Comparative Study of the Photoprotolytic Reactions of D-Luciferin and Oxyluciferin

被引:42
作者
Erez, Yuval [1 ]
Presiado, Itay [1 ]
Gepshtein, Rinat [1 ]
da Silva, Luis Pinto [2 ]
Esteves da Silva, Joaquim C. G. [2 ]
Huppert, Dan [1 ]
机构
[1] Tel Aviv Univ, Raymond & Beverly Sackler Fac Exact Sci, Sch Chem, IL-69978 Tel Aviv, Israel
[2] Univ Porto, Fac Ciencias, Dept Quim, Ctr Invest Quim, P-4169007 Oporto, Portugal
基金
以色列科学基金会;
关键词
INTERMOLECULAR PROTON-TRANSFER; FIREFLY LUCIFERASE; PHOTINUS-PYRALIS; BIOLUMINESCENCE; COLOR; LIGHT; PH; MODULATION; MECHANISM; DYNAMICS;
D O I
10.1021/jp301910p
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Optical steady-state and time-resolved spectroscopic methods were used to study the photoprotolytic reaction of oxyluciferin, the active bioluminescence chromophore of the firefly's luciferase-catalyzed reaction. We found that like D-luciferin, the substrate of the firefly bioluminescence reaction, oxyluciferin is a photoacid with pK(a)* value of similar to 0.5, whereas the excited-state proton transfer (ESPT) rate coefficient is 2.2 x 10(10) s(-1), which is somewhat slower than that of D-luciferin. The kinetic isotope effect (KIE) on the fluorescence decay of oxyluciferin is 2.5 +/- 0.1, the same value as that of D-luciferin. Both chromophores undergo fluorescence quenching in solutions with a pH value below 3.
引用
收藏
页码:7452 / 7461
页数:10
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