Presented as part of a commemorative issue for Wolfgang Kiefer on the occasion of his 65th birthday.
Time-resolved resonance Raman, time-resolved UV–visible absorption and DFT calculation study on photo-oxidation of the reduced form of nicotinamide adenine dinucleotide†
Version of Record online: 12 JAN 2006
Copyright © 2006 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy
Special Issue: Commemorative Issue: for Wolfgang Kiefer on the Occasion of his 65th Birthday
Volume 37, Issue 1-3, pages 283–290, January - March 2006
How to Cite
Takahashi, N., Shinno, T., Tachikawa, M., Yuzawa, T. and Takahashi, H. (2006), Time-resolved resonance Raman, time-resolved UV–visible absorption and DFT calculation study on photo-oxidation of the reduced form of nicotinamide adenine dinucleotide. J. Raman Spectrosc., 37: 283–290. doi: 10.1002/jrs.1472
- Issue online: 12 JAN 2006
- Version of Record online: 12 JAN 2006
- Manuscript Accepted: 6 JUL 2005
- Manuscript Received: 4 MAY 2005
- The Ministry of Education, Culture, Sports, Science and Technology of Japan. Grant Number: 15550018.
- nicotinamide adenine dinucleotide;
- time-resolved Raman spectroscopy;
- time-resolved absorption spectroscopy;
- DFT/B3LYP calculation
Photochemical reaction of the reduced form of nicotinamide adenine dinucleotide (NADH) was studied in aqueous solutions using nanosecond time-resolved resonance Raman and UV–visible absorption spectroscopies combined with DFT/B3LYP calculations. Four transients were detected. A transient exhibiting absorption bands at 370 and 560 nm was assigned to the cation radical NADH+•. A transient having an absorption band at 394 nm was assigned to the deprotonated neutral radical NAD•. A transient exhibiting an absorption band at 493 nm was considered to be attributable to the anion radical NADH−•. The broad and strong band at about 700 nm was assigned to hydrated electrons. It was concluded that the photo-oxidation of NADH to NAD+ proceeded stepwise via NADH+• and NAD•. The Raman band at 1627 cm−1 of NADH+• was assigned to the CC symmetric stretch of the protonated pyridyl ring of the dihydronicotinamide moiety. It was shown that the CC symmetric stretch of the protonated pyridyl ring exhibited a low-wavenumber shift from 1688 cm−1 to 1627 cm−1 on going from the ground state to NADH+•. This implies that the protonated pyridyl ring is weakened considerably on ionization in good accord with the DFT calculations. Copyright © 2006 John Wiley & Sons, Ltd.