Chemical Mechanism of Fireworm Bioluminescence - A Theoretical Proposition.

is a marine worm, commonly known as a fireworm, that exhibits bluish-green bioluminescence (BL). The luciferin () and oxyluciferin () during fireworm BL have been experimentally identified in vitro. The and are the respective starting point and ending point of a series of complicated chemical reactions in the BL. However, the chemical mechanism of the fireworm BL remains largely unknown. Before the experiments provided strong evidence for the mechanism, based on our previously successful studies on several bioluminescent systems, we theoretically proposed the chemical mechanism of the fireworm BL in this article. By means of the spin-flip and time-dependent density functional calculations, we clearly described the complete process from to : under the catalysis of luciferase, undergoes deprotonation and reacts with O to form a dioxetanone anion via the single-electron transfer mechanism; the dioxetanone anion decomposes into the at the first singlet excited state (S) by the gradually reversible charge-transfer-induced luminescence mechanism; and the S- emits light and deexcites to in the ground state.