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Hydroxide ion is a common electrolyte when electrode reactions take place in alkaline media. In the case of oxygen reduction reaction on Pt(111), we demonstrate by ab initio molecular dynamics calculations that the desorption of hydroxyl (OH*) from the electrode surface to form a solvated OH- is a cross-sphere process, with the OH* reactant in the inner sphere and the OH- product directly generated in the aqueous outer sphere. Such a mechanism is distinct from the typical inner sphere and outer sphere reactions. It is dictated by the strong hydrogen bonding interactions between a hydroxide ion and water molecules and is facilitated by proton transfer through solvation layers. It should play a significant role whenever OH* desorption, or its reverse, OH- adsorption, is involved in an electrochemical reaction.Previously, Gao et al. reported the isolation and structural determination of three natural products, hyperibrin B (HB), hyperscabrone H (HH), and hyperscabrone I (HI), from Hypericum scabrum. HB and HH had different NMR spectroscopic data, but they were assigned identical structures. Furthermore, these compounds should be derived from bicyclic polyprenylated acylphloroglucinols (BPAPs) via degradation, but the assigned structural features of the prenyl and prenylmethyl groups being cis and meta-substituted on the cyclohexanone core were not consistent with their biosynthetic origin. In this note, we revise the structures of HB, HH, and HI via NMR and MS spectroscopic analyses and biosynthetic considerations. We also complete a total synthesis of the revised structure of HB as well as its analogue, hyperibrin A, to further confirm the revision. The revised structures of HB, HH, and HI have not been reported.The Ir-catalyzed asymmetric hydrogenation of cyclic pyridinium salts is presented as a new strategy for the convenient and efficient synthesis of chiral indolizidines. The asymmetric hydrogenation of cyclic pyridinium salts derived from 2-(2-acylphenyl)pyridines proceeded smoothly in the presence of [Ir(cod)Cl]2 and (R)-DM-SegPhos to provide the desired chiral 7,8-benzoindolizidines 6 in high to excellent yields with moderate enantioselectivity (up to 8614 er) and excellent diastereoselectivity (>201 dr). The enantiomeric purity of 6j was increased to 928 through recrystallization.4-Silyl-5,6-dihydropyrans undergo remarkably selective [1,4]-Wittig rearrangements to give silylcyclopropanes in good yields. The selectivity is independent of the silyl group, but it is influenced by the electronic character of the migrating center. Electron-rich and electron-neutral (hetero)aryl groups and aliphatic substituents at the migrating center lead to exclusive [1,4]-migration, whereas electron-deficient aryl groups predominantly afford [1,2]-Wittig products.Global bottom-up mass spectrometry (MS)-based proteomics is widely used for protein identification and quantification to achieve a comprehensive understanding of the composition, structure, and function of the proteome. However, traditional sample preparation methods are time-consuming, typically including overnight tryptic digestion, extensive sample cleanup to remove MS-incompatible surfactants, and offline sample fractionation to reduce proteome complexity prior to online liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Thus, there is a need for a fast, robust, and reproducible method for protein identification and quantification from complex proteomes. Herein, we developed an ultrafast bottom-up proteomics method enabled by Azo, a photocleavable, MS-compatible surfactant that effectively solubilizes proteins and promotes rapid tryptic digestion, combined with the Bruker timsTOF Pro, which enables deeper proteome coverage through trapped ion mobility spectrometry (TIMS) and parallel accumulation-serial fragmentation (PASEF) of peptides. We applied this method to analyze the complex human cardiac proteome and identified nearly 4000 protein groups from as little as 1 mg of human heart tissue in a single one-dimensional LC-TIMS-MS/MS run with high reproducibility. Overall, we anticipate this ultrafast, robust, and reproducible bottom-up method empowered by both Azo and the timsTOF Pro will be generally applicable and greatly accelerate the throughput of large-scale quantitative proteomic studies. Raw data are available via the MassIVE repository with identifier MSV000087476.An efficient methodology for synthesis of α-keto acids via oxidation of alkenes using TBHP as oxidant catalyzed by a bifunctional iron nanocomposite has been established. A variety of alkenes with different functional groups were smoothly oxidized into their corresponding α-keto acids in up to 80% yield. Moreover, the bifunctional iron nanocomposite catalyst showed outstanding catalytic stability for successive recycles without appreciable loss of activity.Oxygen is the second-largest-volume industrial gas that is mainly produced using cryogenic air separation. However, the state-of-the-art cryogenic technology thermodynamic efficiency has approached a theoretical limit as near as is practicable. Therefore, there is stimulus to develop an alternative technology for efficient oxygen separation from air. Mixed ionic electronic-conducting (MIEC) ceramic membrane-based oxygen separation technology could become this alternative, but commercialization aspects, including cost, have revealed inadequacies in ceramic membrane materials. Currently, diffusion-bubbling molten oxide membrane-based oxygen separation technology is being developed. It is a potentially disruptive technology that would propose an improvement in oxygen purity and a reduction in capital costs. https://www.selleckchem.com/ Bubbles play an important role in ensuring the oxygen mass transfer in diffusion-bubbling membranes. However, there is not sufficient understanding of the bubble dynamics. This understanding is important to be able to control transport properties of these membranes and assess their potential for technological application. The aim of this feature article is to highlight the progress made in developing this understanding and specify the directions for future research.
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