Hao Yuanqiang, Yang Yewen, Wang Wenhui, Gu Hui, Chen Wansong, Li Chunlan, Zhang Peisheng, Zeng Rongjin, Xu Maotian, Chen Shu
Key Laboratory of Theoretical Organic Chemistry and Functional Molecule, Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201, China.
Hunan Provincial Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China.
Anal Chem. 2024 Dec 10;96(49):19822-19832. doi: 10.1021/acs.analchem.4c05336. Epub 2024 Nov 22.
Hydrogen sulfide (HS) is an important bioactive molecule that plays a significant role in various functions, particularly in the living brain, where it is closely linked to cognition, memory, and several neurological diseases. Consequently, developing effective detection methods for HS is essential for studying brain functions and the underlying mechanisms of these diseases. This study aims to construct a novel photoelectrochemical (PEC) microelectrode Ti/TiO@HSP for the quantitative monitoring of HS levels in the living brain. The PEC microelectrode Ti/TiO@HSP is formed by covalently bonding a specifically designed organic PEC probe HSP, which possesses a D-π- structure, to the surface of TiO nanotubes generated via in situ anodic oxidation of titanium wire. The PEC probe HSP can effectively react with HS and generate significant photocurrent response under long-wavelength excitation light (560 nm), thereby achieving quantitative detection of HS. The sensor demonstrates high sensitivity and good selectivity. In vivo experiments utilizing the PEC microelectrode Ti/TiO@HSP enable the monitoring of dynamic changes in HS levels across various regions of the mouse brain. The findings reveal that in normal mice, the concentration of HS in the hippocampus is significantly higher than in the striatum and cerebral cortex. Additionally, following propargylglycine drug stimulation, HS concentrations in different brain regions were observed to decrease, with the most substantial reduction noted in the hippocampus. This suggests that cystathionine γ-lyase (CSE) is the primary enzyme responsible for HS production in this area, while the striatum exhibits a less pronounced decrease in HS concentration, indicating a reliance on alternative enzymatic pathways for HS production. Therefore, this study not only successfully develops a high-performance HS detection sensor but also provides new experimental tools and theoretical foundations for further exploring the roles of HS in neurophysiological and pathological processes.
硫化氢（HS）是一种重要的生物活性分子，在各种功能中发挥着重要作用，特别是在活脑功能中，它与认知、记忆以及多种神经疾病密切相关。因此，开发有效的HS检测方法对于研究脑功能和这些疾病的潜在机制至关重要。本研究旨在构建一种新型光电化学（PEC）微电极Ti/TiO@HSP，用于定量监测活脑内的HS水平。PEC微电极Ti/TiO@HSP是通过将一种具有D-π-结构的特殊设计的有机PEC探针HSP共价键合到通过钛丝原位阳极氧化生成的TiO纳米管表面而形成的。PEC探针HSP能与HS有效反应，并在长波长激发光（560 nm）下产生显著的光电流响应，从而实现对HS的定量检测。该传感器具有高灵敏度和良好的选择性。利用PEC微电极Ti/TiO@HSP进行的体内实验能够监测小鼠大脑不同区域HS水平的动态变化。研究结果表明，在正常小鼠中，海马体中的HS浓度显著高于纹状体和大脑皮层。此外，在炔丙基甘氨酸药物刺激后，观察到不同脑区的HS浓度降低，其中海马体中的降低最为显著。这表明胱硫醚γ-裂解酶（CSE）是该区域HS产生的主要酶，而纹状体中HS浓度的降低不太明显，表明其HS产生依赖于其他酶促途径。因此，本研究不仅成功开发了一种高性能的HS检测传感器，还为进一步探索HS在神经生理和病理过程中的作用提供了新的实验工具和理论基础。
