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Oxygen Pathways and Allostery in Monomeric Sarcosine Oxidase via Single-Sweep Free-Energy Reconstruction
Journal article   Open access   Peer reviewed

Oxygen Pathways and Allostery in Monomeric Sarcosine Oxidase via Single-Sweep Free-Energy Reconstruction

Anthony Bucci and Cameron F Abrams
Journal of chemical theory and computation, v 10(7), pp 2668-2676
08 Jul 2014
PMID: 25061440
url
https://doi.org/10.1021/ct500088zView
Published, Version of Record (VoR) Open

Abstract

Monomeric sarcosine oxidase (MSOX) is a flavoprotein D-amino acid oxidase with reported sarcosine and oxygen activation sites on the and faces of the flavin ring, respectively. O transport routes to the catalytic interior are not well understood and are difficult to ascertain solely from MSOX crystal structures. A composite free-energy method known as single-sweep is used to map and thermodynamically characterize oxygen sites and routes leading to the catalytically active Lys265 from the protein surface. The result is a network of pathways and free energies within MSOX illustrating that oxygen can access two free-energy minima on the face of the reduced flavin from four separate solvent portals. No such minimum is observed on the face. The pathways are geometrically similar for three major states of the enzyme: (1) apo with a closed flavin cleft, (2) apo with an open flavin cleft, and (3) inhibitor-bound with a closed flavin cleft. Interestingly, free energies along these transport pathways display significantly deeper minima when the substrate-mimicking inhibitor 2-furoic acid is bound at the sarcosine site, even at locations far from this site. This suggests a substrate-dependent allosteric modulation of the kinetics of O transport from the solvent to the active site.

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Chemistry, Physical
Physics, Atomic, Molecular & Chemical
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