METAL-METAL BONDING IN BIOLOGY - EXAFS EVIDENCE FOR A 2.5-ANGSTROM COPPER-COPPER BOND IN THE CU-A CENTER OF CYTOCHROME-OXIDASE

被引:139
作者
BLACKBURN, NJ
BARR, ME
WOODRUFF, WH
VANDEROOOST, J
DEVRIES, S
机构
[1] LOS ALAMOS NATL LAB,DIV CHEM SCI & TECHNOL,LOS ALAMOS,NM 87545
[2] FREE UNIV AMSTERDAM,DEPT MICROBIOL,1081 HV AMSTERDAM,NETHERLANDS
[3] DELFT UNIV TECHNOL,DEPT MICROBIOL & ENZYMOL,2628 BC DELFT,NETHERLANDS
关键词
D O I
10.1021/bi00200a022
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Evidence for a direct Cu-Cu bond in the Cu-A center of cytochrome oxidase is reported. Simulation of the X-ray absorption spectrum of a recombinant Cu-A-binding domain of Bacillus subtilis cytochrome oxidase, and comparison with a structurally characterized directly-bonding Cu(1.5)...Cu(1.5) inorganic complex, suggests that a Cu-Cu interaction of 2.5 +/- 0.1 Angstrom together with a short 2.2 Angstrom Cu-S interaction may be present in the Cu-A site. In light of these data, previous interpretations of the EXAFS of a number of cytochrome oxidase and nitrous oxide reductase enzymes which modeled the 2.6 Angstrom interaction as a long Cu-S(methionine) bona are possibly incorrect. A structural model based on the new data is presented which suggests that the Cu-A sites in cytochrome oxidase and N2O reductase are likely composed of a pair of modified type 1 copper centers with one histidine, one cysteine, and one weakly bound ligand (Met and/or Gln) joined by a Cu-Cu bond.
引用
收藏
页码:10401 / 10407
页数:7
相关论文
共 45 条
[1]  
ADMAN ET, 1991, ADV PROTEIN CHEM, V42, P145
[2]   A COMPARATIVE EPR INVESTIGATION OF THE MULTICOPPER PROTEINS NITROUS-OXIDE REDUCTASE AND CYTOCHROME-C-OXIDASE [J].
ANTHOLINE, WE ;
KASTRAU, DHW ;
STEFFENS, GCM ;
BUSE, G ;
ZUMFT, WG ;
KRONECK, PMH .
EUROPEAN JOURNAL OF BIOCHEMISTRY, 1992, 209 (03) :875-881
[3]   OXYGEN ACTIVATION AND THE CONSERVATION OF ENERGY IN CELL RESPIRATION [J].
BABCOCK, GT ;
WIKSTROM, M .
NATURE, 1992, 356 (6367) :301-309
[4]   CRYSTALLOGRAPHIC, SPECTROSCOPIC AND THEORETICAL-STUDIES OF AN ELECTRON-DELOCALIZED CU(1.5)-CU(1.5) COMPLEX [J].
BARR, ME ;
SMITH, PH ;
ANTHOLINE, WE ;
SPENCER, B .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (21) :1649-1652
[5]  
BEINERT H, 1962, J BIOL CHEM, V237, P2337
[6]  
BINSTED N, 1988, EXCURV88 SERC DAR LA
[7]  
BLACKBURN NJ, 1991, J BIOL CHEM, V266, P23120
[8]  
BLACKBURN NJ, 1989, SYNCHROTRON RAD BIOP, P63
[9]   CYTOCHROME-C-OXIDASE IN PARACOCCUS-DENITRIFICANS - PROTEIN, CHEMICAL, STRUCTURAL, AND EVOLUTIONARY ASPECTS [J].
BUSE, G ;
STEFFENS, GCM .
JOURNAL OF BIOENERGETICS AND BIOMEMBRANES, 1991, 23 (02) :269-289
[10]   CYTOCHROME-C OXIDASE - UNDERSTANDING NATURES DESIGN OF A PROTON PUMP [J].
CHAN, SI ;
LI, PM .
BIOCHEMISTRY, 1990, 29 (01) :1-12