Theoretical insights into the effect of pH values on oxidation processes in the emission of firefly luciferin in aqueous solution

被引：3

作者：

Hiyama, Miyabi ^{[1
]}

Akiyama, Hidefumi ^{[1
]}

Koga, Nobuaki ^{[2
]}

机构：

[1] Univ Tokyo, Inst Solid State Phys, Kashiwa, Chiba 2778581, Japan

[2] Nagoya Univ, Grad Sch Informat Sci, Nagoya, Aichi, Japan

来源：

LUMINESCENCE | 2017年 / 32卷 / 06期

关键词：

the coupled cluster method with single and double substitutions (CCSD); firefly; free energy; potential energy profile; TDDFT; FLUORESCENCE-SPECTRA; QUANTUM YIELD; PK(A) VALUES; OXYLUCIFERIN; ABSORPTION; BIOLUMINESCENCE; PHOTOLUMINESCENCE; DERIVATIVES; DYNAMICS;

D O I：

10.1002/bio.3308

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

To elucidate the emission process of firefly d-luciferin oxidation across the pH range of 7-9, we identified the emission process by comparison of the potential and free-energy profiles for the formation of the firefly substrate and emitter, including intermediate molecules such as d-luciferyl adenylate, 4-membered dioxetanone, and their deprotonated chemical species. From these relative free energies, it is observed that the oxidation pathway changes from D-luciferin -> deprotonated D-luciferyl adenylate -> deprotonated 4-membered dioxetanone -> oxyluciferin to deprotonated D-luciferin -> deprotonated D-luciferyl adenylate -> deprotonated 4-membered dioxetanone oxyluciferin with increasing pH value. This indicates that deprotonation on 6'OH occurs during the formation of dioxetanone at pH7-8, whereas luciferin in the reactant has a 6'OH-deprotonated form at pH9.

引用

页码：1100 / 1108

页数：9

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