Publications by authors named "Christopher D James"

Noncommunicable diseases (NCDs) such as cardiovascular diseases, diabetes, and cancers are major global health concerns, disproportionately impacting low- and middle-income countries (LMICs). Adolescents in LMICs are particularly vulnerable due to urbanization, lifestyle changes, and limited preventive care access. This study evaluates the effectiveness of educational interventions in improving adolescents' knowledge, and behaviors, for NCD prevention in LMICs.

View Article and Find Full Text PDF

The Wood-Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel-iron-sulfur proteins: CO dehydrogenase and acetyl-CoA synthase (CODH/ACS). Here, we describe the nickel-methyl and nickel-acetyl intermediates in ACS completing the characterization of all its proposed organometallic intermediates.

View Article and Find Full Text PDF

The kinetics of the transfer of the chelate, ethylenediamine tetraacetate (EDTA), from Calcium(II) to Copper(II) in imidazole (Im) buffers near neutral pH, corresponding to the conversion, [Cu(II)Im]→ [Cu(II)EDTA], are characterized with stopped-flow absorption spectroscopy and implemented as a tool for calibrating the interval between mixing and freezing, the freeze-quench time ( ), of a rapid freeze-quench (RFQ) apparatus. The kinetics of this reaction are characterized by monitoring changes in UV-visible spectra (300 nm) due to changes in the charge-transfer band associated with the Cu ions upon EDTA binding. Stopped-flow measurements show that the rates of conversion of the Cu ions exhibit exponential kinetics on millisecond time scales at pH values less than 6.

View Article and Find Full Text PDF

Spore photoproduct lyase is a radical -adenosyl-l-methionine (SAM) enzyme with the unusual property that addition of SAM to the [4Fe-4S] enzyme absent substrate results in rapid electron transfer to SAM with accompanying homolytic S-C5' bond cleavage. Herein, we demonstrate that this unusual reaction forms the organometallic intermediate Ω in which the unique Fe atom of the [4Fe-4S] cluster is bound to C5' of the 5'-deoxyadenosyl radical (5'-dAdo). During catalysis, homolytic cleavage of the Fe-C5' bond liberates 5'-dAdo for reaction with substrate, but here, we use Ω formation without substrate to determine the thermal stability of Ω.

View Article and Find Full Text PDF

EPR and Electron Nuclear Double Resonance spectroscopies here characterize CO binding to the active-site A cluster of wild-type (WT) Acetyl-CoA Synthase (ACS) and two variants, F229W and F229A. The A-cluster binds CO to a proximal Ni (Ni) that bridges a [4Fe-4S] cluster and a distal Ni. An alcove seen in the ACS crystal structure near the A-cluster, defined by hydrophobic residues including F229, forms a cage surrounding a Xe mimic of CO.

View Article and Find Full Text PDF

Radical SAM (RS) enzymes use -adenosyl-l-methionine (SAM) and a [4Fe-4S] cluster to initiate a broad spectrum of radical transformations throughout all kingdoms of life. We report here that low-temperature photoinduced electron transfer from the [4Fe-4S] cluster to bound SAM in the active site of the hydrogenase maturase RS enzyme, HydG, results in specific homolytic cleavage of the S-CH bond of SAM, rather than the S-C5' bond as in the enzyme-catalyzed (thermal) HydG reaction. This result is in stark contrast to a recent report in which photoinduced ET in the RS enzyme pyruvate formate-lyase activating enzyme cleaved the S-C5' bond to generate a 5'-deoxyadenosyl radical, and provides the first direct evidence for homolytic S-CH bond cleavage in a RS enzyme.

View Article and Find Full Text PDF

Aliphatic oxidative carbon-carbon bond cleavage reactions involving Cu(II) catalysts and O2 as the terminal oxidant are of significant current interest. However, little is currently known regarding how the nature of the Cu(II) catalyst, including the anions present, influence the reaction with O2. In previous work, we found that exposure of the Cu(II) chlorodiketonate complex [(6-Ph2TPA)Cu(PhC(O)CClC(O)Ph)]ClO4 (1) to O2 results in oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit, leading to the formation of benzoic acid, benzoic anhydride, benzil, and 1,3-diphenylpropanedione as organic products.

View Article and Find Full Text PDF

Background: Distal radius fractures are among the most common fractures seen in the hospital emergency department. Of these, over 40% are considered unstable and require some form of fixation. In recent years with the advent of low profile plating, open reduction and internal fixation (ORIF) using volar plates has become the surgical treatment of choice in many hospitals.

View Article and Find Full Text PDF