Activating SERS Signals of Inactive Analytes: Creating an Energy Bridge between Metal/Molecule Energy Alignment via Metal/Semiconductor Transitions.
| Title: | Activating SERS Signals of Inactive Analytes: Creating an Energy Bridge between Metal/Molecule Energy Alignment via Metal/Semiconductor Transitions. |
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| Authors: | Mai QD; Phenikaa University Nano Institute (PHENA), Phenikaa University, Hanoi 12116, Vietnam.; Dang THT; Phenikaa University Nano Institute (PHENA), Phenikaa University, Hanoi 12116, Vietnam.; Nguyen TT; Phenikaa University Nano Institute (PHENA), Phenikaa University, Hanoi 12116, Vietnam.; Faculty of Materials Science and Engineering (MSE), Phenikaa University, Hanoi 12116, Vietnam.; Nguyen TTT; Laboratory of Biomedical Materials, Hanoi University of Science and Technology (HUST), Hanoi 10000, Vietnam.; Ngoc Bach T; Institute of Materials Science (IMS), Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Hanoi 10000, Vietnam.; Nguyen AS; Phenikaa University Nano Institute (PHENA), Phenikaa University, Hanoi 12116, Vietnam.; Faculty of Biotechnology, Chemistry and Environmental Engineering, Phenikaa University, Hanoi 12116, Vietnam.; Quang Thuc D; Phenikaa University Nano Institute (PHENA), Phenikaa University, Hanoi 12116, Vietnam.; Faculty of Biotechnology, Chemistry and Environmental Engineering, Phenikaa University, Hanoi 12116, Vietnam.; Vu TT; Faculty of Physics-Biophysics, Vietnam Military Medical University (VMMU), 160 Phung Hung, Hanoi 10000, Viet Nam.; Hung ND; Faculty of Electronic Materials and Devices, Ha Noi University of Science and Technology (HUST), 01 Dai Co Viet, Ha Noi 10000, Viet Nam.; Pham AT; Faculty of Biotechnology, Chemistry and Environmental Engineering, Phenikaa University, Hanoi 12116, Vietnam.; Faculty of Materials Science and Engineering (MSE), Phenikaa University, Hanoi 12116, Vietnam.; Le AT; Phenikaa University Nano Institute (PHENA), Phenikaa University, Hanoi 12116, Vietnam.; Faculty of Materials Science and Engineering (MSE), Phenikaa University, Hanoi 12116, Vietnam. |
| Source: | Analytical chemistry [Anal Chem] 2025 Jan 14; Vol. 97 (1), pp. 994-1002. Date of Electronic Publication: 2024 Dec 27. |
| Publication Type: | Journal Article |
| Language: | English |
| Journal Info: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 0370536 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-6882 (Electronic) Linking ISSN: 00032700 NLM ISO Abbreviation: Anal Chem Subsets: MEDLINE; PubMed not MEDLINE |
| Imprint Name(s): | Original Publication: Washington, American Chemical Society. |
| Abstract: | Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical technique, yet it faces challenges with certain probe molecules exhibiting weak or inactive signals, limiting their applicability. In a recent study, we investigated this phenomenon using a set of four probe molecules─chloramphenicol (CAP), 4-nitrophenol (4-NP), amoxicillin (AMX), and furazolidone (FZD)─deposited on Ag-based nanostructured SERS substrates. Despite being measured under identical conditions, CAP and 4-NP exhibited SERS activity, while AMX and FZD did not. We also demonstrated that the alignment of the target molecule's lowest unoccupied molecular orbital (LUMO) energy level with the substrate's Fermi level plays a critical role in influencing the SERS signal. When the LUMO level diverges from the Fermi level, hindrance of the charge transfer process occurs due to a high potential barrier, leading to weak or absent SERS signals. To overcome this challenge, in this study, we introduce an approach inspired by metal-semiconductor interfacial charge transfer dynamics. By employing TiO2/Ag nanostructures, we not only enhance SERS signals for CAP and 4-NP but also activate signals for inactive molecules AMX and FZD. Importantly, we demonstrate that controlling the crystalline phase composition of the TiO2 semiconductor allows for tailored conduction band minimum energy level (ECBM) positions, significantly impacting the overall SERS efficiency of the TiO2/Ag substrate. Our findings highlight the pivotal role of the semiconductor's ECBM position in the energy alignment of the metal-semiconductor-analyte three-body interaction for an optimal SERS sensing platform. These findings also offer a novel strategy to enhance and activate the SERS phenomenon of important yet underexplored analytes. |
| Entry Date(s): | Date Created: 20241227 Latest Revision: 20250115 |
| Update Code: | 20260130 |
| DOI: | 10.1021/acs.analchem.4c05978 |
| PMID: | 39727338 |
| Database: | MEDLINE |
Journal Article