Low Temperature 65Cu NMR Spectroscopy of the Cu+ Site in Azurin

详细信息    查看全文

• 作者：Andrew S. Lipton ; Robert W. Heck ; Wibe A. de Jong ; Amy R. Gao ; Xiongjian Wu ; Adrienne Roehrich ; Gerard S. Harbison ; Paul D. Ellis
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：October 7, 2009
• 年：2009
• 卷：131
• 期：39
• 页码：13992-13999
• 全文大小：217K
• 年卷期：v.131,no.39(October 7, 2009)
• ISSN：1520-5126

文摘

⁶⁵Cu central-transition NMR spectroscopy of the blue copper protein azurin in the reduced Cu(I) state, conducted at 18.8 T and 10 K, gave a strongly second order quadrupole perturbed spectrum, which yielded a ⁶⁵Cu quadrupole coupling constant of ±71.2 ± 1 MHz, corresponding to an electric field gradient of ±1.49 atomic units at the copper site, and an asymmetry parameter of approximately 0.2. Quantum chemical calculations employing second order Møller−Plesset perturbation theory and large basis sets successfully reproduced these experimental results. Sensitivity and relaxation times were quite favorable, suggesting that NMR may be a useful probe of the electronic state of copper sites in proteins.