Coordination Chemistry Heviews. 27 zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFE (1978) 109-140 109 @ EIsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands zyxwvutsrqponmlkjihgfe BLUE-COPPER PROTEINS: NUCLEAR MAGNETIC RESONANCE INVESTIGATIONS ELDON L. ULRICH * Department of Biochemistry, Purdue University, West Lafayette, Indiana 47907 (U.S.A.) JOHN L. MARKLEY ** Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 (U.S.A.) (Received 24 April 1978) CONTENTS 5 A. Introduction . . 110 (i) Properties of blue-c~pper zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA p&t&s _ 1 1 1 1 1 :* 1 1 1 1 1 1 1 _ 110 (ii) Chemical and physical studies _ _ . _ _ . . _ _ . . . _ . . . 110 (iii) NMR studies . . . . . _ . . . . . . . . . . . . . . . 111 B. Plastocyanins . . . . . . . . _ . . . . . . . . . . . . 113 (i) Proton NMR spectroscopy . . . . . . . . . . . . . . . . . 113 (ii) Carbon-13 NMR spectroscopy . . . . . . . _ . . . _ . . . . 116 (iii) Histidine residue pH-titration curves . . (iv) Conformationai differences between oxidized andreduced~pla&cyax&s f 119 : 120 C.Azurins. . . . 122 (i) Proton NMR~pe&roscbpy : : : : : : : : 1 1 : : : : : : . 122 (ii) Carbon-13 NMR spectroscopy . . . . . . . . . . . . . . . . . 127 (iii) Distances of protein groups from the copper . . . . . . _ . . . . 131 (iv) Conformationai heterogeneity . . . . . . . . . . . . . . . . 132 D. Discussion . . . . . . . . . . . . . . . _ . . . . . . . . 133 Acknowledgements . . . . . . . . . . . . . . . . . . . . .. . 137 References . . . . . . . . . . . _ . . . _ _ _ _ . . . _ . 137 ABBREVIATIONS EPR: electron paramagnetic resonance NMR: nuclear magnetic resonance UV: ultraviolet TMS: tetramethylsilane DSS: 2,2_dimethyl-2-silapentane-5-sulfonate TSP: 3-trimethylsilylpropionate-2,2,3,3& PH *: uncorrected pH meter reading of a *Hz0 solution measured with a glass electrode standardized with ‘H,O buffers * Supported by National Science Foundation Grant Number 389564. ** Supported by Public Health Service Career Development Award HL 00061 from the Heart and Lung Institute.