CAS Key Laboratory of Bio-Inspired Materials and Interfacial Science, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Key Laboratory for Intelligent Nano Materials and Devices of Ministry of Education, Institute for Frontier Science of Nanjing University of Aeronautics and Astronautics, Nanjing, 210016, China.
Biosens Bioelectron. 2022 Dec 15;218:114741. doi: 10.1016/j.bios.2022.114741. Epub 2022 Sep 28.
Light-driven proton directional transport is important in living beings as it could subtly realize the light energy conversion for living uses. In the past years, 2D materials-based nanochannels have shown great potential in active ion transport due to controllable properties, including surface charge distribution, wettability, functionalization, electric structure, and external stimuli responsibility, etc. However, to fuse the inorganic materials into bio-membranes still faces several challenges. Here, we proposed peptide-modified WS nanosheets via cysteine linkers to realize tunable band structure and, hence, enable light-driven proton transmembrane transport. The modification was achieved through the thiol chemistry of the -SH groups in the cysteine linker and the S vacancy on the WS nanosheets. By tuning the amino residues sequences (lysine-rich peptides, denoted as KFC; and aspartate-rich peptides, denoted as DFC), the ζ-potential, surface charge, and band energy of WS nanosheets could be rationally regulated. Janus membranes formed by assembling the peptide-modified WS nanosheets could realize the proton transmembrane transport under visible light irradiation, driven by a built-in potential due to a type II band alignment between the KFC-WS and DFC-WS. As a result, the proton would be driven across the formed nanochannels. These results demonstrate a general strategy to build bio-semiconductor materials and provide a new way for embedding inorganic materials into biological systems toward the development of bioelectronic devices.
光驱动质子定向输运在生物体内很重要，因为它可以巧妙地实现光能转换以供生物使用。在过去的几年中，基于二维材料的纳米通道由于其可控的性质，包括表面电荷分布、润湿性、功能化、电结构和对外界刺激的响应等，在主动离子输运中显示出巨大的潜力。然而，将无机材料融合到生物膜中仍然面临着一些挑战。在这里，我们通过半胱氨酸连接体将肽修饰的 WS 纳米片，实现了可调谐的能带结构，从而实现了光驱动质子跨膜传输。这种修饰是通过半胱氨酸连接体中的 -SH 基团和 WS 纳米片上的 S 空位的硫醇化学实现的。通过调节氨基酸残基序列（富含赖氨酸的肽，记为 KFC；和富含天冬氨酸的肽，记为 DFC），WS 纳米片的 ζ 电位、表面电荷和能带能量可以得到合理的调节。由肽修饰的 WS 纳米片组装而成的 Janus 膜可以在可见光照射下实现质子跨膜传输，这是由于 KFC-WS 和 DFC-WS 之间的 II 型能带排列产生的内置电势驱动的。结果，质子会被驱动穿过形成的纳米通道。这些结果展示了一种构建生物半导体材料的通用策略，并为将无机材料嵌入生物系统以开发生物电子器件提供了一种新方法。
