Radiationless decay from the ligand-to-metal charge-transfer state in the blue copper protein plastocyanin

被引:33
作者
Edington, MD
Diffey, WM
Doria, WJ
Riter, RE
Beck, WF
机构
[1] Department of Chemistry, Vanderbilt University, 5134 Stevenson Center, P.O. Box 1822-B, Nashville
[2] Department of Chemistry, Colorado State University, Fort Collins
关键词
D O I
10.1016/S0009-2614(97)00738-0
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
The cysteine S(p pi) --> Cu(2+)d(x2-y2) ligand-to-metal charge-transfer (LMCT) state in plastocyanin exhibits a time-resolved pump-probe spectrum that has excited-state absorption and stimulated-emission components to the blue and red, respectively, of the absorbtion maximum. The LMCT state returns to the ground state by populating the d(xz+yz) --> d(x2-y2) ligand-field (LF) state. The lack of hole-burned features in the time-resolved spectra implies the presence of intramolecular vibrational redistribution and/or protein-matrix solvation dynamics on a time scale that is shorter than the 125 fs lifetime of the LMCT state. (C) 1997 Elsevier Science B.V.
引用
收藏
页码:119 / 126
页数:8
相关论文
共 35 条
[21]   ELECTRON TRANSFERS IN CHEMISTRY AND BIOLOGY [J].
MARCUS, RA ;
SUTIN, N .
BIOCHIMICA ET BIOPHYSICA ACTA, 1985, 811 (03) :265-322
[22]   ENERGETICS AND DYNAMICS OF DETERMINISTIC PROTEIN MOTION [J].
MILLER, RJD .
ACCOUNTS OF CHEMICAL RESEARCH, 1994, 27 (05) :145-150
[23]   VIBRATIONAL-ENERGY RELAXATION AND STRUCTURAL DYNAMICS OF HEME-PROTEINS [J].
MILLER, RJD .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1991, 42 :581-614
[24]   LARGE-SCALE PREPARATION OF PURE PLASTOCYANIN FROM SPINACH [J].
MORAND, LZ ;
KROGMANN, DW .
BIOCHIMICA ET BIOPHYSICA ACTA, 1993, 1141 (01) :105-106
[25]   Protein-matrix solvation dynamics in the alpha subunit of C-phycocyanin [J].
Riter, RR ;
Edington, MD ;
Reck, WF .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (33) :14198-14205
[26]   FEMTOSECOND SOLVATION DYNAMICS IN ACETONITRILE - OBSERVATION OF THE INERTIAL CONTRIBUTION TO THE SOLVENT RESPONSE [J].
ROSENTHAL, SJ ;
XIE, XL ;
DU, M ;
FLEMING, GR .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (06) :4715-4718
[27]  
SCHERER NF, 1996, ULTRAFAST PHENOMENA, V10, P361
[28]   SPECTROSCOPIC STUDIES AND A STRUCTURAL MODEL FOR BLUE COPPER CENTERS IN PROTEINS [J].
SOLOMON, EI ;
HARE, JW ;
GRAY, HB .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1976, 73 (05) :1389-1393
[29]   ELECTRONIC-STRUCTURES OF ACTIVE-SITES IN COPPER PROTEINS - CONTRIBUTIONS TO REACTIVITY [J].
SOLOMON, EI ;
BALDWIN, MJ ;
LOWERY, MD .
CHEMICAL REVIEWS, 1992, 92 (04) :521-542
[30]   ELECTRONIC-STRUCTURE CONTRIBUTIONS TO FUNCTION IN BIOINORGANIC CHEMISTRY [J].
SOLOMON, EI ;
LOWERY, MD .
SCIENCE, 1993, 259 (5101) :1575-1581