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@ARTICLE{Liao:858904,
author = {Liao, Qinghua and Kulkarni, Yashraj and Sengupta, Ushnish
and Petrović, Dušan and Mulholland, Adrian J. and van der
Kamp, Marc W. and Strodel, Birgit and Kamerlin, Shina
Caroline Lynn},
title = {{L}oop {M}otion in {T}riosephosphate {I}somerase {I}s {N}ot
a {S}imple {O}pen and {S}hut {C}ase},
journal = {Journal of the American Chemical Society},
volume = {140},
number = {46},
issn = {1520-5126},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2018-07740},
pages = {15889 - 15903},
year = {2018},
abstract = {Conformational changes are crucial for the catalytic action
of many enzymes. A prototypical and well-studied example is
loop opening and closure in triosephosphate isomerase (TIM),
which is thought to determine the rate of catalytic turnover
in many circumstances. Specifically, TIM loop 6 “grips”
the phosphodianion of the substrate and, together with a
change in loop 7, sets up the TIM active site for efficient
catalysis. Crystal structures of TIM typically show an open
or a closed conformation of loop 6, with the tip of the loop
moving ∼7 Å between conformations. Many studies have
interpreted this motion as a two-state, rigid-body
transition. Here, we use extensive molecular dynamics
simulations, with both conventional and enhanced sampling
techniques, to analyze loop motion in apo and
substrate-bound TIM in detail, using five crystal structures
of the dimeric TIM from Saccharomyces cerevisiae. We find
that loop 6 is highly flexible and samples multiple
conformational states. Empirical valence bond simulations of
the first reaction step show that slight displacements away
from the fully closed-loop conformation can be sufficient to
abolish most of the catalytic activity; full closure is
required for efficient reaction. The conformational change
of the loops in TIM is thus not a simple “open and shut”
case and is crucial for its catalytic action. Our detailed
analysis of loop motion in a highly efficient enzyme
highlights the complexity of loop conformational changes and
their role in biological catalysis.},
cin = {ICS-6},
ddc = {540},
cid = {I:(DE-Juel1)ICS-6-20110106},
pnm = {551 - Functional Macromolecules and Complexes (POF3-551)},
pid = {G:(DE-HGF)POF3-551},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:30362343},
UT = {WOS:000451496800048},
doi = {10.1021/jacs.8b09378},
url = {https://juser.fz-juelich.de/record/858904},
}