NDLI: Nucleophilic reactivity of Zinc-bound thiolates: subtle interplay between coordination set and conformational flexibility

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Nucleophilic reactivity of Zinc-bound thiolates: subtle interplay between coordination set and conformational flexibility

Content Provider	Royal Society of Chemistry (RSC)
Author	Sénèque, Olivier Latour, Jean-Marc Isaac, Manon
Copyright Year	2012
Abstract	During the past decades it has been established that zinc-bound cysteines in proteins can react with various electrophiles to perform physiological functions such as alkyl transfer reactions or oxidative stress sensing. Electrophiles targeting especially vulnerable structural zinc fingers have also been proposed as therapeutic agents against cancers or HIV. However, the nucleophilic reactivity of zinc fingers remains poorly understood. In this article, we investigate the nucleophilic reaction of zinc finger model peptides with H2O2 in order to get deeper insight into the factors governing the reactivity of zinc-bound cysteines of zinc finger sites. We use a set of nine peptides belonging to two different peptide families with (Cys)4, (Cys)3(His) and (Cys)2(His)2 coordination sets. One family is derived from the consensus peptide of classical ββα zinc fingers and the other one derived from the zinc finger site of the oxidative stress sensor Hsp33 that adopts a loosened zinc ribbon fold. The coordination properties and the structural behaviors of the new members of the latter family were carefully characterized. The rate constants of the reaction of the nine zinc finger models with H2O2 were measured at various temperatures to determine the activation parameters. In all cases, the reaction is characterized by a small enthalpy of activation, which shows that the nucleophilic reaction of zinc-bound cysteines is easy, and large unfavorable negative entropy of activation. Neutral Zn(Cys)2(His)2 cores are intrinsically less reactive than negatively charged Zn(Cys)4 and Zn(Cys)3(His). Interestingly, we observe that the more flexible zinc finger sites are the more reactive. Indeed the entropies of activation are strongly linked to the conformational behavior of the peptide in solution. This work reveals important factors that govern the reactivity of zinc-bound cysteines in these two structural classes of zinc fingers and can be used to identify reactive zinc fingers in proteins.
Starting Page	3409
Ending Page	3420
Page Count	12
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	3
Issue Number	12
Journal	Chemical Science
DOI	10.1039/c2sc21029k
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Oxidative stress Classical physics Hydrogen peroxide HIV Alkyl Zinc finger Enthalpy Hsp33 Entropy Peptide Zinc Nucleophile
Content Type	Text
Resource Type	Article
Subject	Chemistry

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