxidized by electrochemical method to generate strongly reducing substance (TPrA)·) Then with electrochemically oxidized emitter (TPE-CMP)·+) The reaction forming an excited species for the reaction (TPE-CMP)*) The stimulus returns from the excited state to the ground state, thereby generating an ECL signal.
The invention has the beneficial technical effects that:
1. use of covalent microporous polymers: the present invention synthesizes three TPE-CMP (i.e., TPE-CMP-1, -2, -3) using three different molecules, including tris (4-ethynylphenyl) amine (TEPA), 4,4' diacetylene biphenyl (DEBP), and 2,4,6 tris (4-ethynylphenyl) -1,3, 5-triazine (TEPT). Wherein the TPE-based conjugated microporous polymer (TPE-CMP) generates aggregation-induced electrochemiluminescence (AIECL).
2. High sensitivity: the TPE-CMP-1 adopted by the invention can be used for constructing an ECL sensor to detect electrooxidation products (such as bright dopamine chromium (LDC), Dopamine Chromium (DC), 5, 6-Dihydroxyindole (DHI) and 5, 6-Indoloquinone (IDQ)) of the ECL sensor, and the ECL sensor can serve as an energy receptor to quench ECL emission of the TPE-CMP-1.
3. Potential application: the electrochemical luminescence biosensor designed by the invention can be used for analyzing biological samples (human serum), and has potential application value in biomedical research.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a diagram of the synthesis and mechanism of the present invention. FIG. 1A is a schematic diagram of the synthesis of TPE-CMP-1; FIG. 1B is the proposed ECL mechanism of the TPE-CMP-1/TPrA system and the mechanism of quenching ECL by dopamine via Resonance Energy Transfer (RET).
FIG. 2 is a schematic synthesis of the present invention. FIG. 2A is a schematic diagram of the synthesis of TPE-CMP-2, and FIG. 2B is a schematic diagram of the synthesis of TPE-CMP-3.
FIG. 3 is a representation of TPE-CMP-1 polymers of the present invention. FIG. 3A is a Scanning Electron Microscope (SEM) of TPE-CMP-1, FIG. 3B is a Transmission Electron Microscope (TEM), FIG. 3C is a nitrogen adsorption and desorption isotherm measured at 77K, FIG. 3D is a pore size distribution curve of TPE-CMP-1, FIG. 3E is an X-ray powder diffraction pattern (XRD) of TPE-CMP-1, FIG. 3F is a Fourier transform infrared spectrum (FT-IR) of TPE (a) and TPE-CMP-1(B), FIG. 3G is a Diffuse Reflectance Spectrum (DRS) of TPE-CMP-1, and FIG. 3H is an ultraviolet-visible absorption spectrum (UV-vis) and a fluorescence spectrum (PL) of TPE-CMP-1 dispersed in DMF at an excitation wavelength of 390 nm.
FIG. 4 is a representation of TPE-CMP-2, TPE-CMP-3 polymers of the present invention. FIG. 4A is an XRD diagram of TPE-CMP-2(a) and TPE-CMP-3(B), FIG. 4B is FT-IR spectrum of TPE-CMP-2(a) and TPE-CMP-3(B), and FIG. 4C is UV-vis diffuse reflectance spectrum of TPE-CMP-2(a) and TPE-CMP-3 (B).
FIG. 5 is an ECL-potential plot of the ECL of TPE-CMP-1 of the present invention, FIG. 5A is the ECL-potential curves of bare GCE (a) and TPE-CMP-1-modified GCE (B) in 0.1M PBS (pH7.4), FIG. 5B is the ECL-potential curves (a) and CV curves (B) of TPE-CMP-1 modified GCE in 0.1M PBS (pH7.4) with 10mM TPrA as coreactant, and C is the ECL response curve of bare GCE (a), electrodes modified with TPE (B), (TEPA), (C) and TPE-CMP-1(d) in 0.1M PBS containing 10mM TPrA (pH7.4) (FIG. 5C is shown enlarged in inset). FIG. 5D is an ECL response curve for 27 consecutive cycles of TPE-CMP-1 in 0.1M PBS (pH7.4) solution containing 10mM TPrA at a potential in the range of 0 to +1.4V (vs Ag/AgCl) with a scan rate of 500mV s-1。
FIG. 6 is a graph showing the electrochemiluminescence signals of TPE-CMP-2 and TPE-CMP-3 of the present invention. Figure 6A is the ECL-potential curve (a) and CV curve (B) for TPE-CMP-2 and GCE modified in 0.1M PBS with 10mM TPrA as co-reactant (pH7.4), and figure 6B is the ECL-potential curve (a) and CV curve (B) for TPE-CMP-3 and GCE modified in 0.1M PBS with 10mM TPrA as co-reactant (pH 7.4).
FIG. 7 is a graph of the amplitude of the molecular orbital amplitudes of the optimized HOMO and LUMO molecules and the energy levels of the TPE, TEPA, DEBP and TEPT molecules calculated separately.
FIG. 8 is a schematic diagram of electrochemical cyclic voltammetry in accordance with the present invention. FIG. 8A shows bare electrode at 1mM ferrocene (Fc) at 0.1MBu4NPF60.1M Bu in (1)4NPF6In acetonitrile solution (vs. Ag/Ag)+Measured potential), FIG. 8B is TPE-CMP-1 at 0.1M Bu4NPF6FIG. 8C shows the cyclic voltammogram of TPE-CMP-2 at 0.1MBu4NPF6Cyclic voltammogram of acetonitrile solution of (5), FIG. 8D is TPE-CMP-3 at 0.1M Bu4NPF6Cyclic voltammogram in acetonitrile solution.
FIG. 9 is a graph showing CV and ECL experiments according to the present invention. FIG. 9A shows TPE-CMP-1 at 0.1M Bu4NPF6CV curves and ECL curves in acetonitrile solution, FIG. 9B shows TPE-CMP-2 at 0.1M Bu4NPF6CV curves and ECL curves in acetonitrile solution, FIG. 9C is TPE-CMP-3 at 0.1M Bu4NPF6CV curve and ECL curve in acetonitrile solution, FIG. 9D TBTPE monomer at 0.1MBu4NPF6CV curve of molecules in acetonitrile solution and corresponding ECL curve.
Fig. 10 shows uv-vis absorption spectra of dopamine (a) and oxidized dopamine (b) according to the present invention.
FIG. 11 is a graph representing the results of the sensitivity test according to the present invention. Figure 11A is ECL strength of TPE-CMP-1 modified GCE in 0.1M PBS (pH7.4) containing 10mM TPrA and varying concentrations of dopamine from a to i: 0. 0.001, 0.01, 0.1, 1, 10, 100, 1000 μ M, fig. 11B is a line-graph of ECL intensity versus dopamine concentration in the range of 0.001-1000 μ M.
FIG. 12 is a graph representing the results of selectivity and stability experiments according to the present invention. Fig. 12A is a graph of ECL of TPE-CMP-1-modified electrodes in 0.1M PBS (pH7.4) with 10mM TPrA in the absence and presence of 1 μ M ascorbic acid, fig. 12B is a graph of ECL of TPE-CMP-1-modified electrodes in 0.1M PBS (pH7.4) with 10mM TPrA in the absence and presence of 1 μ M uric acid, and fig. 12C is a graph of ECL of TPE-CMP-1-modified electrodes in 0.1M PBS (pH7.4) with 10mM TPrA in the absence and presence of 1 μ M dopamine.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, 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 invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
As mentioned previously, there has been no work reported using tetraphenylethylene-covalent microporous polymers (TPE-CMP) as ECL emitters.
In view of this, in the present invention, three TPE-CMP were synthesized using TPE derivative TBTPE as a single component. TPE monomers do not produce ECL signals, but the unique ECL signals of TPE-CMP can be obtained using tri-n-propylamine (TPrA) as a co-reactant. Three TPE-CMP (i.e., TPE-CMP-1, TPE-CMP-2 and TPE-CMP-3) were used to study the ECL mechanism combining the advantages of luminescence and electrochemical techniques, and further used to construct an ECL sensor for detecting dopamine.
In another embodiment of the present invention, there is provided a method of manufacturing an electrochemiluminescence sensor, the method comprising:
(1) preparing a TPE-CMP modified electrode: fully ultrasonically adding the TPE-CMP solution to the surface of the GCE dropwise to obtain TPE-CMP/GCE; and drying to obtain the TPE-CMP/GCE electrode.
(2) Transferring the electrode to a solution of dopamine to be detected for electrochemical luminescence detection.
In yet another embodiment of the present invention, there is provided a method for detecting dopamine in a human serum sample, said method comprising: diluting a human serum sample with 0.1M PBS (PH7.4) to obtain a sample to be detected, immersing the electrochemiluminescence sensor into the sample to be detected, and performing electrochemiluminescence detection by using a three-electrode system, wherein a coreactant is TPrA.
Further, during detection, a co-reactant is added into the reaction system, so that the luminous efficiency of the luminous group and the sensitivity of the ECL sensor are improved, and the co-reactant is tri-n-propylamine (TPrA).
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Examples
The principle of the embodiment is as shown in fig. 1:
the ECL signal of TPE-CMP-1 can be measured in the potential range of 0 to +1.4V using TPrA as a co-reactant. Electrooxidation products of dopamine (e.g., Leudopaminechromide (LDC), Dopaminechromide (DC), 5,6 Dihydroxyindole (DHI), and 5, 6-Indoloquinone (IDQ)) can be used as energy receptors to quench ECL emissions. Dopamine was detected by Resonance Energy Transfer (RET) from electrochemically excited TPE-CMP-1 to a quencher.
The specific process comprises the following steps:
and (3) synthesis of TPE-CMP-1: TPE-CMP-1 was synthesized based on the Sonogashira-Hagihara coupling reaction. 0.2mmol of TEPA and 0.15mmol of TBTPE were mixed in 1.5mL of anhydrous triethylamine and 3mL of N, N' -Dimethylformamide (DMF), degassed and then treated with N2And (5) purging. 0.06mmol of CuI and 0 was added under a stream of nitrogen.03mmol of CuI/Pd (PPh)3)4Thereafter, the reaction solution was refluxed at 100 ℃ for 72h, then cooled to room temperature, filtered, washed with methanol to obtain a yellow precipitate, and purified by soxhlet extraction.
And (3) synthesis of TPE-CMP-2: 0.2mmol of DEBP and 0.15mmol of TBTPE were mixed in 1.5mL of anhydrous triethylamine and 3mL of N, N' -Dimethylformamide (DMF), degassed and then treated with N2And (5) purging. 0.06mmol of CuI and 0.03mmol of CuI/Pd (PPh) were added under a nitrogen stream3)4Thereafter, the reaction solution was refluxed at 100 ℃ for 72h, then cooled to room temperature, filtered, washed with methanol to obtain a yellow precipitate, and purified by soxhlet extraction.
And (3) synthesis of TPE-CMP-3: 0.2mmol of TEPT and 0.15mmol of TBTPE were mixed in 1.5mL of anhydrous triethylamine and 3mL of N, N' -Dimethylformamide (DMF), degassed and then treated with N2And (5) purging. 0.06mmol of CuI and 0.03mmol of CuI/Pd (PPh) were added under a nitrogen stream3)4Thereafter, the reaction solution was refluxed at 100 ℃ for 72h, then cooled to room temperature, filtered, washed with methanol to obtain a yellow precipitate, and purified by soxhlet extraction.
Preparing electrochemical luminous sensor, the electrochemical sensor is built on GCE electrode, before modification, 1.0, 0.3 and 0.05 micron α -Al are used respectively2O3The GCE electrodes were powder polished and then sonicated with pure water and ethanol for 3 minutes, respectively. TPE-CMP modified GCE was prepared by mixing 20. mu.L of TPE-CMP-1 (10. mu.g mL)-1) Dripping on the surface of GCE and drying at room temperature.
And (3) performing electrochemiluminescence detection on dopamine: dopamine solutions with different concentrations are prepared in 0.1M PBS (PH7.4), TPE-CMP-1 modified electrodes are immersed in the dopamine solutions with different concentrations, and electrochemiluminescence detection is carried out by using a typical three-electrode system.
And (3) detecting the recovery rate of the human serum biological sample: human serum samples were diluted 40-fold with 0.1M PBS (PH7.4), and then buffered to prepare dopamine solutions of various concentrations, and subjected to electrochemiluminescence detection using a typical three-electrode system.
Results of the experiment
1. Characterization of materials
This example characterizes the morphology of the synthesized TPE-CMP-1 by Scanning Electron Microscopy (SEM). FIG. 3A shows that TPE-CMP-1 is composed of platelet-like particles. Interestingly, Transmission Electron Microscope (TEM) images showed aggregation of small spherical particles with a size of about 30nm (fig. 3B). The porosity and surface area of TPE-CMP-1 were measured by nitrogen adsorption (FIG. 3C). TPE-CMP-1 has both type I and type IV adsorption types. At lower relative pressures, the sharp nitrogen uptake reflects the microporous nature of the TPE-CMP-1 network. P/P0>The increase in nitrogen uptake at 0.9 and the unsaturation in the adsorption isotherm may be due to the condensation gap and N in the larger pores2The distribution of the molecules. The specific surface area of Brunauer-Emmet-Teller (BET) is 497m2g-1Pore volume of 0.3854cm3g-1(FIG. 3D). According to the non-local density functional theory (NLDFT), the pore diameter is mainly concentrated around 1.1 nm. The XRD pattern of TPE-CMP-1 (FIG. 3E) showed a characteristic broad peak (halo) distributed over a wide range of 5 deg. -80 deg., indicating no stacking of long range order in the structure. Fourier transform infrared (FT-IR) spectroscopy was used to characterize the polymer structure (fig. 3F). FT-IR spectrum of TBTPE at 1072cm-1And (3) shows C-Br tensile vibration. The absence of this characteristic bond in TPE-CMP-1 indicates that a phenyl-alkynyl coupling is formed. At 1592cm-1And 1498cm-1Two major vibrational peaks were observed, corresponding to the C ═ C vibration of the aromatic groups in TPE-CMP-1, 830cm-1The vibration peak at (C-H) belongs to C-H vibration (out-of-plane bending of the C-H plane of the benzene ring). The ultraviolet-visible Diffuse Reflectance Spectrum (DRS) provides information about the electronic transitions of the different orbitals of the solid and the band gap energy (Eg) of the polymer. The UV-vis DRS of TPE-CMP (FIGS. 3G and 4C) showed strong absorption over almost the entire visible range of 200-600nm with a broad peak in the range of 250-450 nm. We further measured the UV-visible absorption and PL spectra of TPE-CMP-1 dispersed in N, N' -dimethylformamide (FIG. 3H). TPE-CMP-1 exhibited a broad range of luminescence with a peak at 560nm under 390nm excitation. The bandgap of TPE-CMP can be derived from the absorption edge using the equation:
Eg(eV)＝hc/λ (1)
the band gaps of TPE-CMP-1, TPE-CMP-2 and TPE-CMP-3 were calculated to be 2.08eV, 2.07eV and 2.14eV, respectively.
2. ECL signals for TPE-CMP-1
The TPE-CMP-1 modified GCE showed anodic ECL emission in 0.1M pH7.4PBS (FIG. 5A, curve b) compared to bare GCE (FIG. 5A, curve a). TPrA as a co-reactant can be oxidized electrochemically to form a strongly reducing substance (TPrA)·) Then can be combined with electrochemically oxidized emitters (TPE-CMP)·+) The reaction forming an excited species for the reaction (TPE-CMP)*) The excimer returns from the excited state to the ground state, thereby generating an ECL signal (fig. 5B). In 0.1M PBS with 10mM TPrA as co-reactant, the ECL strength of TPE-CMP-1 was found to be 17610, 47 and 139 times higher than that of TPE-CMP-2 (FIG. 6A), and TPE-CMP-3 (FIG. 6B). Anodic ECL emission of TPE-CMP-1 modified GCE (fig. 3C, curve d) also occurred at 1.35V potential, but the ECL intensity of TPE-CMP-1 was 443, 207 and 46 times higher than that of bare GCE (fig. 5C, curve a), TPE (fig. 5C, curve b) and TEPA (fig. 5C, curve C) modified electrodes, respectively, with 10mM TPrA as co-reactant in 0.1M PBS. FIG. 3D shows the good ECL stability of TPE-CMP-1/TPrA system with a relative standard deviation of 1.15% under the same experimental conditions under 27 consecutive potential sweeps. In addition, the CV curve shows a unique oxidation wave with an initial potential of +0.9V (fig. 5B, curve a).
3. Density functional theory calculation (DFT)
We performed semi-empirical calculations to investigate the effect of electronic structure on ECL emission of TPE-CMP (figure 7). TEPA (4.01eV) has a smaller HOMO-LUMO bandgap than DEBP (4.75eV) and TEPT (4.22eV), which facilitates electron transition from valence state to conduction band. Furthermore, only TPE (E)LUMO＝-1.85eV，EHOMO-5.75eV) to TEPA (E)LUMO＝-1.15eV，EHOMO-5.16eV) to enable efficient electron transfer reactions to be achieved, resulting in enhanced ECL signals.
4. Electrochemical measurement of energy bands of TPE-CMP-1, TPE-CMP-2 and TPE-CMP-3 materials
The energy levels of TPE-CMP-1, -2, -3 were modified by using TPE-CMP GCE at 0.1MBu4NPF6Introducing N into acetonitrile solution2Cyclic Voltammetry (CV) was performed for 30 minutes (fig. 8 and table 1). The HOMO and LUMO levels are calculated using the equation:
EHOMO＝-(Eonset Ox–EFc/Fc++4.8)eV (2)
ELUMO＝-(Eonset Red-EFc/Fc++4.8)eV (3)
wherein EHOMOIs the highest energy occupying the molecular orbital, ELUMOIs the lowest unoccupied molecular orbital energy, EonsetOx is the oxidation onset potential, Eonset Red is the reduction onset potential. Based on Eg ═ ELUMO-EHOMO(EFc+/Fc＝0.27Vvs.Ag/Ag+) The band gaps (Eg) of TPE-CMP-1, -2, -3 are calculated as 2.247, 2.503 and 2.357eV, respectively). The values obtained are consistent with those theoretically obtained by the DRS algorithm (2.08eV, 2.07eV, and 2.14 eV).
TABLE 1 electrochemical data and calculated energy level tables for TBPE-CMPs
5. Research on TPE-CMPs/TPrA principle
We further performed CV and ECL measurements of TBTPE and TPE CMP-1, -2, -3 in acetonitrile to investigate the mechanism of aggregation-induced ECL enhancement. As shown in fig. 9D, a single TBTPE molecule shows a weak ECL peak intensity of 140 at-1.4V due to its wide energy gap (2.247 eV). In contrast, the ECL peak intensity of TPE-CMP-1 increased to 330 (FIG. 9A), which is 2.5 times the ECL peak intensity of free TPE. In addition, the peak intensity of ECL at-1.4V for TPE-CMP-2 (FIG. 9B) and TPE-CMP-3 (FIG. 9C) was close to that of TBTPE (FIG. 9D). The high ECL emission of TPE-CMP-1 can be attributed to three factors: (1) the energy gap of TPE-CMP-1 is reduced (2.247eV), so that the efficiency of electron-hole recombination is higher, and the excited state can release energy in the form of electrochemiluminescence more easily to return to the ground state; (2) the TPE and TBPE are limited in the molecule due to the formation of polymerThe intramolecular phenyl movement of TEPA and TBPE effectively inhibits a non-radioactive transition channel and enhances ECL; (3) like TPrA, TEPA contains aliphatic sp3Nitrogen, and DEBP does not contain aliphatic sp3Nitrogen, the heterocycle in TEPT, does not enhance ECL signaling. We have further investigated the anodic ECL emission mechanism of TPE CMP-1 with TPrA as a co-reactant. In the present invention, TPE-CMP-1 (FIG. 1A) was synthesized by a very mild and simple strategy by mixing TBTPE with TEPA at 100 ℃. One TPE molecule is surrounded by four benzene rings that are highly distorted by strong steric hindrance to form a hindrance by a rotatable C — C single bond. These asymmetric propeller-like molecules are likely to form a three-dimensional (3D) charge transport network, thereby facilitating hole transport. We further synthesized TPE-CMP-2 and TPE-CMP-3 for comparison (FIGS. 9B, 9C). Interestingly, the ECL strength of TPE-CMP-1 (about 17610) was greater than that of its raw materials, including TBTPE (about 82) and TEPA (about 49) and 10mM TPrA as co-reactants. The ECL mechanism of the TPE-CMP-1/TPrA system is presented in FIG. 1B. During the anode scanning process, the TPE-CMP-1 is oxidized to form the TPE-CMP-1·+Cationic radical (equation 4). Simultaneously, the co-reactant TPrA is oxidized to form TPrAH·+Cationic radical (equation 5), which is subsequently deprotonated to yield a strongly reducing TPrA·Free radical (equation 6). TPrA·Free radical and TPE-CMP-1·+The cations meet to generate TPE-CMP in the excited state by the electron transfer process (equation 7)*. Finally, when TPE CMP-1*Upon decay back to the ground state (equation 8), a strong emission is obtained.
TPE-CMP-1–e-→TPE-CMP-1·+(4)
TPrA–e-→TPrAH·+(5)
TPrAH·+-H+→TPrA·(6)
TPE-CMP-1·++TPrA·→TPE-CMP-1*+Pr2N+HC＝CH2CH3(7)
TPE-CMP-1*→TPE-CMP-1+hv (8)
6. Detection of dopamine
ECL signal for TPE-CMP-1 can be measured over a potential range of 0 to +1.4V using TPrA as a co-reactant. We further demonstrate the construction of a TPE-CMP-1 based ECL sensor for dopamine detection. Electrooxidation products of dopamine (e.g., Leuprolinechromium (LDC), Dopamine Chromium (DC), 5, 6-Dihydroxyindole (DHI), and 5, 6-Indoloquinone (IDQ)) can be used as energy receptors to quench ECL emission TPE-CMP-1 is analyzed by Resonance Energy Transfer (RET) from the excited TPE-CMP-1 to the quencher. ECL strength of TPE-CMP-1 decreased with increasing dopamine concentration (FIG. 11A). This was verified by UV-Vis absorption spectroscopy (fig. 10). There was a clear overlap between the oxidized dopamine absorption spectrum and the TPE-CMP-1 fluorescence emission spectrum in the 500-600nm range (fig. 3H), but no dopamine absorption spectrum was observed in this wavelength range, indicating a possible RET between oxidized dopamine and excited TPE-CMP-1 (fig. 1B). Furthermore, the linear correlation between ECL intensity and the logarithm of dopamine concentration was in the range of 0.001-1000 μ M (fig. 11B), and the linear regression equation was Δ IECL＝2727lg C+8558(R20.9921), wherein Δ IECL＝I0I, I is the ECL intensity in the presence of dopamine, I0Is the ECL intensity in the absence of dopamine and C is the dopamine concentration (μ M). The limit of detection (LOD) calculated by evaluating the mean of the controls plus 3 times the standard deviation was 0.85 nM.
7. Selectivity and recovery studies of ECL sensors
We investigated the selectivity of the proposed ECL sensor with ascorbic acid and uric acid as interferents. As shown in fig. 8, the ECL intensity of ascorbic acid (fig. 12A) and uric acid (fig. 12B) was not different compared to the blank, but the ECL intensity of dopamine (fig. 12C) was much smaller than the blank. The quenching efficiency (E) can be calculated based on the following formula:
E(％)＝(I0-I)/I0×100％ (9)
wherein I is the ECL intensity in the presence of dopamine or interferon, I0ECL intensity is blank. Quenching efficiency in response to 1 μ M dopamine (46.8%, FIG. 12C) was much higher than in response to ascorbic acid (0.94%, FIG. 12A) and uric acid (1.16%Fig. 12B), indicating that the prepared ECL sensor has good selectivity for dopamine. To evaluate the reliability of the proposed ECL sensor, we performed recovery experiments (table 2) using human serum as a real sample, and the obtained average recovery was in the range of 98.72% ± 2.5% to 101.1% ± 8.4%, indicating that the proposed ECL sensor has good accuracy.
Table 2 reference table for use of ECL sensor of the present invention in serum recovery test
It should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the examples given, those skilled in the art can modify the technical solution of the present invention as needed or equivalent substitutions without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A tetraphenyl vinyl conjugated microporous polymer characterized in that said conjugated microporous polymer has any one of the following structures (I) to (III):
2. the method of claim 1, wherein the method comprises a Sonogashira-Hagihara coupling reaction using 1,1,2, 2-tetrakis (4-bromophenyl) ethylene and an aromatic alkynyl benzene as starting materials.
3. The method according to claim 2, wherein the molar ratio of the aromatic alkynylbenzene to 1,1,2, 2-tetrakis (4-bromophenyl) ethylene is 1:0.1 to 1, preferably 1: 0.75.
4. The method of claim 3, wherein the aromatic alkynylbenzenes comprise tris (4-ethynylphenyl) amine, 4,4' diacetylbiphenyl, and 2,4,6 tris (4-ethynylphenyl) -1,3, 5-triazine.
5. The method according to claim 4,
when the conjugated microporous polymer is a compound represented by the formula (I), the preparation method comprises the following steps:
mixing TPE and TEPA in an organic solvent, adding a catalyst under the protection of inert atmosphere, refluxing at high temperature, and purifying to obtain the TPE/TEPA catalyst;
when the conjugated microporous polymer is a compound represented by the formula (II), the preparation method comprises the following steps:
mixing TPE and DEBP in an organic solvent, adding a catalyst under the protection of inert atmosphere, refluxing at high temperature, and purifying to obtain the catalyst;
when the conjugated microporous polymer is a compound represented by the formula (III), the preparation method comprises the following steps:
mixing TPE and TEPT in an organic solvent, adding a catalyst under the protection of inert atmosphere, refluxing at high temperature, and purifying to obtain the TPE/TEPT catalyst.
6. The preparation method according to claim 5, wherein the organic solvent is a mixed solution of anhydrous triethylamine and N, N '-dimethylformamide, and the volume ratio of the anhydrous triethylamine to the N, N' -dimethylformamide is 1: 1-5, preferably 1: 2;
the high-temperature reflux condition is specifically as follows: carrying out reflux treatment at 90-100 ℃ for 60-80 h, preferably 100 ℃ for 72 h;
the catalyst is CuI and CuI/Pd (PPh)3)4Any one or more of them.
7. Use of the conjugated microporous polymer of claim 1 in an electrochemiluminescence sensor.
8. An electrochemiluminescence sensor, comprising the conjugated microporous polymer of claim 1;
preferably, the electrochemiluminescence sensor comprises: an electrode, and a conjugated microporous polymer supported on the electrode; preferably, the electrode is a glassy carbon electrode.
9. Use of the conjugated microporous polymer of claim 1 and/or the electrochemiluminescence sensor of claim 8 for detecting dopamine in an environment or biological sample;
preferably, the biological sample comprises serum.
10. A method of detecting dopamine, the method comprising: immersing the electrochemiluminescence sensor of claim 8 in a sample to be tested, and performing electrochemiluminescence detection using a three-electrode system;
preferably, during detection, a co-reactant is added into the reaction system, and the co-reactant is preferably tri-n-propylamine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558396A (en) * | 2020-05-12 | 2020-08-21 | 山东师范大学 | Electron-rich tetraphenyl ethylene catalyst and preparation method and application thereof |
| CN111751435A (en) * | 2020-06-22 | 2020-10-09 | 济南大学 | Preparation method and application of ferroportin-based encapsulated tetraphenylethylene immunosensor |
| CN113173996A (en) * | 2021-04-26 | 2021-07-27 | 广东省医疗器械质量监督检验所 | Aggregation-induced emission peptide assembly, preparation method, detection method and application thereof |
| CN113501937A (en) * | 2021-04-23 | 2021-10-15 | 山东师范大学 | Electrochemical luminescence sensor based on bipolar aggregation induction of thiophene tetraphenyl vinyl conjugated microporous polymer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442873A (en) * | 2010-10-08 | 2012-05-09 | 国家纳米科学中心 | Fluorescence nanometer organic porous material as well as preparation method and application thereof |
| CN106898492A (en) * | 2017-01-16 | 2017-06-27 | 华南师范大学 | A kind of preparation method and applications for being conjugated microporous polymer film |
-
2019
- 2019-12-12 CN CN201911278434.7A patent/CN110982046B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442873A (en) * | 2010-10-08 | 2012-05-09 | 国家纳米科学中心 | Fluorescence nanometer organic porous material as well as preparation method and application thereof |
| CN106898492A (en) * | 2017-01-16 | 2017-06-27 | 华南师范大学 | A kind of preparation method and applications for being conjugated microporous polymer film |
Non-Patent Citations (3)
| Title |
|---|
| LEE HYUNPYO: ""Preparation of microporous polymers consisting of tetraphenylethene and alkyne units"", 《MACROMOLECULAR RESEARCH》 * |
| SURESH, VENKATA M. ET AL.: ""Synthesis, Characterization, and Modeling of a Functional Conjugated Microporous Polymer: CO2 Storage and Light Harvesting"", 《J. PHYS. CHEM. C》 * |
| YUAN WANG ZHANG ET AL.: ""Conjugated Hyperbranched Poly(aryleneethynylene)s: Synthesis, Photophysical Properties, Superquenching by Explosive, Photopatternability, and Tunable High Refractive Indices"", 《CHEMISTRY - A EUROPEAN JOURNA》 * |
Cited By (5)
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|---|---|---|---|---|
| CN111558396A (en) * | 2020-05-12 | 2020-08-21 | 山东师范大学 | Electron-rich tetraphenyl ethylene catalyst and preparation method and application thereof |
| CN111751435A (en) * | 2020-06-22 | 2020-10-09 | 济南大学 | Preparation method and application of ferroportin-based encapsulated tetraphenylethylene immunosensor |
| CN113501937A (en) * | 2021-04-23 | 2021-10-15 | 山东师范大学 | Electrochemical luminescence sensor based on bipolar aggregation induction of thiophene tetraphenyl vinyl conjugated microporous polymer and preparation method and application thereof |
| CN113501937B (en) * | 2021-04-23 | 2023-09-12 | 山东师范大学 | Electrochemical luminescence sensor based on thiophene tetrastyryl conjugated microporous polymer bipolar aggregation induction and preparation method and application thereof |
| CN113173996A (en) * | 2021-04-26 | 2021-07-27 | 广东省医疗器械质量监督检验所 | Aggregation-induced emission peptide assembly, preparation method, detection method and application thereof |
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