Journal
ACS SENSORS
Volume 7, Issue 2, Pages 415-422Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acssensors.1c02595
Keywords
photoelectrochemical sensor; small-molecule photosensitizer; in situ formation; coumarin dye; thiophenol
Funding
- National Natural Science Foundation of China [21804085, 52073087, 22074089, 51873058, 21877034]
- Key Research and Development Program of Hunan province [2019GK2237]
- science and technology innovation Program of Hunan Province [2021RC5028]
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This paper proposes a new strategy for PEC analysis by in situ generation of organic photosensitizers, achieving highly selective turn-on PEC response. The proposed strategy is expected to expand the paradigm of PEC sensing and holds potential for detecting various other analytes.
Small-molecule photosensitizers have great application prospects in photoelectrochemical (PEC) sensing due to their defined composition, diversified structure, and adjustable photophysical properties. Herein, we propose a new strategy for PEC analysis based on the target-induced in situ formation of the organic photosensitizer. Taking thiophenol (PhSH) as a model analyte, we designed and synthesized a 2,4-dinitrophenyl (DNP)-caged coumarin precursor (Dye-PhSH), which was then covalently coupled onto the TiO2 nanoarray substrate to obtain the working photoanode. Due to the intramolecular photoinduced electron transfer process, Dye-PhSH has only a very weak photoelectric response. Upon reacting with the target, Dye-PhSH undergoes a tandem reaction of the detachment of the DNP moiety and the intramolecular cyclization process, which leads to a coumarin dye with a pronounced photoelectric effect, thus achieving a highly selective turn-on PEC response to PhSH. For the first time, this study was to construct a PEC sensor by exploiting specific organic reactions for the in situ generation of small molecule-based photoactive material. It can be anticipated that the proposed strategy will expand the paradigm of PEC sensing and holds great potential for detecting various other analytes.
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