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Location dependent coordination chemistry and MRI relaxivity, in de novo designed lanthanide coiled coils

Berwick, Matthew R.; Slope, Louise N.; Smith, Caitlin F.; King, Siobhan M.; Newton, Sarah L.; Gillis, Richard B.; Adams, Gary G.; Rowe, Arthur J.; Harding, Stephen E.; Britton, Melanie M.; Peacock, Anna F. A.


Matthew R. Berwick

Louise N. Slope

Caitlin F. Smith

Siobhan M. King

Sarah L. Newton

Richard B. Gillis

Gary G. Adams

Arthur J. Rowe

Melanie M. Britton

Anna F. A. Peacock


Herein, we establish for the first time the design principles for lanthanide coordination within coiled coils, and the important consequences of binding site translation. By interrogating design requirements and by systematically translating binding site residues, one can influence coiled coil stability and more importantly, the lanthanide coordination chemistry. A 10 °A binding site translation along a coiled coil, transforms a coordinatively saturated Tb(Asp) ₃(Asn) ₃ site into one in which three exogenous water molecules are coordinated, and in which the Asn layer is no longer essential for binding, Tb(Asp)₃(H₂O ) ₃. This has a profound impact on the relaxivity of the analogous Gd(III) coiled coil, with more than a fourfold increase in the transverse relaxivity (21 to 89 mM⁻¹ s⁻¹), by bringing into play, in addition to the outer sphere mechanism present for all Gd(III) coiled coils, an inner sphere mechanism. Not only do these findings warrant further investigation for possible exploitation as MRI contrast agents, but understanding the impact of binding site translation on coordination chemistry has important repercussions for metal binding site design, taking us an important step closer to the predictable and truly de novo design of metal binding sites, for new functional applications.


Berwick, M. R., Slope, L. N., Smith, C. F., King, S. M., Newton, S. L., Gillis, R. B., …Peacock, A. F. A. (in press). Location dependent coordination chemistry and MRI relaxivity, in de novo designed lanthanide coiled coils. Chemical Science, 7(3),

Journal Article Type Article
Acceptance Date Dec 22, 2015
Online Publication Date Dec 22, 2015
Deposit Date Apr 3, 2017
Publicly Available Date Apr 3, 2017
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 7
Issue 3
Public URL
Publisher URL!divAbstract


c5sc04101e Harding Chem Sc.pdf (711 Kb)

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