308 research outputs found

    Reactions of Mg and Mg<sub>2</sub> with SO<sub>2</sub> in Low-Temperature Matrices: Association or Insertion?

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    Laser-ablated magnesium species were codeposited with SO<sub>2</sub> in excess argon or neon on the substrate at 4 K. The reactions mainly produced Mg­(η<sup>2</sup>-O<sub>2</sub>S), Mg­(η<sup>2</sup>-O<sub>2</sub>S)<sub>2</sub>, Mg<sub>2</sub>(η<sup>2</sup>-O<sub>2</sub>S), OMg<sub>2</sub>(η<sup>2</sup>-SO), and Mg­(η<sup>2</sup>-SO) complexes, which were identified by isotopic substitutions and density functional frequency calculations (B3LYP and BPW91). In addition, the collected infrared spectra suggest that the single Mg atoms could react with SO<sub>2</sub> to form the Mg­(η<sup>2</sup>-O<sub>2</sub>S) complex on annealing, which further reacts with SO<sub>2</sub> to produce the Mg­(η<sup>2</sup>-O<sub>2</sub>S)<sub>2</sub> complex on irradiation. In contrast, the reactions of magnesium dimers lead to cleavage of the SO bond in SO<sub>2</sub> on irradiating. Structural and bonding characteristics of these generated complexes, which shed light on the different performances of single Mg atom and its dimer in their reactions with small molecules, are discussed

    DataSheet1_LC–MS/MS-based multiplex antibacterial platform for therapeutic drug monitoring in intensive care unit patients.PDF

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    Empirically prescribed standard dosing regimens of antibacterial agents may result in insufficient or excess plasma concentrations with persistently poor clinical outcomes, especially for patients in intensive care units (ICUs). Therapeutic drug monitoring (TDM) of antibacterial agents can guide dose adjustments to benefit patients. In this study, we developed a robust, sensitive, and simple liquid chromatography-tandem mass spectrometry (LC–MS/MS) platform for the quantification of 14 antibacterial and antifungal agents (beta-lactams piperacillin, cefoperazone, and meropenem; beta-lactamase inhibitors tazobactam and sulbactam; antifungal agents fluconazole, caspofungin, posaconazole, and voriconazole; and daptomycin, vancomycin, teicoplanin, linezolid, and tigecycline) that can be used for patients with severe infection. This assay requires only 100 µL of serum with rapid protein precipitation. Chromatographic analysis was performed using a Waters Acquity UPLC C8 column. Three stable isotope-labeled antibacterial agents and one analogue were used as internal standards. Calibration curves ranged from 0.1–100 μg/mL, 0.1–50 μg/mL, and 0.3–100 μg/mL for different drugs, and all correlation coefficients were greater than 0.9085. Intra- and inter-day imprecision and inaccuracy values were below 15%. After validation, this new method was successfully employed for TDM in routine practice.</p

    Infrared Spectra of IrCCH<sub>2</sub>, HIrCCH, and Ir‑η<sup>2</sup>‑C<sub>2</sub>H<sub>2</sub> Prepared in Reaction of Laser-Ablated Iridium Atom with Acetylene

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    Laser-ablated iridium atom has been codeposited at 4 K with acetylene in excess argon. The vinylidene IrCCH<sub>2</sub>, insertion product HIrCCH, and metallacycle complexes Ir-η<sup><i>2</i></sup>-(C<sub>2</sub>H<sub>2</sub>) and Ir-η<sup><i>2</i></sup>-(C<sub>2</sub>H<sub>2</sub>)<sub>2</sub> are produced in present experiments and identified on the basis of the <sup>13</sup>C<sub>2</sub>H<sub>2</sub>, C<sub>2</sub>D<sub>2</sub>, and mixed C<sub>2</sub>HD isotopic substitutions and the comparison with theoretical predictions. The agreement between the experimental and calculated vibrational frequencies supports the identification of these molecules. Two alternative reaction mechanism of formation of IrCCH<sub>2</sub> complex has been found on the potential energy surface of the studied system to account for the product formation. The conversion of acetylene to vinylidene on a Ir atom is exothermic by 3.4 kcal/mol based on the B3LYP functional calculations

    A 2-D dysprosium glutarate exhibiting slow magnetic relaxation and luminescent properties

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    <p>A 2-D dysprosium glutarate [Dy<sub>2</sub>(glu)<sub>3</sub>(phen)<sub>2</sub>]<sub>n</sub> (<b>1</b>, glu = glutarate, phen =1,10-phenanthroline) has been synthesized from the hydrothermal reaction of DyCl<sub>3</sub>, glutaric acid, and phen ligand. Compound <b>1</b> displays a classical 2-D (4,4) grid structure constructed by the linkages of Dy<sup>3+</sup> ions and three types of glutarate ligands. Compound <b>1</b> shows slow magnetic relaxation and luminescent properties. Although some lanthanide glutarates have been reported, they do not exhibit slow magnetic relaxation properties. Compound <b>1</b> offers the only example of a dysprosium coordination polymer with field-induced single-molecule magnets (SMMs) based on aliphatic dicarboxylic acids in the absence of ancillary aromatic carboxylic acids.</p> <p>This work offers the only example of a dysprosium coordinatination polymer with field-induced SMM based on aliphatic dicarboxylic acids without aromatic carboxylic acids.</p

    Supplementary document for Coded aperture temporal compressive digital holographic microscopy - 6616732.pdf

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    This document presents the details of the transmissive coded aperture temporal compressive digital holographic microscopy setup~\cite{yamaguchi2006phase} and a comparative assessment of the reconstruction algorithm

    Negative Regulation of TLR Inflammatory Signaling by the SUMO-deconjugating Enzyme SENP6

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    <div><p>The signaling of Toll-like receptors (TLRs) induces host defense against microbial invasion. Protein posttranslational modifications dynamically shape the strength and duration of the signaling pathways. It is intriguing to explore whether de-SUMOylation could modulate the TLR signaling. Here we identified SUMO-specific protease 6 (SENP6) as an intrinsic attenuator of the TLR-triggered inflammation. Depletion of SENP6 significantly potentiated the NF-κB-mediated induction of the proinflammatory genes. Consistently, SENP6-knockdown mice were more susceptible to endotoxin-induced sepsis. Mechanistically, the small ubiquitin-like modifier 2/3 (SUMO-2/3) is conjugated onto the Lysine residue 277 of NF-κB essential modifier (NEMO/IKKγ), and this impairs the deubiquitinase CYLD to bind NEMO, thus strengthening the inhibitor of κB kinase (IKK) activation. SENP6 reverses this process by catalyzing the de-SUMOylation of NEMO. Our study highlights the essential function of the SENP family in dampening TLR signaling and inflammation.</p></div

    Palladium-Catalyzed C(sp<sup>3</sup>)–H Nitrooxylation of Aliphatic Carboxamides with Practical Oxidants

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    Here we report the palladium-catalyzed β-C(sp3)−H nitrooxylation of aliphatic carboxamides using a modified quinoline auxiliary. Notably, Al(NO3)3·9H2O was used as a nitrate source as well as a practical oxidant. The 5-chloro-8-aminoquinoline auxiliary was nitrated in situ during the reaction, which may enhance its directing ability and help its removal. The reaction has a broad substrate scope with a variety of aliphatic carboxamides. The multiple substituted auxiliary can be easily removed and recovered. Two C–H-insertion palladacycle intermediates were isolated and characterized to elucidate the mechanism

    Expression profile of <i>FASN</i> gene and association of its polymorphisms with intramuscular fat content in Hu sheep

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    The content of intramuscular fat (IMF) is one of the most important factors that has a large impact on meat quality, and it is an effective way to improve IMF according to marker-assisted selection (MAS). Fatty-acid synthase (FASN) is a key gene in meat lipid deposition and fatty acid composition. Thus, this study was conducted to investigate the expression profile of FASN in mRNA and protein levels using real-time quantitative PCR (RT-qPCR) and western-blot methods. In addition, single nucleotide polymorphisms (SNPs) within FASN in 921 Hu rams with IMF content records were investigated using DNA-pooling sequencing and improved multiple ligase detection reaction (iMLDR) methods. Consequently, the highest mRNA expression level of FASN was observed in the perinephric fat, and the lowest in the liver among the 11 tissues analyzed, while no significant difference was found in mRNA and protein expression levels in longissimus dorsi among individuals with different IMF contents. A total of 10 putative SNPs were identified within FASN, and 9 of them can be genotyped by iMLDR method. Notably, two SNPs were significantly associated with IMF content, including NC_040262.1: g.5157 A > G in intron 5 (p = 0.046) and NC_040262.1: g.9413 T > C in intron 16 (p = 0.041), which supply molecular markers for improving meat quality in sheep breeding.</p

    Inhibition of α adrenoceptor and β 2 adrenoceptor attenuated the elevation of the proportion of EPCs in peripheral circulation.

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    <p>Cells from peripheral blood were lysed and analyzed with flow cytometry. Cells were sequentially gated based on CD45 (A), CD34 and KDR expression (C). Circulating EPCs were defined as CD45-/CD34+/KDR+ cells. A gate was used to select the total CD45- cell population (A). Corresponding flow cytometric analysis was used to detect CD34+/KDR+ cells in the gated CD45- cell population. Co-treatment of either phentolamine or I127 with NE significantly attenuated the increases of EPCs in peripheral circulation, but Metoprolol didn't (B, *P<0.05 compared with the model group.). Representative flow cytometric analysis of EPCs (CD34/Flk-1 cells) were showed in part C.</p

    DataSheet_1_Large-scale analyses of angiosperm Flowering Locus T genes reveal duplication and functional divergence in monocots.docx

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    FLOWERING LOCUS T (FT) are well-known key genes for initiating flowering in plants. Delineating the evolutionary history and functional diversity of FT genes is important for understanding the diversification of flowering time and how plants adapt to the changing surroundings. We performed a comprehensive phylogenetic analysis of FT genes in 47 sequenced flowering plants and the 1,000 Plant Transcriptomes (1KP) database with a focus on monocots, especially cereals. We revealed the evolutionary history of FT genes. The FT genes in monocots can be divided into three clades (I, II, and III), whereas only one monophyletic group was detected in early angiosperms, magnoliids, and eudicots. Multiple rounds of whole-genome duplications (WGD) events followed by gene retention contributed to the expansion and variation of FT genes in monocots. Amino acid sites in the clade II and III genes were preferentially under high positive selection, and some sites located in vital domain regions are known to change functions when mutated. Clade II and clade III genes exhibited high variability in important regions and functional divergence compared with clade I genes; thus, clade I is more conserved than clade II and III. Genes in clade I displayed higher expression levels in studied organs and tissues than the clade II and III genes. The co-expression modules showed that some of the FT genes might have experienced neofunctionalization and subfunctionalization, such as the acquisition of environmental resistance. Overall, FT genes in monocots might form three clades by the ancient gene duplication, and each clade was subsequently subjected to different selection pressures and amino acid substitutions, which eventually led to different expression patterns and functional diversification. Our study provides a global picture of FT genes’ evolution in monocots, paving a road for investigating FT genes’ function in future.</p
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