The Confluence of Structure and Dynamics in Lanthanide(III) Chelates: How Dynamics Help Define Structure in Solution
The authors thank the National Institutes of Health (EB-11687). Oregon Nanoscience and Microtechnologies Institute (N00014-11-1-0193), Portland State University and the Oregon Opportunity for Biomedical Research for financial support of this work.
Lanthanide shift reagents, Chelates, Contrast media (Diagnostic imaging), Solution (Chemistry)
Coordination exchange processes tend to dominate the solution state behaviour of lanthanide chelates and generally prohibit the study of small conformational changes. In this article we take advantage of coordinatively rigid Eu3+ chelates to examine the small conformational changes that occur in these chelates as water dissociatively exchanges in and out of the inner coordination sphere. The results show that the time-averaged conformation of the chelate alters as the water exchange rate increases. This conformational change reflects a change in the hydration state (q/rLnH6) of the chelate. The hydration state has recently come to be expressed as two separate parameters q and rLnH. However, these two parameters simultaneously describe the same structural considerations which in solution are indistinguishable and intrinsically related to, and dependent upon, the dissociative water exchange rate. This realization leads to the broader understanding that a solution state structure can only be appreciated with reference to the dynamics of the system.
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Published as: Webber, B.C. and Woods, M. (2014). The confluence of structure and dynamics in lanthanide(III) chelates: how dynamics help define structure in solution. Dalton Trans., 43, 251–258.
This is the author’s version of a work that was accepted for publication in Dalton Transactions. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Dalton Transactions, 2014, 43, 251-258.