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Creators/Authors contains: "Sitter, James D"

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  1. Wildland-urban interface (WUI) fires consume fuels, such as vegetation and structural materials, leaving behind ash composed primarily of pyrogenic carbon and metal oxides. However, there is currently limited understanding of the role of WUI fire ash from different sources as a source of paramagnetic species such as environmentally persistent free radicals (EPFRs) and transition metals in the environment. Electron paramagnetic resonance (EPR) was used to detect and quantify paramagnetic species, including organic persistent free radicals and transition metal spins, in fifty-three fire ash and soil samples collected following the North Complex Fire and the Sonoma-Lake-Napa Unit (LNU) Lightning Complex Fire, California, 2020. High concentrations of organic EPFRs (e.g., 1.4 × 1014 to 1.9 × 1017 spins g−1) were detected in the studied WUI fire ash along with other paramagnetic species such as iron and manganese oxides, as well as Fe3+ and Mn2+ ions. The mean concentrations of EPFRs in various ash types decreased following the order: vegetation ash (1.1 × 1017 ± 1.1 × 1017 spins g−1) > structural ash (1.6 × 1016 ± 3.7 × 1016 spins g−1) > vehicle ash (6.4 × 1015 ± 8.6 × 1015 spins g−1) > soil (3.2 × 1015 ± 3.7 × 1015 spins g−1). The mean concentrations of EPFRs decreased with increased combustion completeness indicated by ash color; black (1.1 × 1017 ± 1.1 × 1017 spins g−1) > white (2.5 × 1016 ± 4.4 × 1016 spins g−1) > gray (1.8 × 1016 ± 2.4 × 1016 spins g−1). In contrast, the relative amounts of reduced Mn2+ ions increased with increased combustion completeness. Thus, WUI fire ash is an important global source of EPFRs and reduced metal species (e.g., Mn2+). Further research is needed to underpin the formation, transformation, and environmental and human health impacts of these paramagnetic species in light of the projected increased frequency, size, and severity of WUI fires. 
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  2. Bioorthogonal reactions are powerful tools for studying and manipulating biological systems, yet achieving precise spatial and temporal control remains a major challenge. Here, we introduce cyclopropanol (CPol) as a compact, energy-loaded warhead that remains inert under physiological conditions and is selectively activated by mild electrochemical stimuli. This strategy generates reactive β-haloketone moieties in situ, enabling dual-function bioconjugation for cellular labeling and proteomic analysis. Upon oxidative ring opening, CPol preferentially modifies carboxylic acid-containing residues, such as glutamate and aspartate, rather than the expected tyrosine or tryptophan. The electrochemical activation of CPol is biocompatible in living systems, enabling direct protein labeling, real-time visualization with a fluorogenic CPol probe, and selective targeting of membrane-associated and cytoplasmic proteins with a choline-derived probe through integration into cellular phosphatidylcholine metabolism. Coupling bioorthogonality with electrochemical control, this approach enables precise protein profiling, live-cell imaging, and broader applications in chemical biology. 
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    Free, publicly-accessible full text available February 14, 2026
  3. A review on the selective catalytic hydrodeoxygenation of lignin biomass derived compounds. The focus is on recent reports which highlight achievements in selectively and reactivity trends which lead to deoxygenated aromatic products. 
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  4. Homogeneous molecular catalysts are valued for their reaction specificity but face challenges in manufacturing scale-up due to complexities in final product separation, catalyst recovery, and instability in the presence of water. Heterogenizing these molecular catalysts, by attachment to a solid support, could transform the practical utility of molecular catalysts, simplify catalyst separation and recovery, and prevent catalyst decomposition by impeding bimolecular catalyst interactions. Previous strategies to heterogenize molecular catalysts via ligand-first binding to supports have suffered from reduced catalytic activity and leaching (loss) of catalyst, especially in environmentally friendly solvents like water. Herein, we describe an approach in which molecular catalysts are first attached to a metal oxide support through acidic ligands and then “encapsulated” with a metal oxide layer via atomic layer deposition (ALD) to prevent molecular detachment from the surface. For this initial report, which is based upon the well-studied Suzuki carbon–carbon cross-coupling reaction, we demonstrate the ability to achieve catalytic performance using a non-noble metal molecular catalyst in high aqueous content solvents. The catalyst chosen exhibits limited catalytic reactivity under homogeneous conditions due to extremely short catalyst lifetimes, but when heterogenized and immobilized with an optimal ALD layer thickness product yields >90% can be obtained in primarily aqueous solutions. Catalyst characterization before and after ALD application and catalytic reaction is achieved with infrared, electron paramagnetic resonance, and X-ray spectroscopies. 
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