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@ARTICLE{Pavlin:820510,
author = {Pavlin, Matic and Rossetti, Giulia and De Vivo, Marco and
Carloni, Paolo},
title = {{C}arnosine and {H}omocarnosine {D}egradation {M}echanisms
by the {H}uman {C}arnosinase {E}nzyme {CN}1: {I}nsights from
{M}ultiscale {S}imulations},
journal = {Biochemistry},
volume = {55},
number = {19},
issn = {1520-4995},
address = {Columbus, Ohio},
publisher = {American Chemical Society},
reportid = {FZJ-2016-05803},
pages = {2772 - 2784},
year = {2016},
abstract = {The endogenous dipeptide l-carnosine, and its derivative
homocarnosine, prevent and reduce several pathologies like
amytrophic lateral sclerosis (ALS), Alzheimer’s disease,
and Parkinson’s disease. Their beneficial action is
severely hampered because of the hydrolysis by carnosinase
enzymes, in particular the human carnosinase, hCN1. This
belongs to the metallopeptidase M20 family, where a
cocatalytic active site is formed by two Zn2+ ions, bridged
by a hydroxide anion. The protein may exist as a monomer and
as a dimer in vivo. Here we used hybrid quantum
mechanics/molecular mechanics simulations based on the
dimeric apoenzyme’s structural information to predict the
Michaelis complexes with l-carnosine and its derivative
homocarnosine. On the basis of our calculations, we suggest
that (i) l-carnosine degradation occurs through a
nucleophilic attack of a Zn2+-coordinated bridging moiety
for both monomer and dimer. This mechanistic hypothesis for
hCN1 catalysis differs from previous proposals, while it is
in agreement with available experimental data. (ii) The
experimentally measured higher affinity of homocarnosine for
the enzyme relative to l-carnosine might be explained, at
least in part, by more extensive interactions inside the
monomeric and dimeric hCN1’s active site. (iii) Hydrogen
bonds at the binding site, present in the dimer but absent
in the monomer, might play a role in the experimentally
observed higher activity of the dimeric form. Investigations
of the enzymatic reaction are required to establish or
disprove this hypothesis. Our results may serve as a basis
for the design of potent hCN1 inhibitors.},
cin = {IAS-5 / INM-9 / JSC},
ddc = {570},
cid = {I:(DE-Juel1)IAS-5-20120330 / I:(DE-Juel1)INM-9-20140121 /
I:(DE-Juel1)JSC-20090406},
pnm = {572 - (Dys-)function and Plasticity (POF3-572) / 511 -
Computational Science and Mathematical Methods (POF3-511)},
pid = {G:(DE-HGF)POF3-572 / G:(DE-HGF)POF3-511},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000376224000010},
pubmed = {pmid:27105448},
doi = {10.1021/acs.biochem.5b01263},
url = {https://juser.fz-juelich.de/record/820510},
}