Paramagnetic Lanthanide NMR Probes Signalling Changes in Zinc Concentration by Emission and Chemical Shift: A Proof of Concept Study.

Autor: Harnden AC; Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK., Batsanov AS; Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK., Parker D; Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2019 Apr 26; Vol. 25 (24), pp. 6212-6225. Date of Electronic Publication: 2019 Apr 04.
DOI: 10.1002/chem.201900609
Abstrakt: A zinc-selective probe based on a set of rare earth complexes of a modified DO3A macrocyclic ligand incorporating a tris-pyridylamine (TPA) moiety has been structurally characterised in solution and in the solid-state. One pyridine group possesses a tert-butyl substituent to serve as an NMR reporter group. The mono-capped square-antiprismatic Dy complex has a long bond (2.83 Å) to an apical N atom (pK a 5.70 Eu) and binds to one water molecule on zinc binding. Zinc binding is reversible and involves all of the exocyclic ligand N donors; it is signalled by large (ratiometric) changes in Eu emission intensity, and by dramatic changes in the size (>50 ppm) and sign of the chemical shift of the paramagnetically shifted tBu resonances in Tb, Dy and Tm complexes. Slow trans-metallation was observed, leading to formation of an unusual di-zinc species in which one zinc ion is seven-coordinate and the other is six-coordinate.
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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