Activated barrier crossing dynamics in the non-radiative decay of NADH and NADPH

被引:47
作者
Blacker, Thomas S. [1 ,2 ,3 ]
Marsh, Richard J. [2 ]
Duchen, Michael R. [3 ]
Bain, Angus J. [1 ,2 ]
机构
[1] UCL, Ctr Math & Phys Life Sci & Expt Biol CoMPLEX, London WC1E 6BT, England
[2] UCL, Dept Phys & Astron, London WC1E 6BT, England
[3] UCL, Res Dept Cell & Dev Biol, London WC1E 6BT, England
基金
英国工程与自然科学研究理事会;
关键词
NADH; NADPH; NAD(P)H; Fluorescence lifetime; Fluorescence anisotropy; Rotational dynamics; Non-radiative decay; Activated barrier crossing; Kramers equation; Kramers-Hubbard equation; Conformational relaxation; NICOTINAMIDE ADENINE-DINUCLEOTIDE; ROTATIONAL REORIENTATION DYNAMICS; FLUORESCENCE DEPOLARIZATION; TEMPERATURE-DEPENDENCE; INTERNAL-CONVERSION; MOLECULAR-DYNAMICS; INTRACELLULAR NADH; RELAXATION; GLYCEROL; CONFORMATION;
D O I
10.1016/j.chemphys.2013.02.019
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
In live tissue, alterations in metabolism induce changes in the fluorescence decay of the biological coenzyme NAD(P) H, the mechanism of which is not well understood. In this work, the fluorescence and anisotropy decay dynamics of NADH and NADPH were investigated as a function of viscosity in a range of water-glycerol solutions. The viscosity dependence of the non-radiative decay is well described by Kramers and Kramers-Hubbard models of activated barrier crossing over a wide viscosity range. Our combined lifetime and anisotropy analysis indicates common mechanisms of non-radiative relaxation in the two emitting states (conformations) of both molecules. The low frequencies associated with barrier crossing suggest that non-radiative decay is mediated by small scale motion (e. g. puckering) of the nicotinamide ring. Variations in the fluorescence lifetimes of NADH and NADPH when bound to different enzymes may therefore be attributed to differing levels of conformational restriction upon binding. (C) 2013 Elsevier B. V. All rights reserved.
引用
收藏
页码:184 / 194
页数:11
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