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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. 

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. 

Absorption of electronic acceptors in the accessible channels of an assembled triphenylamine (TPA) bis -urea macrocycle 1 enabled the study of electron transfer from the walls of the TPA framework to the encapsulated guests. The TPA host is isoskeletal in all host–guest structures analyzed with guests 2,1,3-benzothiadiazole, 2,5-dichlorobenzoquinone and I 2 loading in single-crystal-to-single-crystal transformations. Analysis of the crystal structures highlights how the spatial proximity and orientation of the TPA host and the entrapped guests influence their resulting photophysical properties and allow direct comparison of the different donor–acceptor complexes. Diffuse reflectance spectroscopy shows that upon complex formation 1·2,5-dichlorobenzoquinone exhibits a charge transfer (CT) transition. Whereas, the 1·2,1,3-benzothiadiazole complex undergoes a photoinduced electron transfer (PET) upon irradiation with 365 nm LEDs. The CT absorptions were also identified with the aid of time dependent density functional theory (TD-DFT) calculations. Cyclic voltammetry experiments show that 2,1,3-benzothiadiazole undergoes reversible reduction within the host–guest complex. Moreover, the optical band gaps of the host 1·2,5-dichlorobenzoquinone (1.66 eV), and host 1·2,1,3-benzothiadiazole (2.15 eV) complexes are significantly smaller as compared to the free host 1 material (3.19 eV). Overall, understanding this supramolecular electron transfer strategy should pave the way towards designing lower band gap inclusion complexes. 

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. 

UV-irradiation of assembled urea-tethered triphenylamine dimers results in the formation of persistent radicals, whereas radicals generated in solution are reactive and quickly degrade. In the solid-state, high quantities of radicals (approximately 1 in 150 molecules) are formed with a half-life of one week with no significant change in the single crystal X-ray diffraction. Remarkably, after decay, re-irradiation of the solid sample regenerates the radicals to their original concentration. The photophysics upon radical generation are also altered. Both the absorption and emission are significantly quenched without external oxidation likely due to the delocalization of the radicals within the crystals. The factors that influence radical stability and generation are correlated to the rigid supramolecular framework formed by the urea tether of the triphenylamine dimer. Electrochemical evidence demonstrates that these compounds can be oxidized in solution at 1.0 V vs. SCE to generate radical cations, whose EPR spectra were compared with spectra of the solid-state photogenerated radicals. Additionally, these compounds display changes in emission due to solvent effects from fluorescence to phosphorescence. Understanding how solid-state assembly alters the photophysical properties of triphenylamines could lead to further applications of these compounds for magnetic and conductive materials.