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  • Gammelgaard McConnell posted an update 1 week, 1 day ago

    g., the hexagonal pores in an xly network, manifested >50% decrease in their emission QY with faster decay profiles relative to their corresponding solution dissolved linkers. This is due to an efficient migration of photogenerated excitons at the crystallite peripheral sites to internal sites, which was facilitated by polarized absorption-emission overlap among the parallelly aligned linkers. In contrast, symmetric MOFs, such as those with sqc-a topological net, orient elongated linkers along two perpendicular crystal axes, which hinders efficient exciton migration. The present study underscores that MOFs are promising to develop artificial LHCs, but that to achieve an efficient exciton displacement, appropriate topology-guided assembly is required to fully realize the true potential of linkers with low electronic symmetry.Ribosome profiling and mass spectrometry have revealed thousands of small and alternative open reading frames (sm/alt-ORFs) that are translated into polypeptides variously termed as microproteins and alt-proteins in mammalian cells. Some micro-/alt-proteins exhibit stress-, cell-type-, and/or tissue-specific expression; understanding this regulated expression will be critical to elucidating their functions. While differential translation has been inferred by ribosome profiling, quantitative mass spectrometry-based proteomics is needed for direct comparison of microprotein and alt-protein expression between samples and conditions. However, while label-free quantitative proteomics has been applied to detect stress-dependent expression of bacterial microproteins, this approach has not yet been demonstrated for analysis of differential expression of unannotated ORFs in the more complex human proteome. Here, we present global micro-/alt-protein quantitation in two human leukemia cell lines, K562 and MOLT4. We identify 12 unannotated proteins that are differentially expressed in these cell lines. The expression of six micro/alt-proteins from cDNA was validated biochemically, and two were found to localize to the nucleus. Thus, we demonstrate that label-free comparative proteomics enables quantitation of micro-/alt-protein expression between human cell lines. We anticipate that this workflow will enable the discovery of regulated sm/alt-ORF products across many biological conditions in human cells.Drug-drug self-delivery systems serving as both carriers and cargos have been explored as advanced combination chemotherapy strategies to overcome the limitations of the traditional single-drug chemotherapy. However, most known drug-drug self-delivery systems may cause a rapid increase in drug concentration when the single covalent bond is broken, thus leading to high toxicity to organs and low therapeutic efficiency against tumors. To address the above problem, in this study, a novel supramolecular drug-drug complex (SDDC) simultaneously containing both covalent and noncovalent bonds was proposed to realize the sequential release of two drugs in tumor cells for enhanced combination therapy. PF-06821497 solubility dmso The SDDC could self-assemble into uniform bilayer supramolecular vesicles (SVs) with a remarkable drug loading capacity and stable drug transport. Notably, the SVs with controlled sequential release ability in tumor cells exhibited a superior synergistic effect and significantly improved therapeutic efficiency with reduced toxicity in in vivo antitumor activity and histological analyses in comparison to either individual free drugs or a mixture of two free drugs. Therefore, by combining the advantages of noncovalent interactions with the dynamic nature and stable covalent bonds, this study opens a new way for cancer therapy.In this work, well-ordered platinum (Pt) nanocubes (NCs), with precise control on the size and the spatial arrangement, are synthesized from a microemulsion overgrowth in a block copolymer (BC) nanotemplate. The nanovials on this self-assembled BC template serve as microreactors for the reduction of the HCl/H2PtCl6 precursor and direct the ordered periodic arrangement of the reduced Pt nanoparticles (NPs). As the content of HCl increases from 0% to 25%, the Pt NPs evolve from quasi-spheres to NCs, for which the density functional theory (DFT) computation reveals that the different adsorption energies of Cl and HCl dominate this morphology transition. For their potential application in fuel cells, the electrochemical catalysis of the Pt NCs demonstrates a 2.8-fold mass activity in contrast to the commercial JM 40% catalyst at the same Pt loading in ethanol oxidation reaction (EOR) and a good stability of 2.2% ECSA loss over 10 000 CV cycling.The relative stereochemistry and isomeric substitution pattern of organic molecules is typically determined using nuclear magnetic resonance spectroscopy (NMR). However, NMR spectra are sometimes nonconclusive, e.g., if spectra are extremely crowded, coupling patterns are not resolved, or if symmetry reasons preclude interpretation. Infrared spectroscopy (IR) can provide additional information in such cases, because IR represents a molecule comprehensively by depiction of the complete set of its normal vibrations. The challenge is thereby that diastereomers and substitution isomers often give rise to highly similar IR spectra, and visual distinction is insufficient and may be biased. Here we show the adaptation of an alignment algorithm, originally developed for vibrational circular dichroism (VCD) spectroscopy, to automatically match IR spectra and provide a quantitative measure of the goodness of fit, which can be used to distinguish isomers. The performance of the approach is demonstrated for different use cases diastereomers of flexible druglike molecules, E/Z-isomers, and substitution isomers of pyrazine and naphthalene. It can be applied to IR spectra measured both in the gas phase (gas chromatography IR) and in solution.We report here the synthesis of a series of metal-organic frameworks (MOFs), FeX@Zr6-Cu, comprising cuprous photosensitizing linkers (Cu-PSs) and catalytically active FeII centers supported on secondary building units (SBUs) for photocatalytic H2 evolution. Close proximity (∼1 nm) between Cu-PS and SBU-supported Fe sites and stabilization of Fe sites by periodically ordered SBUs led to exceptionally high H2 evolution activity for FeX@Zr6-Cu, with turnover numbers of up to 33 700 and turnover frequencies of up to 880 h-1. Photocatalytic H2 evolution activities of FeX@Zr6-Cu correlate with the lability of X counteranions, suggesting that open coordination environments of Fe sites generated by labile X groups facilitate the formation of Fe-hydride intermediates before hydrogen evolution. This work highlights the potential of using MOFs to integrate Earth-abundant components for solar energy utilization.

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