PMID- 34186304 OWN - NLM STAT- MEDLINE DCOM- 20210819 LR - 20210819 IS - 1873-4235 (Electronic) IS - 0956-5663 (Linking) VI - 191 DP - 2021 Nov 1 TI - High-efficiency charge transfer on SERS-active semiconducting K(2)Ti(6)O(13) nanowires enables direct transition of photoinduced electrons to protein redox centers. PG - 113452 LID - S0956-5663(21)00489-9 [pii] LID - 10.1016/j.bios.2021.113452 [doi] AB - Photoinduced charge transfer (PICT) plays a crucial role in the chemical mechanism of surface-enhanced Raman scattering (SERS), in which small organic molecules are generally used as probes. Herein, semiconducting K(2)Ti(6)O(13) nanowires (NWs) are synthesized and are found to exhibit high SERS activity probed by 4-mercaptobenzoic acid (4-MBA). Density functional theory (DFT) calculations reveal high-efficiency CT on the K(2)Ti(6)O(13) nanowires. Furthermore, PICT on the K(2)Ti(6)O(13) NWs is for the first time evidenced by a redox protein, cytochrome c (Cyt c). Under optimized experimental conditions, the transformation of oxidized Cyt c to its reduced state clearly verifies the electron transfer (ET) from the K(2)Ti(6)O(13) nanowire to the protein. The ET mechanism is explored based on energy levels of semiconductors and molecular dynamics simulations, thus revealing the importance of energy level matching and electron tunneling from the semiconductor surface to the redox center. This study indicates a great potential of multiple-layered K(2)Ti(6)O(13) NWs in the application of SERS on semiconducting materials and more importantly, it provides a new route for the rational design of protein-semiconductor interfaces for investigating electron transfer processes of redox proteins and biocatalytic reactions. CI - Copyright (c) 2021 Elsevier B.V. All rights reserved. FAU - Chen, Lei AU - Chen L AD - Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, China. FAU - Tang, Jinping AU - Tang J AD - State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. FAU - Ma, Hao AU - Ma H AD - State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. FAU - Jin, Sila AU - Jin S AD - Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University, Chunchon, 24341, South Korea. FAU - Xue, Xiangxin AU - Xue X AD - Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, China. FAU - Han, Xiao Xia AU - Han XX AD - State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China. Electronic address: hanxiaoxia@jlu.edu.cn. FAU - Jung, Young Mee AU - Jung YM AD - Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University, Chunchon, 24341, South Korea. Electronic address: ymjung@kangwon.ac.kr. LA - eng PT - Journal Article DEP - 20210619 PL - England TA - Biosens Bioelectron JT - Biosensors & bioelectronics JID - 9001289 RN - D1JT611TNE (Titanium) SB - IM MH - *Biosensing Techniques MH - Electrons MH - *Nanowires MH - Oxidation-Reduction MH - Titanium OTO - NOTNLM OT - Charge transfer OT - Cytochrome c OT - K(2)Ti(6)O(13) nanowires OT - SERS OT - Semiconductor EDAT- 2021/06/30 06:00 MHDA- 2021/08/20 06:00 CRDT- 2021/06/29 20:18 PHST- 2021/06/04 00:00 [received] PHST- 2021/06/16 00:00 [accepted] PHST- 2021/06/30 06:00 [pubmed] PHST- 2021/08/20 06:00 [medline] PHST- 2021/06/29 20:18 [entrez] AID - S0956-5663(21)00489-9 [pii] AID - 10.1016/j.bios.2021.113452 [doi] PST - ppublish SO - Biosens Bioelectron. 2021 Nov 1;191:113452. doi: 10.1016/j.bios.2021.113452. Epub 2021 Jun 19.