authors |
Sardo, M; Ruano, C; Castro, JL; Lopez-Tocon, I; Soto, J; Ribeiro-Claro, P; Otero, JC |
nationality |
International |
journal |
PHYSICAL CHEMISTRY CHEMICAL PHYSICS |
keywords |
CHARGE-TRANSFER MECHANISM; NUCLEIC-ACID BASES; RESONANCE RAMAN; VIBRATIONAL-SPECTRUM; DFT CALCULATIONS; SELECTION-RULES; AB-INITIO; URACIL; SPECTROSCOPY; NANOPARTICLES |
abstract |
Raman and surface-enhanced Raman scattering (SERS) of 5-fluorouracil (5-FU) have been recorded under several experimental conditions. SERS spectra have been analysed according to a resonant charge-transfer (CT) mechanism similar to a resonance Raman (RR) process, involving the photoinduced transfer of an electron from the Fermi level of the metal to vacant orbitals of the adsorbate (SERS-CT). In order to detect the enhancement mechanism and to identify the chemical species that give rise to the spectra, the theoretical SERS-CT intensities for the dienolic and diketo forms, and its respective N1 and N3 deprotonated anions (5-FU(-)), have been calculated and compared with the experimental results. In this way, the presence of N1 deprotonated anion is confirmed by SERS given that the calculated SERS-CT intensities predict the selective enhancement of the band at ca. 1680 cm(-1) in agreement with the experiment. Therefore, the metal-to-adsorbate CT process involves the transient formation of the respective radical dianion (5-FU(center dot 2-)), which is new evidence of the relevance of the CT enhancement mechanism in SERS. |
publisher |
ROYAL SOC CHEMISTRY |
issn |
1463-9076 |
year published |
2009 |
volume |
11 |
issue |
34 |
beginning page |
7437 |
ending page |
7443 |
digital object identifier (doi) |
10.1039/b903823j |
web of science category |
Chemistry, Physical; Physics, Atomic, Molecular & Chemical |
subject category |
Chemistry; Physics |
unique article identifier |
WOS:000269082000013
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ciceco authors
impact metrics
journal analysis (jcr 2019):
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journal impact factor |
3.43 |
5 year journal impact factor |
3.735 |
category normalized journal impact factor percentile |
69.267 |
dimensions (citation analysis):
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altmetrics (social interaction):
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