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  • Juarez Teague posted an update 11 hours, 7 minutes ago

    Hydroxysulfinyl radical (HOSO) is important due to its involvement in climate geoengineering upon SO2 injection and generation of the highly hygroscopic H2SO4. Its photochemical behavior in the upper atmosphere is, however, uncertain. Here we present the ultraviolet-visible photochemistry and photodynamics of this species by simulating the atmospheric conditions with high-level quantum chemistry methods. Photocleavage to HO + SO arises as the major solar-induced channel, with a minor contribution of H + SO2 photoproducts. The efficient generation of SO is relevant due to its reactivity with O3 and the consequent depletion of ozone in the stratosphere.Herein, we report the ribosomal elongation of linear γ4- and β-hydroxy-γ4-amino acids (statines) to expand the nonproteinogenic amino acid repertoire of natural product-like combinatorial peptide libraries. First, we demonstrated the successful ribosomal incorporation of four linear γ4-amino acids (γ4Gly, (S)-γ4Ala, (S)-γ4Nva, and (R)-γ4Leu) into a 10-mer macrocyclic peptide scaffold. Given the promising effects reported for statines on the cell permeability of macrocyclic peptides, we also designed and tested the ribosomal incorporation of six statines derived from Ala and d-val. Four Ala-derived statines were successfully incorporated into peptides, and γ4SAla3R-OH (GP2) showed a similar efficiency of incorporation to that of (S)-β2hAla and l-Ala. These new building blocks might confer the important pharmacological properties of protease resistance and membrane permeability to macrocyclic peptides and expand the diversity of future combinatorial peptide libraries that can be translated by the ribosome.The hierarchical heterostructure of NiMoO4@NiMnCo2O4 (NMO@NMCO) with furry structures of NMCO juxtaposed with NMO nanowires are endowed with multiple electrochemically active and accessible sites for ion storage, thus delivering an ultrahigh specific capacitance of 2706 F g-1, nearly two-fold times greater than that of sole NMCO. Electrodeposition of an overlayer of a highly robust and electrically conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT), not only improves the energy storage performance but also assists the binary oxide cathode in retaining its structural integrity during redox cycling. Coupling with an anode of porous flaky carbon (FC) derived from groundnut shells results in an asymmetric supercapacitor of FC//PProDOT@NiMoO4@NiMnCo2O4, which delivers an outstanding capacitance of 552 F g-1, energy and power density ranges of 172-40 Wh kg-1 and 0.75-10 kW kg-1, respectively, and a remarkable cycle life of 50 000 cycles, with ∼97.8% capacitance retention, over an operational voltage window of 1.5 V. From an application perspective, the charged supercapacitor was connected to a complementary coloring reversible electrochromic device (ECD) of Prussian blue//PProDOT, and the ECD state transformed from a pale-blue to a deep blue hue, thus signaling the efficient utilization of energy stored in the supercapacitor. The energy-saving attribute of the ECD was realized in terms of an integrated visible-light modulation of 39% that accompanied the optical transition. Deployment of low-cost devices at homes and commercial spaces, capable of storing and saving energy, is the way forward, and this is one significant step in this direction.Studies of cellular metabolism can provide profound insights into the underlying molecular mechanisms and metabolic function. To date, the majority of cellular metabolism studies based on chromatography-mass spectrometry (MS) require population cells to obtain informative metabolome. These methods are not only time-consuming but also not suitable for amount-limited cell samples such as circulating tumor cells, stem cells, and neurons. Therefore, it is extremely essential to develop analytical methods enabling to detect metabolome from tens of cells in a high-throughput and high-sensitivity way. In this work, a novel platform for rapid and sensitive detection of lipidome in 20 mammalian cells was proposed using capillary microsampling combined with high-resolution spectral stitching nanoelectrospray ionization direct-infusion MS. It can be used to collect cells rapidly and accurately via the capillary microprobe, extract lipids directly in a 96-well plate using a spray solvent, and detect more than 500 lipids covering 19 lipid subclasses within 3 min. This novel platform was successfully applied to study the lipid features of different cancer cell types and subtypes as well as target cells from tissue samples. This study provides a strategy for determining the lipid species with rich information in tens of cells and demonstrates great potential for clinical applications.Severe internal trauma results in millions of hospitalizations each year, including thousands of deaths caused by subsequent multiple organ failure. The majority of these deaths occur within the first 24 h, and thus, rapid diagnosis of internal trauma severity is necessary for immediate treatment. For early organ damage identification, diagnosis in point-of-care settings is crucial for rapid triage and treatment. Recent reports suggest that circulating histones may serve as a biomarker for severe organ damage and the risk of multiple organ failure. Here, we report a point-of-care diagnostic system that utilizes the inherent interactions between histones and DNA for the fluorescence-based detection of histones in whole blood. In the assay, histones within the sample are wrapped by DNA, thus preventing an intercalating dye from binding the DNA and fluorescing. selleck chemicals llc To allow for quantitative fluorescent measurements to be made in a point-of-care setting, we integrate a rapid, automated blood separation step into our assay. Furthermore, we eliminate manual reagent additions using a thermally responsive alkane partition (TRAP), thus making the system sample-to-answer. Finally, we demonstrate the assay in a portable fluorescence reader compatible with a point-of-care environment. We report a limit of detection 112 ng/mL in whole blood, suggesting that our device can be used to rapidly diagnose internal trauma severity and the likelihood of multiple organ failure in near-patient settings.

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