Excited-State Intermolecular Proton Transfer of Firefly Luciferin IV. Temperature and pH Dependence

被引:29
作者
Erez, Yuval [1 ]
Presiado, Itay [1 ]
Gepshtein, Rinat [1 ]
Huppert, Dan [1 ]
机构
[1] Tel Aviv Univ, Raymond & Beverly Sackler Fac Exact Sci, Sch Chem, IL-69978 Tel Aviv, Israel
基金
以色列科学基金会;
关键词
GEMINATE RECOMBINATION; QUANTUM YIELD; BIOLUMINESCENCE; OXYLUCIFERIN; FLUORESCENCE; DIFFUSION; PYRANINE; ORIGIN; ICE;
D O I
10.1021/jp110889v
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
Time-resolved emission as well as steady-state UV-vis techniques were employed to study the photoprotolytic processes that D-luciferin, the natural substrate of the firefly luciferase, undergoes in both acidic aqueous solutions and ice. The emission spectrum of D-luciferin in a 20 mM HCl aqueous solution or higher has an additional emission band at 590 nm red-shifted with respect to the strongest emission band positioned at 530 nm of the deprotonated NRO-* form in a pH-neutral aqueous solution. We attribute this emission band to the zwitterion form designated as +HNRO-. The time-resolved emission signals show that the NRO-* emission band at 530 nm and the zwitterion emission band at 590 are strongly quenched by a recombination process with a proton in an acidic solution and in ice. In ice, the quenching rate is 10 times faster than in the liquid state:. We attribute the fast quenching rate to the high value of the proton diffusion constant in ice.
引用
收藏
页码:1617 / 1626
页数:10
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