CN-121975113-A - Self-catalytic perylene bisimide electrochemiluminescence material and application thereof in phosphorus iminothiolate detection

Abstract

The invention discloses an autocatalytic perylene imide electrochemiluminescence material and application thereof in phosphorus iminothiolate detection, and relates to the technical field of analytical chemistry. The electrochemical luminescent material is formed by condensing 3,4,9, 10-perylene tetracarboxylic dianhydride and a nitrogenous precursor through hydrothermal reaction, so that a polymer with a linear conjugated structure is formed, carbonyl in a main chain of the polymer is used as an endogenous active site, persulfate can be efficiently adsorbed and activated, and self-catalyzed cathode electrochemical luminescence without an additional catalyst is realized. The material can generate strong and stable luminous signals under the ultralow potential, and is obviously superior to the traditional system. Based on the method, the invention constructs the electrochemiluminescence biosensor with high sensitivity and high selectivity, and combines a carboxylesterase inhibition mechanism to detect the trace organic phosphorus pesticide, namely the iminothiolane. The method has the advantages of quick response and strong anti-interference capability, and is suitable for actual analysis of pesticide residues in food and environmental samples.

Inventors

• NIE YAMIN
• ZHANG CONGRUI
• ZHAO LONGGE
• ZHOU YANMEI

Assignees

• 河南大学

Dates

Publication Date

20260505

Application Date

20260211

Claims (10)

1. 1. An autocatalytic electrochemical light emitting emitter characterized by any one of the following structures: ; wherein, the value of n is an integer of 2-300.
2. 2. The method of preparing an autocatalytic electrochemical light emitting emitter according to claim 1, comprising the steps of: mixing 3,4,9, 10-perylene tetracarboxylic dianhydride and a nitrogen-containing precursor, and obtaining the self-catalytic electrochemical luminescence emitter through hydrothermal reaction; The nitrogen-containing precursor is urea, oxamide, semicarbazide or biurea.
3. 3. The preparation method according to claim 2, wherein the hydrothermal reaction is carried out at a temperature of 140-200 ℃ for a time of 5-12 hours.
4. 4. The method of claim 2, wherein the molar ratio of the nitrogen-containing precursor to 3,4,9, 10-perylenetetracarboxylic dianhydride is from 25:1 to 200:1.
5. 5. The method of claim 2, wherein when the nitrogen-containing precursor is urea, the molar ratio of 3,4,9, 10-perylenetetracarboxylic dianhydride to urea is 1:65.3.
6. 6. Use of the self-catalyzed electrochemical luminescence emitter according to claim 1 for constructing a thioimine detection system.
7. 7. An electrochemiluminescence biosensor, comprising a working electrode, wherein the surface of the working electrode is modified with the self-catalyzed electrochemiluminescence emitter according to claim 1.
8. 8. A method for detecting iminothiolane using the electrochemiluminescence biosensor of claim 7, comprising the steps of: Incubating a sample to be tested and carboxylesterase to enable the iminothiolane in the sample to be tested to inhibit the activity of the carboxylesterase, then adding a specific substrate of the carboxylesterase to continue incubation, and completing enzymatic reaction to obtain an enzymatic reaction bottom solution to be tested; And carrying out electrochemiluminescence detection on the substrate solution to be detected of the enzymatic reaction in electrolyte containing peroxodisulfate by using the electrochemiluminescence biosensor, and quantitatively analyzing the content of the iminothiolate according to the intensity of an electrochemiluminescence signal.
9. 9. The method of claim 8, wherein the specific substrate is 1-naphthalate acetate.
10. 10. The method of claim 8, wherein the concentration of peroxodisulfate is 1 mmol/L.

Description

Self-catalytic perylene bisimide electrochemiluminescence material and application thereof in phosphorus iminothiolate detection Technical Field The invention relates to the technical field of analytical chemistry, in particular to an autocatalytic perylene bisimide electrochemiluminescence material and application thereof in phosphorus iminothiolate detection. Background Electrochemiluminescence (ECL) is a technology for triggering luminescence through electrochemical reaction at an electrode interface, and by virtue of the unique space-time controllability and near zero background noise advantages, the ECL becomes an important technical tool in the fields of sensitive clinical diagnosis, super-resolution imaging, photoelectric device preparation, electro-catalyst mechanism research and the like. ECL systems are mainly divided into annihilation type and co-reaction type, wherein the co-reaction type ECL systems have been developed into practical platforms widely used at present due to higher detection sensitivity and stability. However, the coreactive ECL system has fundamental technical limitations in that the coreactant has a slow rate of charge transfer through chemical bonds during electrochemical generation, resulting in lower kinetic efficiency of the reaction. To solve this problem, technical strategies of introducing co-reaction promoters (such as monoatomic catalysts, transition metal oxides, transition metal sulfides, etc.) are generally adopted in the industry, and active free radicals are generated by the dissociation of the catalytic co-reactants, so that ECL luminous efficiency is improved, and sensitivity requirements required by actual detection are met (Zhou et al, 2024; li et al, 2025; guo et al, 2021). Although the strategy has advanced to some extent, the conventional ternary ECL system of 'luminophor/coreactant' still has inherent defects, which are specifically characterized by low interfacial mass transfer efficiency, complex system composition, poor reaction controllability, significant background interference, non-ideal signal-to-noise ratio and the like, and seriously affect the reliability of detection results. In order to overcome the limitation of the ternary system, the high-activity catalytic site is directly integrated in the ECL luminophor, and the activation of the coreactant is realized through the luminophor, so that the method has become a broad-prospect technical direction for designing an advanced ECL system. For example, researchers construct Ru-OH-Zr catalytic centers in a metal organic framework to enhance the activation efficiency of persulfate (S 2O82-), and finally realize high-efficiency ECL luminescence (Xu et al, 2024) at a potential of-1.9V, and further develop the idea to directly anchor gold nanoparticles and single atoms on carbon nitride to form double active sites for activating S 2O82-, so that the luminescence potential is reduced to-1.5V, and meanwhile, high-strength ECL signals (Xu et al, 2024) are obtained. Although the above technical solution improves the performance, such a synergistic ECL system still needs to apply a higher potential to achieve satisfactory detection sensitivity. However, too high an operating potential inevitably causes serious electrochemical interference, causes damage to biomolecules, and produces unfavorable signal crosstalk, which all prevent the application of the system in reliable quantitative bioassays. Therefore, developing an ECL luminophore that can operate in a simple binary ECL system (containing only luminophores and coreactants) and that has both ultra-low potential triggering characteristics and ultra-high detection sensitivity remains a key and challenging research goal for driving the development of practical biological analysis techniques. Disclosure of Invention The invention aims to provide an autocatalytic perylene imide electrochemiluminescence material and application thereof in phosphorus iminothiolate detection, so as to solve the problems in the prior art. In order to achieve the above object, the present invention provides the following solutions: the technical scheme of the invention is to provide an autocatalytic electrochemiluminescence emitter which is any one of the following structures: ; wherein, the value of n is an integer of 2-300. The second technical scheme of the invention is to provide a preparation method of the self-catalytic electrochemical luminescence emitter, which comprises the following steps: Mixing 3,4,9, 10-perylene tetracarboxylic dianhydride (PTCDA) and a nitrogen-containing precursor, and performing hydrothermal reaction to obtain the self-catalytic electrochemical luminescence emitter; the nitrogen-containing precursor is Urea (Urea), oxamide (OA), semicarbazide (SEM), or biurea (DCH). Further, the temperature of the hydrothermal reaction is 140-200 ℃ and the time is 5-12h. Further, the temperature of the hydrothermal reaction is 180 ℃ and the time is 8 hours. Further,