2019
DOI: 10.1002/cphc.201900329
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Short‐Lived Radical Intermediates in the Photochemistry of Glucose Oxidase

Abstract: Glucose oxidase is a flavoprotein that is relatively well‐studied as a physico‐chemical model system. The flavin cofactor is surrounded by several aromatic acid residues that can act as direct and indirect electron donors to photoexcited flavin. Yet, the identity of the photochemical product states is not well established. We present a detailed full spectral reinvestigation of this issue using femtosecond fluorescence and absorption spectroscopy. Based on a recent characterization of the unstable tyrosine cati… Show more

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Cited by 18 publications
(38 citation statements)
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“…EAS1 (1 ps) and EAS2 (3 ps) both contain spectral features ascribed to the excited flavin, as well as a 1483 cm −1 band and the flavin anionic peak (1515 cm −1 ). Similar to TrmFO, the tyrosine cation radical in GOX is formed in 1 ps upon excitation [22], and in the TRIR of GOX the 1483 cm −1 band appears to reflect the vibrational mode of the tyrosine cation radical, in agreement with the above assignment for C51A TrmFO.…”
Section: Glucose Oxidasesupporting
confidence: 82%
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“…EAS1 (1 ps) and EAS2 (3 ps) both contain spectral features ascribed to the excited flavin, as well as a 1483 cm −1 band and the flavin anionic peak (1515 cm −1 ). Similar to TrmFO, the tyrosine cation radical in GOX is formed in 1 ps upon excitation [22], and in the TRIR of GOX the 1483 cm −1 band appears to reflect the vibrational mode of the tyrosine cation radical, in agreement with the above assignment for C51A TrmFO.…”
Section: Glucose Oxidasesupporting
confidence: 82%
“…3). We recently characterized the relatively complex photochemistry of glucose oxidase using transient visible absorption and fluorescence spectroscopy [22]. We found evidence for multiphasic FAD* decay leading initially to the FAD ⋅− TyrOH ⋅+ state in ~ 1 ps, and subsequently also to some FADH ⋅ TyrO ⋅ in ~ 4 ps and to some TrpH ⋅+ in ~ 30 ps, all these electron and proton transfer steps occur in competition with recombination reactions.…”
Section: Glucose Oxidasementioning
confidence: 99%
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“…Fluorescence lifetimes of the flavin in the dark-and light-adapted state. Ultrafast electron transfer from the neighbouring aromatic amino acid residues (Trp and Tyr) to the electronically excited flavin chromophore has been observed in many flavoproteins (including glucose oxidase, flavodoxin, riboflavin binding protein, photolyase/cryptochromes and ThyX) [52][53][54][55][56] . This photoinduced electron transfer (PET) results Table 2.…”
Section: Comparison Of the Fret Obtained Distances With Those From Crmentioning
confidence: 99%
“…The setup employs a Kerr shutter 67,68 and allows measuring fluorescence spectra with a resolution of ~100 fs and up to the nanoseconds timescale 57 . The setup was described elsewhere 52,72 but briefly, the excitation pulse centered at 390 nm is obtained by frequency-doubling, using a BBO crystal, part of the 780 nm pulse from the Ti:sapphire laser/amplifier system (Quantronix Integra-C) operating at 1 kHz. The remaining 780 nm beam is led through a motorized delay-line and focused into the Kerr medium where it spatially overlapped the fluorescence from the sample.…”
Section: Steady State Optical and Fluorescence Measurements Absorptimentioning
confidence: 99%