TY - JOUR
T1 - A proposed mechanism for light emission by bacterial luciferase involving dissociative electron transfer
AU - Kosower, E. M.
PY - 1980/1/29
Y1 - 1980/1/29
N2 - A new mechanism that involves dissociative electron transfer in the energy transducing step is set forward for bacterial luciferase catalyzed light emission. The proposal involves (1) dissociation of the 4a-hydroperoxyflavin to a flavin radical and •O2-, accounting for 570 and 620nm absorption, (2) •O2- addition to the aldehyde carbonyl to form a peroxyl radical, (3) abstraction of H from an enzyme thiol group to form RCH(OOH)OH, (4) thiyl radical abstraction of the H on C in RCH(OOH)OH, a step which can show a kH kD of ca. 4, and (5) dissociative electron- transfer, a highly exothermic step that leads to a protonated flavin excited state, a carboxylic acid and water.
AB - A new mechanism that involves dissociative electron transfer in the energy transducing step is set forward for bacterial luciferase catalyzed light emission. The proposal involves (1) dissociation of the 4a-hydroperoxyflavin to a flavin radical and •O2-, accounting for 570 and 620nm absorption, (2) •O2- addition to the aldehyde carbonyl to form a peroxyl radical, (3) abstraction of H from an enzyme thiol group to form RCH(OOH)OH, (4) thiyl radical abstraction of the H on C in RCH(OOH)OH, a step which can show a kH kD of ca. 4, and (5) dissociative electron- transfer, a highly exothermic step that leads to a protonated flavin excited state, a carboxylic acid and water.
UR - http://www.scopus.com/inward/record.url?scp=0019334872&partnerID=8YFLogxK
U2 - 10.1016/0006-291X(80)90341-1
DO - 10.1016/0006-291X(80)90341-1
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AN - SCOPUS:0019334872
SN - 0006-291X
VL - 92
SP - 356
EP - 364
JO - Biochemical and Biophysical Research Communications
JF - Biochemical and Biophysical Research Communications
IS - 2
ER -