Johnson Destinee K, Stevenson Michael J, Almadidy Zayed A, Jenkins Sharon E, Wilcox Dean E, Grossoehme Nicholas E
Department of Chemistry, Physics and Geology, Winthrop University, Rock Hill, SC 27933, USA.
Dalton Trans. 2015 Oct 7;44(37):16494-505. doi: 10.1039/c5dt02689j.
Conditions have been developed for the comproportionation reaction of Cu(2+) and copper metal to prepare aqueous solutions of Cu(+) that are stabilized from disproportionation by MeCN and other Cu(+)-stabilizing ligands. These solutions were then used in ITC measurements to quantify the thermodynamics of formation of a set of Cu(+) complexes (Cu(I)(MeCN)3(+), Cu(I)Me6Trien(+), Cu(I)(BCA)2(3-), Cu(I)(BCS)2(3-)), which have stabilities ranging over 15 orders of magnitude, for their use in binding and calorimetric measurements of Cu(+) interaction with proteins and other biological macromolecules. These complexes were then used to determine the stability and thermodynamics of formation of a 1 : 1 complex of Cu(+) with the biologically important tri-peptide glutathione, GSH. These results identify Me6Trien as an attractive Cu(+)-stabilizing ligand for calorimetric experiments, and suggest that caution should be used with MeCN to stabilize Cu(+) due to its potential for participating in unquantifiable ternary interactions.
已开发出用于Cu(2+)与金属铜发生氧化亚反应的条件，以制备Cu(+)的水溶液，该溶液可通过乙腈和其他Cu(+)稳定配体防止歧化。然后将这些溶液用于等温滴定量热法测量，以量化一组Cu(+)配合物（Cu(I)(MeCN)3(+)、Cu(I)Me6Trien(+)、Cu(I)(BCA)2(3-)、Cu(I)(BCS)2(3-)）形成的热力学，这些配合物的稳定性范围超过15个数量级，用于Cu(+)与蛋白质和其他生物大分子相互作用的结合和量热测量。然后使用这些配合物来确定Cu(+)与具有生物学重要性的三肽谷胱甘肽（GSH）形成1:1配合物的稳定性和热力学。这些结果表明Me6Trien是用于量热实验的一种有吸引力的Cu(+)稳定配体，并表明由于乙腈可能参与不可量化的三元相互作用，因此在使用乙腈稳定Cu(+)时应谨慎。
