| Electrochemiluminescence（ECL）is a kind of light radiation produced by the chemical reaction between the electrode reaction products or between the electrode reaction products and some components in the solution by applying a certain voltage on the electrode.Electrochemiluminescence has the advantages of both electrochemistry and chemiluminescence,such as high sensitivity,low detection limit,broad linear range,simple instrument,convenient operation,easy automation and so on.Electrochemiluminescence（ECL）is a new detection technology,which can not only provide luminous intensity and electrochemical signals,but also provide more information about optical detection and imaging.At present,commercial applications mainly rely on the traditional system of bipyridine ruthenium and its derivatives with positive potential response.Many organic dyes,such as polycyclic aromatic hydrocarbons and heterocyclic compounds,including boron-dipyrrole methylene（BODIPY）series,have shown their outstanding potential in ECL.Due to low solubility in aqueous solution,the instability of reaction transition state and free radical intermediates and the narrow potential window of working electrodes in aqueous solution,resulting the ECL of a less luminescence molecular can be reproduced in the aqueous phase.Therefore,the new materials of natural light pigment and biomimetic light pigment ECL have been developed and studied in this paper.This strategy is in line with the green development strategy.The main works include:（1）In Situ electropolymerization of Zinc aminoporphyrin on the electrode surface was used as ECL emitter of the covalent organic framework of Zinc porphyrin,and the Helicobacter Pylori immunosensor was successfully constructed by modifying the antibody.Zinc porphyrin itself is a good ECL emitter,but because of its poor solubility,π-πstack effect,seriously affect its application.The structure of Zinc Porphyrin covalent organic framework（COF）with large specific surface area is favorable to stabilize the morphology of Porphyrin on the electrode surface and form stable luminescence region.If antibodies on the surface of the electrode trap Helicobacter Pylori,the bacteria block electron transfer and energy transfer,causing ECL to weaken.A broad linear range of 10 cfu m L-1 to 105 cfu m L-1 with a linear correlation coefficient of 0.98 was obtained based on the Helicobacter Pylori sensor.（2）An ECL emitter based on phycocyanobilin was used as an ECL emitter to construct an unlabeled copper ion detection sensor.Phycocyanin is a natural blue pigment and one of the important Porphyrin metabolites.It is often used as a fluorescent detection molecule.In this experiment,it was found that phycocyanobilin has good ECL emission characteristics in organic phase and aqueous phase electrolyte,in which there are two significant emission potentials（-2.2 V and-0.2V vs Ag/Ag Cl）in acetonitrile electrolyte solution and an obvious luminous potential（-1.5 V vs Ag/Ag Cl）in the aqueous buffer.At the same time,the ECL spectrum of phycocyanobilin was studied,and it was found that the ECL spectrum of phycocyanin can be different from that of porphyrin,which proved that phycocyanobilin have different luminescence mechanism from porphyrin.The possible ECL luminescence mechanism was inferred by electrochemical and spectroscopic characterization.Finally,according to quenching effect of copper ion on the ECL of phycocyanobilin,it is applied to the determination of copper ion.The linear range of 0.05μM to 10μM with a linear correlation coefficient of 0.99 is obtained,and the detection limit is lower. |
