X-RAY-ABSORPTION SPECTROSCOPY OF CUPROUS THIOLATE CLUSTERS IN PROTEINS AND MODEL SYSTEMS

被引:149
作者
PICKERING, IJ
GEORGE, GN
DAMERON, CT
KURZ, B
WINGE, DR
DANCE, IG
机构
[1] STANFORD UNIV, STANFORD LINEAR ACCELERATOR CTR, STANFORD SYNCHROTRON RADIAT LAB,POB 4349, BIN 69, STANFORD, CA 94309 USA
[2] UNIV UTAH, MED CTR, DEPT MED, SALT LAKE CITY, UT 84132 USA
[3] UNIV UTAH, MED CTR, DEPT BIOCHEM, SALT LAKE CITY, UT 84132 USA
[4] UNIV NEW S WALES, SCH CHEM, KENSINGTON, NSW 2033, AUSTRALIA
关键词
D O I
10.1021/ja00074a014
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Cuprous-thiolate multimetallic clusters exist in a range of different biological molecules for which no structural information exists from X-ray crystallography. Spectroscopic tools such as X-ray absorption spectroscopy have provided the major structural insights into this family of biological molecules. Recent nuclear magnetic resonance data on silver-substituted metallothionein, thought to be analogous with the copper proteins, have suggested the presence of digonal coordination [Narula, S. S.; Mehra, R. K.; Winge, D. R.; Armitage, 1. M. J. Am. Chem. Soc. 1991, 113, 9354-9358]. In order to test this in the copper case, we have examined a series of structurally characterized cuprous-thiolate model compounds, containing different proportions of digonal and trigonal copper sites, using copper K-edge X-ray absorption spectroscopy. The edge spectra, which have been previously used as a probe for the average copper coordination environment in proteins, show little variation between the models, indicating that these are not useful as a probe of coordination environment in the case of cuprous-thiolate clusters (as opposed to isolated metal sites). We show that systematic trends in the average Cu-S bond length from EXAFS curve-fitting analysis can be used to obtain an estimate of the fraction of digonal and trigonal copper sites. This correlation is applied to a series of different proteins containing cuprous-thiolate clusters which are found to contain significant fractions of digonal copper.
引用
收藏
页码:9498 / 9505
页数:8
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