Firefly luciferase exhibits bimodal action depending on the luciferin chirality

Firefly luciferase is able to convert l-luciferin into luciferyl-CoA even under ordinary aerobic luciferin–luciferase reaction conditions. The luciferase is able to recognize strictly the chirality of the luciferin structure, serving as the acyl-CoA synthetase for l-luciferin, whereas d-luciferin is used for the bioluminescence reaction. d-Luciferin inhibits the luciferyl-CoA synthetase activity of l-luciferin, whereas l-luciferin retards the bioluminescence reaction of d-luciferin, meaning that both enzyme activities are prevented by the enantiomer of its own substrate.