UV Resonance Raman Studies of Cis-Peptide, Diketopiperazine
Analytical Science and Technology / Analytical Science and Technology, (P)1225-0163; (E)2288-8985
1993, v.6 no.1, pp.39-45
Song, Sunho
Song,
S.
(1993). UV Resonance Raman Studies of Cis-Peptide, Diketopiperazine. , 6(1), 39-45.
Abstract
We have examined Raman spectra of cis-peptide model complex, diketopiperazine in water and $D_2O$ with 320 nm through 218 nm excitation. Our study examines assignment of the resonance enhanced amide vibrations and characterizes their enhancement mechanism. Three resonance enhaned cis-peptide marker bands were observed in aqueous solution at 1676, 1533 and $806cm^{-1}$, which were assigned to the cis-amide I, II and S band, respectively. The $1533cm^{-1}$ amide II band, which is almost pure C-N stretching, was most dominant in water and shifted to $1520cm^{-1}$ upon N-deuteration. This band will be probably a potential probe band for cis-peptide moieties in proteins. The excitation profile data and an Albrecht A-term fit indicated that the cis-peptide vibrations derive their intensities from the 188 nm cis-peptide ${\pi}-{\pi}^*$ electronic transition. We Propose that the geometry of cis-peptide ${\pi}^*$ excited state is C-N bond displacement relative to that of electronic ground state.
- keywords
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UV Resonance Ramau Spectroscopy,
Cis-Peptides