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CN-121994900-A - Copper porphyrin conjugated acetylene polymer composite material, preparation method and application thereof in biological thiol photoelectric detection

CN121994900ACN 121994900 ACN121994900 ACN 121994900ACN-121994900-A

Abstract

The invention discloses a copper porphyrin conjugated acetylene polymer composite material, a preparation method and application thereof in biological mercaptan photoelectric detection, the composite material comprises an electrochemical reduction graphene oxide layer, a poly-1, 4-diacetylene benzene layer and a copper porphyrin conjugated acetylene copolymer layer, wherein the three layers form a layered composite structure through pi-pi interaction. The copper porphyrin conjugated acetylene copolymer is prepared by copolymerizing a1, 4-diacetylene benzene monomer and a copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer through a Sonogashira coupling reaction, and the composite material utilizes a porphyrin center The double recognition site mechanism of Cu-S coordination bond formed with sulfhydryl and click reaction of alkyne bond and sulfhydryl under illumination realizes high sensitivity and high selectivity detection of L-cysteine and reduced glutathione, and the detection limit of L-cysteine can reach 2.3 mu M.

Inventors

  • YIN DONGHANG
  • QUAN JING
  • CHANG SIYUAN
  • CHEN TIANYI
  • LIU XIAOLE
  • SUN JINGXUAN
  • PENG JING

Assignees

  • 南京科技职业学院

Dates

Publication Date
20260508
Application Date
20251117

Claims (10)

  1. 1. The copper porphyrin conjugated acetylene polymer composite material is characterized by comprising an electrochemical reduction graphene oxide layer, a poly-1, 4-diacetylene benzene layer and a copper porphyrin conjugated acetylene copolymer layer, wherein the copper porphyrin conjugated acetylene copolymer layer is formed by copolymerizing a1, 4-diacetylene benzene monomer and a copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer through a Sonogashira coupling reaction, and the copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer is coordinated on the central ring The poly-1, 4-diacetylene benzene layer is formed by polymerizing 1, 4-diacetylene benzene monomers through a Sonogashira coupling reaction, and the electrochemical reduction graphene oxide layer, the poly-1, 4-diacetylene benzene layer and the copper porphyrin conjugated acetylene copolymer layer are sequentially deposited on the surface of the conductive substrate and form a layered composite structure through pi-pi interaction.
  2. 2. The copper porphyrin conjugated acetylene polymer composite material according to claim 1, wherein the molar ratio of the 1, 4-diacetylene benzene monomer to the copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer is (80-98): 2-20.
  3. 3. The copper porphyrin conjugated acetylene polymer composite material according to claim 1, wherein the thickness of the electrochemical reduction graphene oxide layer is 50-200 nm, the thickness of the poly 1, 4-diacetylene benzene layer is 100-300 nm, and the thickness of the copper porphyrin conjugated acetylene copolymer layer is 150-400 nm.
  4. 4. The copper porphyrin conjugated acetylene polymer composite material according to claim 1, wherein the conductive substrate is any one of an indium tin oxide glass electrode, a fluorine doped tin oxide glass electrode, a gold electrode or a carbon-based electrode.
  5. 5. A method for preparing the cuporphyrin conjugated acetylene polymer composite material according to any one of claims 1 to 4, which comprises the following steps: (1) Dripping graphene oxide dispersion on the surface of a conductive substrate, and reducing 3-8 min under the voltage of-1.0 to-1.5V by an electrochemical reduction method to obtain an electrochemical reduction graphene oxide layer modified conductive substrate; (2) Placing the conductive substrate modified by the electrochemical reduction graphene oxide layer obtained in the step (1) into a reaction solution containing a1, 4-diacetylene benzene monomer, a catalyst and alkali, reacting at 70-90 ℃ for 1-3 h, and generating a poly 1, 4-diacetylene benzene layer on the surface of the electrochemical reduction graphene oxide layer in situ; (3) Placing the modified electrode obtained in the step (2) into a mixed reaction solution containing a1, 4-diacetylene benzene monomer, a copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer, a catalyst and alkali, reacting at 75-95 ℃ for 2-5 h, and generating a copper porphyrin conjugated acetylene copolymer layer on the surface of the poly 1, 4-diacetylene benzene layer in situ to obtain the copper porphyrin conjugated acetylene polymer composite material modified electrode.
  6. 6. The method according to claim 5, wherein in the step (1), the concentration of the graphene oxide dispersion liquid is 0.2-1.0 mg/mL, the electrochemical reduction voltage is-1.2V, and the reduction time is 5 min.
  7. 7. The method according to claim 5, wherein in the step (2) and the step (3), the catalyst is a combination of bis (triphenylphosphine) palladium dichloride and cuprous iodide, the base is triethylamine or N, N-diisopropylethylamine, and the solvent is at least one of dimethylformamide, tetrahydrofuran or toluene.
  8. 8. The method according to claim 5, wherein in the step (3), the molar ratio of the 1, 4-diacetylene-benzene monomer to the copper-coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer is (85-95): (5-15), the reaction temperature is 85 ℃, and the reaction time is 3 h.
  9. 9. Use of the cuporphyrin conjugated acetylene polymer composite material according to any one of claims 1 to 4 for preparing a bio-thiol photoelectrochemical sensor.
  10. 10. The use according to claim 9, wherein the biological thiol is at least one of L-cysteine, reduced glutathione, homocysteine or cysteamine.

Description

Copper porphyrin conjugated acetylene polymer composite material, preparation method and application thereof in biological thiol photoelectric detection Technical Field The invention belongs to the field of functional polymer materials and photoelectrochemical sensing, and particularly relates to a copper porphyrin conjugated acetylene polymer composite material, a preparation method thereof and application thereof in biological thiol photoelectrochemical detection. Background Biological thiol compounds, such as L-cysteine (L-Cys) and reduced Glutathione (GSH), exert important physiological functions in organisms and are involved in key physiological processes such as protein folding, cell signal transduction, redox homeostasis maintenance and the like. Abnormal changes in biological thiol concentration are closely related to a variety of diseases such as Alzheimer's disease, parkinson's disease, liver injury, cancer, and the like. Therefore, the establishment of a sensitive and selective biological thiol detection method has important significance for disease diagnosis and treatment. The existing biological mercaptan detection method mainly comprises a high performance liquid chromatography method, a capillary electrophoresis method, a mass spectrometry method, an electrochemical method and the like. In recent years, the photoelectrochemical sensing technology has attracted wide attention in the field of biological thiol detection due to the advantages of high sensitivity, rapid response, low background signal and the like. Conjugated microporous polymers (Conjugated Microporous Polymers, CMPs) have a large specific surface area, tunable photoelectric properties and good chemical stability, and have been used in the field of photoelectrochemical sensing. For example, liu et al report on a D-A type porphyrin-phthalocyanine based polymer hollow tube for photodegradation and photoelectrochemical sensing of bisphenol A in Applied Surface Science (2023, vol. 638, page 158129). This study facilitates the separation and transport of photogenerated carriers by constructing a periodic donor-acceptor (D-a) structure. However, this technique is mainly applied to bisphenol a detection and does not involve the application of biological thiol detection. At present, the prior art has the following defects: Firstly, the existing conjugated microporous polymer photoelectrochemical sensor mainly aims at detecting substances such as H 2O2, glucose, bisphenol A and the like, and lacks a specific recognition mechanism and a high-sensitivity detection method aiming at biological thiol molecules. Secondly, although metalloporphyrin has good coordination ability and photoelectric property, the metalloporphyrin is introduced into conjugated acetylene polymer skeleton and is used for photoelectrochemical detection of biological thiol, and the design thought of realizing selective detection by utilizing specific interaction between metal center and thiol group is lacking. Thirdly, the existing photoelectrochemical sensing material has limited light absorption range, and the separation and transmission efficiency of photo-generated carriers are low, so that the photocurrent response is weak, and the detection sensitivity needs to be improved. Therefore, development of a novel photoelectrochemical sensing material capable of achieving high sensitivity and high selectivity detection of biological thiols is highly demanded. Disclosure of Invention Aiming at the problems in the prior art, the invention aims to provide a copper porphyrin conjugated acetylene polymer composite material, a preparation method thereof and application thereof in biological thiol photoelectrochemical detection, so as to solve the technical problems of low biological thiol detection sensitivity, poor selectivity and weak photocurrent response in the prior art. To achieve the above object, a first aspect of the present invention provides a copper porphyrin conjugated acetylene polymer composite material, comprising an electrochemical reduction graphene oxide layer (ERGO), a poly 1, 4-diacetylene benzene layer (PDEB) and a copper porphyrin conjugated acetylene copolymer layer [ P (DEB-CuTP) ], characterized in that: The copper porphyrin conjugated acetylene copolymer layer [ P (DEB-CuTP) ] is formed by copolymerizing a1, 4-diacetylene benzene monomer and a copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer through a Sonogashira coupling reaction, wherein Cu 2+ ions are coordinated on the central ring of the copper coordinated 5,10,15, 20-tetra (4-acetylenyl) porphyrin monomer; The poly 1, 4-diacetylene benzene layer (PDEB) is polymerized by 1, 4-diacetylene benzene monomer through Sonogashira coupling reaction; the electrochemical reduction graphene oxide layer (ERGO), the poly-1, 4-diacetylene benzene layer (PDEB) and the copper porphyrin conjugated acetylene copolymer layer [ P (DEB-CuTP) ] are sequentially deposited on the surface of the cond