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@ARTICLE{Wensien:459162,
author = {Wensien, Marie and von Pappenheim, Fabian Rabe and Funk,
Lisa-Marie and Kloskowski, Patrick and Curth, Ute and
Diederichsen, Ulf and Uranga, Jon and Ye, Jin and Fang, Pan
and Pan, Kuan-Ting and Urlaub, Henning and Mata, Ricardo A.
and Sautner, Viktor and Tittmann, Kai},
title = {{A} lysine–cysteine redox switch with an {NOS} bridge
regulates enzyme function},
journal = {Nature},
volume = {593},
number = {7859},
issn = {0028-0836},
address = {London [u.a.]},
publisher = {Nature Publ. Group},
reportid = {PUBDB-2021-02447},
pages = {460 - 464},
year = {2021},
note = {Copyright © 2021, The Author(s), under exclusive licence
to Springer Nature Limited},
abstract = {Disulfide bonds between cysteine residues are important
post-translational modifications in proteins that have
critical roles for protein structure and stability, as
redox-active catalytic groups in enzymes or allosteric redox
switches that govern protein function1,2,3,4. In addition to
forming disulfide bridges, cysteine residues are susceptible
to oxidation by reactive oxygen species, and are thus
central not only to the scavenging of these but also to
cellular signalling and communication in biological as well
as pathological contexts5,6. Oxidized cysteine species are
highly reactive and may form covalent conjugates with, for
example, tyrosines in the active sites of some redox
enzymes7,8. However, to our knowledge, regulatory switches
with covalent crosslinks other than disulfides have not
previously been demonstrated. Here we report the discovery
of a covalent crosslink between a cysteine and a lysine
residue with a NOS bridge that serves as an allosteric redox
switch in the transaldolase enzyme of Neisseria gonorrhoeae,
the pathogen that causes gonorrhoea. X-ray structure
analysis of the protein in the oxidized and reduced state
reveals a loaded-spring mechanism that involves a structural
relaxation upon redox activation, which is propagated from
the allosteric redox switch at the protein surface to the
active site in the protein interior. This relaxation leads
to a reconfiguration of key catalytic residues and elicits
an increase in enzymatic activity of several orders of
magnitude. The redox switch is highly conserved in related
transaldolases from other members of the Neisseriaceae; for
example, it is present in the transaldolase of Neisseria
meningitides (a pathogen that is the primary cause of
meningitis and septicaemia in children). We surveyed the
Protein Data Bank and found that the NOS bridge exists in
diverse protein families across all domains of life
(including Homo sapiens) and that it is often located at
catalytic or regulatory hotspots. Our findings will inform
strategies for the design of proteins and peptides, as well
as the development of new classes of drugs and antibodies
that target the lysine–cysteine redox switch.},
cin = {EMBL-User},
ddc = {500},
cid = {I:(DE-H253)EMBL-User-20120814},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3)},
pid = {G:(DE-HGF)POF4-6G3},
experiment = {EXP:(DE-H253)P-P14-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:33953398},
UT = {WOS:000647555000003},
doi = {10.1038/s41586-021-03513-3},
url = {https://bib-pubdb1.desy.de/record/459162},
}