Mass yields of aqueous SOA from triplet reactions are large and range from 59 to 99%. Calculations using our data along with previous oxidant measurements indicate that phenols with high KH can be an important source of aqSOA in ALW, with 3C* typically the dominant oxidant.Molecular surface functionalization of metallic catalysts is emerging as an ever-developing approach to tuning their catalytic performance.  https://www.selleckchem.com/products/imd-0354.html  Here, we report the synthesis of hybrid catalysts comprising copper nanocrystals (CuNCs) and an imidazolium ligand for the electrochemical CO2 reduction reaction (CO2RR). We show that this organic modifier steers the selectivity of cubic CuNCs toward liquid products. A comparison between cubic and spherical CuNCs reveals the impact of surface reconstruction on the viability of surface functionalization schemes. Indeed, the intrinsic instability of spherical CuNCs leads to ejection of the functionalized surface atoms. Finally, we also demonstrate that the more stable hybrid nanocrystal catalysts, which include cubic CuNCs, can be transferred into gas-flow CO2RR cells for testing under more industrially relevant conditions.The work described herein demonstrates the exquisite control that the inner coordination sphere of metalloenzymes and transition-metal complexes can have on reactivity. We report one of few crystallographically characterized Mn-peroxo complexes and show that the tight correlations between metrical and spectroscopic parameters, established previously by our group for thiolate-ligated RS-Mn(III)-OOR complexes, can be extended to include an alkoxide-ligated RO-Mn(III)-OOR complex. We show that the alkoxide-ligated RO-Mn(III)-OOR complex is an order of magnitude more stable (t1/2298 K = 6730 s, kobs298 K = 1.03 × 10-4 s-1) than its thiolate-ligated RS-Mn(III)-OOR derivative (t1/2293 K = 249 s, k1293 K = 2.78 × 10-3 s-1). Electronic structure calculations provide insight regarding these differences in stability. The highest occupied orbital of the thiolate-ligated derivative possesses significant sulfur character and π-backdonation from the thiolate competes with π-backdonation from the peroxo π*(O-O). DFT-calculated Mulliken charges show that the Mn ion Lewis acidity of alkoxide-ligated RO-Mn(III)-OOR (+0.451) is greater than that of thiolate-ligated RS-Mn(III)-OOR (+0.306), thereby facilitating π-backdonation from the antibonding peroxo π*(O-O) orbital and increasing its stability. This helps to explain why the photosynthetic oxygen-evolving Mn complex, which catalyzes O-O bond formation as opposed to cleavage, incorporates O- and/or N-ligands as opposed to cysS-ligands.Synthetic aromatic arsenicals such as roxarsone (Rox(V)) and nitarsone (Nit(V)) have been used as animal growth enhancers and herbicides. Microbes contribute to redox cycling between the relatively less toxic pentavalent and highly toxic trivalent arsenicals. In this study, we report the identification of nemRA operon from Enterobacter sp. Z1 and show that it is involved in trivalent organoarsenical oxidation. Expression of nemA is induced by chromate (Cr(VI)), Rox(III), and Nit(III). Heterologous expression of NemA in Escherichia coli confers resistance to Cr(VI), methylarsenite (MAs(III)), Rox(III), and Nit(III). Purified NemA catalyzes simultaneous Cr(VI) reduction and MAs(III)/Rox(III)/Nit(III) oxidation, and oxidation was enhanced in the presence of Cr(VI). The results of electrophoretic mobility shift assays and fluorescence assays demonstrate that the transcriptional repressor, NemR, binds to either Rox(III) or Nit(III). NemR has three conserved cysteine residues, Cys21, Cys106, and Cys116. Mutation of any of the three resulted in loss of response to Rox(III)/Nit(III), indicating that they form an Rox(III)/Nit(III) binding site. These results show that NemA is a novel trivalent organoarsenical oxidase that is regulated by the trivalent organoarsenical-selective repressor NemR. This discovery expands our knowledge of the molecular mechanisms of organoarsenical oxidation and provides a basis for studying the redox coupling of environmental toxic compounds.The electrical control of the conducting state through phase transition and/or resistivity switching in heterostructures of strongly correlated oxides is at the core of the large on-going research activity of fundamental and applied interest. In an electromechanical device made of a ferromagnetic-piezoelectric heterostructure, we observe an anomalous negative electroresistance of ∼-282% and a significant tuning of the metal-to-insulator transition temperature when an electric field is applied across the piezoelectric. Supported by finite-element simulations, we identify the electric field applied along the conducting bridge of the device as the plausible origin stretching the underlying piezoelectric substrate gives rise to a lattice distortion of the ferromagnetic manganite overlayer through epitaxial strain. Large modulations of the resistance are also observed by applying static dc voltages across the thickness of the piezoelectric substrate. These results indicate that the emergent electronic phase separation in the manganites can be selectively manipulated when interfacing with a piezoelectric material, which offers great opportunities in designing oxide-based electromechanical devices.Tin-based materials with high specific capacity have been studied as high-performance anodes for energy storage devices. Herein, a SnOx (x = 0, 1, 2) quantum dots@carbon hybrid is designed and prepared by a binary oxide-induced surface-targeted coating of ZIF-8 followed by pyrolysis approach, in which SnOx quantum dots (under 5 nm) are dispersed uniformly throughout the nitrogen-containing carbon nanocage. Each nanocage is cross-linked to form a highly conductive framework. The resulting SnOx@C hybrid exhibits a large BET surface area of 598 m2 g-1, high electrical conductivity, and excellent ion diffusion rate. When applied to LIBs, the SnOx@C reveals an ultrahigh reversible capacity of 1824 mAh g-1 at a current density of 0.2 A g-1, and superior capacities of 1408 and 850 mAh g-1 even at high rates of 2 and 5 A g-1, respectively. The full cell assembled using LiFePO4 as cathode exhibits the high energy density and power density of 335 Wh kg-1 and 575 W kg-1 at 1 C based on the total active mass of cathode and anode.