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Grady Powers posted an update 6 months, 2 weeks ago
The Rice-Ramsperger-Kassel-Marcus (RRKM) theory was utilized to calculate reaction kinetics and product branching ratios. The RRKM results indicate that the formation of DNB- is exclusively important in the oxidation of DCA-, whereas the same type of reaction is a minor channel in the oxidation of DCBH-. In the latter case, H2 elimination becomes dominating. The RRKM modeling also indicates that the oxidation rate constant of DCBH- is higher than that of DCA- by an order of magnitude. This rationalizes the enhanced preignition performance of DCBH- over DCA- with HNO3.A domain-based local-pair natural-orbital coupled-cluster approach with single, double, and improved linear-scaling perturbative triple correction via an iterative algorithm, DLPNO-CCSD(T1), was applied within the framework of the Feller-Peterson-Dixon approach to derive gas-phase heats of formation of scandium and yttrium trihalides and their dimers via a set of homolytic and heterolytic dissociation reactions. All predicted heats of formation moderately depend on the reaction type with the most and least negative values obtained for homolytic and heterolytic dissociation, respectively. The basis set size dependence, as well as the influence of static correlation effects not covered by the standard (DLPNO-)CCSD(T) approach, suggests that exploitation of the heterolytic dissociation reactions with the formation of M3+ and X- ions leads to the most robust heats of formation. Selleck AUPM-170 The gas-phase formation enthalpies ΔHf°(0 K)/ΔHf°(298.15 K) and absolute entropies S°(298.15 K) were obtained for the first time for the Sc2F6, Sc2Br6, and Sc2I6 species. For ScBr3, ScI3, Sc2Cl6, and Y2Cl6, we suggest a reexamination of the experimental heats of formation available in the literature. For other compounds, the predicted values were found to be in good agreement with the experimental estimates. Extracted MX3 (M = Sc, Y; X = F, Cl, Br, and I) 0 K atomization enthalpies indicate weaker bonding when moving from fluorine to iodine and from yttrium to scandium. Likewise, the stability of yttrium trihalide dimers degrades when going from fluorine to iodine. Respective scandium trihalide dimers are less stable, with 0 K dimer dissociation energy decreasing in the row fluorine – chlorine – bromine ≈ iodine. Correlation of the (n – 1)s2p6 electrons on bromine and iodine, inclusion of zero-point energy, relativistic effects, and the effective-core-potential correction as well as amelioration of the DLPNO localization inaccuracy are shown to be of similar magnitude, which is critical if accurate heats of formation are a goal.Graphitic carbon nitride (g-C3N4) is a well-known two-dimensional conjugated polymer semiconductor that has been broadly applied in photocatalysis-related fields. However, further developments of g-C3N4, especially in device applications, have been constrained by the inherent limitations of its insoluble nature and particulate properties. Recent breakthroughs in fabrication methods of g-C3N4 films have led to innovative and inspiring applications in many fields. In this review, we first summarize the fabrication of continuous and thin films, either supported on substrates or as free-standing membranes. Then, the novel properties and application of g-C3N4 films are the focus of the current review. Finally, some underlying challenges and the future developments of g-C3N4 films are tentatively discussed. This review is expected to provide a comprehensive and timely summary of g-C3N4 film research to the wide audience in the field of conjugated polymer semiconductor-based materials.Managing patients with refractory inflammatory bowel diseases (IBD) is a common clinical challenge. Galli Gigeriae Endothelium Corneum (GGEC), a chicken by-product, has been used for centuries in Asian countries as a functional food and supplement for the treatment of gastrointestinal disorders. In this study, a novel peptide (LNLYP, LP-5) with gastrointestinal stability that can enhance the intestinal barrier function that was first identified in GGEC. Our work demonstrated that aryl hydrocarbon receptor (AhR) activation by LP-5 could inhibit the Src kinase to increase tight junction protein levels and down-regulate the expression of inflammatory cytokines to protect the intestinal barrier and finally alleviate dextran sulfate sodium (DSS)-induced colitis. This study revealed that LP-5 had the potential to develop into a therapeutic agent for the treatment of colitis and provided new high-valued utilization of GGEC.Organic anion-transporting polypeptides (OATPs) 1A2 and OATP2B1 are expressed in the small intestine and are involved in drug absorption. We identified narirutin, which is present in grapefruit juice, as a novel OATP inhibitor. The citrus fruit jabara also contains high levels of narirutin; therefore, we investigated the inhibitory potency of jabara juice against OATPs. The inhibitory effects of various related compounds on the transport activity of OATPs were evaluated using OATP-expressing HEK293 cells. The IC50 values of narirutin for OATP1A2- and OATP2B1-mediated transport were 22.6 and 18.2 μM, respectively. Other flavanone derivatives from grapefruit juice also inhibited OATP1A2/OATP2B1-mediated transport (order of inhibitory potency naringenin > narirutin > naringin). Five percent jabara juice significantly inhibited OATP1A2- and OATP2B1-mediated transport by 67 ± 11 and 81 ± 5.5%, respectively (p less then 0.05). Based on their inhibitory potency and levels in grapefruit juice, the inhibition of OATPs by grapefruit juice is attributable to both naringin and narirutin. Citrus × jabara, which contains narirutin, potently inhibits OATP-mediated transport.Synthetic chemistry enables a bottom-up approach to quantum information science, where atoms can be deterministically positioned in a quantum bit or qubit. Two key requirements to realize quantum technologies are qubit initialization and read-out. By imbuing molecular spins with optical initialization and readout mechanisms, analogous to solid-state defects, molecules could be integrated into existing quantum infrastructure. To mimic the electronic structure of optically addressable defect sites, we designed the spin-triplet, V3+ complex, (C6F5)3trenVCN t Bu (1). We measured the static spin properties as well as the spin coherence time of 1 demonstrating coherent control of this spin qubit with a 240 GHz electron paramagnetic resonance spectrometer powered by a free electron laser. We found that 1 exhibited narrow, near-infrared photoluminescence (PL) from a spin-singlet excited state. Using variable magnetic field PL spectroscopy, we resolved emission into each of the ground-state spin sublevels, a crucial component for spin-selective optical initialization and readout.