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x‐RAY PHOTOELECTRON VALENCE BAND STUDIES ON FIREFLY D‐(‐)‐LUCIFERIN
Author(s) -
WADA NAOHISA,
SHIBATA RIKUO,
SHIBAZAKI MASAVUKI,
SUZUKI NOBUTAKA
Publication year - 1989
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1989.tb09203.x
Subject(s) - x ray photoelectron spectroscopy , chemistry , valence (chemistry) , irradiation , valence band , analytical chemistry (journal) , spectral line , chemiluminescence , electron , atomic physics , photochemistry , nuclear magnetic resonance , physics , organic chemistry , quantum mechanics , chromatography , astronomy , nuclear physics
— The valence band spectrum of firefly D‐(‐)‐luciferin (Ln) was measured for the first time by x‐ray photoelectron spectroscopy (XPS). Since the conversion of Ln to decarboxydehydroluciferin (dcrL) by x‐ray irradiation occurred even within ∼30 min, the effect of the irradiation on the valence band spectrum of Ln was investigated quantitatively. We found that the XPS valence band spectrum of Ln during irradiation for 3 h corresponds to the state density of Ln calculated by the LCAO‐ASMO‐SCF‐CI method for π‐electrons. Moreover, the weak coupling model for π‐electron transfer between Ln and oxygen was proposed for the primary electronic process in Ln chemiluminescence, assuming that the calculated π‐electron state densities of Ln in acidic and basic solutions reflect the characteristics of their XPS valence band spectra.