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Chlorite dismutase (Cld) is a heme enzyme capable of rapidly and selectively decomposing chlorite (ClO(2) (-)) to Cl(-) and O(2). The ability of Cld to promote O(2) formation from ClO(2) (-) is unusual. Heme enzymes generally utilize ClO(2) (-) as an oxidant for reactions such as oxygen atom transfer to, or halogenation of, a second substrate. The X-ray crystal structure of Dechloromonas aromatica Cld co-crystallized with the substrate analogue nitrite (NO(2) (-)) was determined to investigate features responsible for this novel reactivity. The enzyme active site contains a single b-type heme coordinated by a proximal histidine residue. Structural analysis identified a glutamate residue hydrogen-bonded to the heme proximal histidine that may stabilize reactive heme species. A solvent-exposed arginine residue likely gates substrate entry to a tightly confined distal pocket. On the basis of the proposed mechanism of Cld, initial reaction of ClO(2) (-) within the distal pocket generates hypochlorite (ClO(-)) and a compound I intermediate. The sterically restrictive distal pocket probably facilitates the rapid rebound of ClO(-) with compound I forming the Cl(-) and O(2) products. Common to other heme enzymes, Cld is inactivated after a finite number of turnovers, potentially via the observed formation of an off-pathway tryptophanyl radical species through electron migration to compound I. Three tryptophan residues of Cld have been identified as candidates for this off-pathway radical. Finally, a juxtaposition of hydrophobic residues between the distal pocket and the enzyme surface suggests O(2) may have a preferential direction for exiting the active site.
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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2909366 | PMC |
http://dx.doi.org/10.1007/s00775-010-0651-0 | DOI Listing |
Plast Reconstr Surg
December 2024
Department of Plastic Surgery, University of Texas Southwestern Medical Center, Dallas, TX.
Background: Postoperative hand therapy after surgery for distal radius fractures is associated with improved functional outcomes. However, financial impediments can be a potential barrier to adherence to postoperative care requirements. The aim of this study is to evaluate the relationship among the surgical and therapy out-of-pocket (OOP) expenses and therapy visits after operative treatment of a distal radius fracture.
View Article and Find Full Text PDFProtein Sci
January 2025
School of Health, Sport and Bioscience, University of East London, London, UK.
In Escherichia coli AcrB is a major multidrug exporter, which confers the bacterium resistance to many antibiotics with diverse structural and chemical proprieties. Studies have identified three possible tunnels (or channels) within AcrB that different substrates use before reaching the distal pocket, from which they are subsequently extruded. Recently, we reported that mutations in the AcrB gate loop may affect the conformational change kinetics involved in substrate export rather than directly affecting molecular interactions with this loop, and we highlighted the distinct export tunnel preferences between erythromycin and doxorubicin.
View Article and Find Full Text PDFJ Hand Microsurg
December 2024
The Yangzhou School of Clinical Medicine of Dalian Medical University, Dalian, Liaoning Province, China.
Purpose: The completely degloving injury of multiple fingers is a challenging clinical problem. Based on our technical experience, a novel two-stage surgery of abdominal hypodermal pocket followed by separation and full thickness skin grafting was conducted.
Methods: From January 2017 to August 2020, 7 cases (17 fingers) of degloving injury of multiple whole fingers who were treated in a two-stage fashion; an emergency first stage surgery of abdominal hypodermal pocket embedding and a second stage surgery (4 weeks later) of full thickness skin grafting, were retrospectively studied.
During field work on Hon Son Island, we discovered a new species of the genus Cyrtodactylus inferred from genetic and morphological evidence. Phylogenetic analyses based on the mitochondrial gene ND2, delimit Cyrtodactylus borgattaorum sp. nov.
View Article and Find Full Text PDFNat Commun
November 2024
Department of Structural Biology, St. Jude Children's Research Hospital, Memphis, TN, USA.
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