Xiang Yunhui, Kong Yao, Feng Wenqi, Ye Xiaoxue, Liu Zhihong
College of Chemistry and Molecular Sciences, Wuhan University Wuhan 430072 China
College of Chemistry and Chemical Engineering, Hubei University Wuhan 430062 China
Chem Sci. 2021 Sep 1;12(39):12977-12984. doi: 10.1039/d1sc03069h. eCollection 2021 Oct 13.
Photoelectrochemical (PEC) sensing has been developing quickly in recent years, while its application is still in the infancy. The complexity of biological environments poses a high challenge to the specificity and reliability of PEC sensing. We herein proposed the concept of small-molecule organic semiconductor (SMOS)-based ratiometric PEC sensing making use of the structural flexibility as well as readily tunable energy band of SMOS. Xanthene skeleton-based was prepared as a photoactive molecule, and its absorption band and corresponding PEC output can be modulated by an intramolecular charge transfer process. As such, the target mediated shift of absorption offered the opportunity to construct a ratiometric PEC sensor. A proof-of-concept probe was synthesized and assembled on a Ti wire electrode (TiWE) to prepare a highly selective microsensor for thiols. Under two monochromatic laser excitation (808 nm and 750 nm), /TiWE offered a ratiometric signal ( / ), which exhibited pronounced capacity to offset the disturbance of environmental factors, guaranteeing its reliability for application . The ratiometric PEC sensor achieved the observation of bio-thiol release induced by cytotoxic edema and fluctuations of thiols in drug-induced epilepsy in living rat brains.
近年来，光电化学（PEC）传感发展迅速，但其应用仍处于起步阶段。生物环境的复杂性对PEC传感的特异性和可靠性提出了巨大挑战。在此，我们提出了基于小分子有机半导体（SMOS）的比率型PEC传感概念，利用了SMOS的结构灵活性以及易于调节的能带。制备了基于呫吨骨架的光活性分子，其吸收带和相应的PEC输出可通过分子内电荷转移过程进行调制。因此，目标介导的吸收峰移动为构建比率型PEC传感器提供了契机。合成了一个概念验证探针并组装在钛丝电极（TiWE）上，以制备用于检测硫醇的高选择性微传感器。在两种单色激光激发（808 nm和750 nm）下，/TiWE提供了一个比率信号（/），该信号表现出显著的抵消环境因素干扰的能力，保证了其应用的可靠性。该比率型PEC传感器实现了对活大鼠脑中细胞毒性水肿诱导的生物硫醇释放以及药物性癫痫中硫醇波动的观测。
