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Interaction between Histidine and Zn(II) Metal Ions over a Wide pH as Revealed by Solid-State NMR Spectroscopy and DFT Calculations
journal contribution
posted on 2016-02-19, 02:28 authored by Lei Zhou, Shenhui Li, Yongchao Su, Xianfeng Yi, Anmin Zheng, Feng DengThe interactions between histidine
and metal species play essential
roles in a wide range of important biological processes including
enzymes catalysis and signal transduction. In this work, solid-state
NMR techniques were employed to determine the interaction between
histidine and Zn(II) from pH 3.5 to 14. 2D homo- and heteronuclear
correlation NMR experiments were utilized to extract the 1H, 13C, and 15N chemical shifts in various
histidine–Zn(II) binding complexes. Several histidine–Zn(II)
binding models were proposed on the basis of experimental results
as well as DFT theoretical calculations. No direct interaction could
be found between biprotonated histidine and Zn(II) at acidic pH. At
pH 7.5, one zinc ion could be hexa-coordinated with two histidine
molecules on C′, Nα and deprotonated Nδ1 sites. As the pH increases to 11–14, both of
the Nδ1 and Nε2 sites could be deprotonated
as acceptors to be bound to either Zn(II) or water. All of these findings
give a comprehensive set of benchmark values for NMR parameters and
structural geometries in variable histidine–Zn(II) binding
complexes over a wide pH range and might provide insights into the
structure–property relationship of histidine–metal complexes
in biological metalloproteins.
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Keywords
N δ1N ε2 sitespH 3.5biprotonated histidinepH rangeWide pH13 Csignal transductionzinc ionheteronuclear correlation NMR experimentsNMR parameters14. 2 D homoenzymes catalysisZnhistidine moleculesbenchmark valuesDFT CalculationsThe interactions1 Hdeprotonated N δ1 sites15 N chemical shiftspH increasesbindingcomplexmetal speciesNMR techniquesacidic pH
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