Activity

23 V (vs reversible hydrogen electrode) due to the enhanced light absorption and charge transfer efficiency. The superiority of this hybrid catalyst is demonstrated implementing the solar-assisted overall water splitting cells based on the MX@C cathode and MX@C/MoBiVO4 photoanode. These cells show the enhancement of current density from 0.78 to 1.23 mA/cm2 with long-term durability over 8 h. These results are attributed to the facile surface catalytic kinetics of the chemically and electronically coupled MX@C hybrid at the heterointerface for both OER and HER.Azapeptide nitriles are postulated to reversibly covalently react with the active-site cysteine residue of cysteine proteases and form isothiosemicarbazide adducts. We investigated the interaction of azadipeptide nitriles with the cathepsin B1 drug target (SmCB1) from Schistosoma mansoni, a pathogen that causes the global neglected disease schistosomiasis. Azadipeptide nitriles were superior inhibitors of SmCB1 over their parent carba analogs. We determined the crystal structure of SmCB1 in complex with an azadipeptide nitrile and analyzed the reaction mechanism using quantum chemical calculations. The data demonstrate that azadipeptide nitriles, in contrast to their carba counterparts, undergo a change from E- to Z-configuration upon binding, which gives rise to a highly favorable energy profile of noncovalent and covalent complex formation. Finally, azadipeptide nitriles were considerably more lethal than their carba analogs against the schistosome pathogen in culture, supporting the further development of this chemotype as a treatment for schistosomiasis.Iron oxide nanoparticles (NPs) have been extensively used for both health and technological applications. The control over their morphology, crystal microstructure, and oxidation state is of great importance to optimize their final use. However, while mature in understanding, it is still far from complete. Here we report on the effect of the amount of 1,2-hexadecanediol and/or 1-octadecene in the reaction mixture on the thermal decomposition of iron(III) acetylacetonate in oleic acid for two series of iron oxide NPs with sizes ranging from 6 to 48 nm. We show that a low amount of either compound leads to both large, mixed-phase NPs composed of magnetite (Fe3O4) and wüstite (FeO) and high reaction yields. In contrast, a higher amount of either 1,2-hexadecanediol or 1-octadecene gives rise to smaller, single-phase NPs with moderate reaction yields. By infrared spectroscopy, we have elucidated the role of 1,2-hexadecanediol, which mediates the particle nucleation and growth. Finally, we have correlated the magnetic response and the structural features of the NPs for the two series of samples.Graphene films (GFs) are promising ultrathin thermally conductive materials for portable electronic devices because of their excellent thermally conductive property, light weight, high flexibility, and low cost. However, the application of GFs is limited due to their poor mechanical properties and through-plane thermal conductivity. Here, a graphene-(graphitized polydopamine)-(carbon nanotube) (G-gPDA-CNT) all-carbon ternary composite film was fabricated by chemical reduction, carbonization, graphitization, and mechanical compaction of the evaporation-assembled (graphene oxide)-PDA@CNT film. The G-gPDA-CNT film exhibited a uniform all-carbon composite structure in which the components of the graphene, gPDA layers, and CNTs were cross-linked by strong covalent bonds. This unique structure promoted the load transfer and energy dissipation between the components by which the mechanical properties of the G-gPDA-CNT film were substantially improved. Furthermore, electron and phonon transfers were also promoted, greatly improving the electrical and thermal conductivities, especially the through-plane thermal conductivity of the G-gPDA-CNT film. The G-gPDA-CNT film showed a tensile strength of 67.5 MPa, 15.1% ultimate tensile strain, toughness of 6.07 MJ/m3, electrical conductivity of 6.7 × 105 S·m-1, in-plane thermal conductivity of 1597 W·m-1·K-1, and through-plane thermal conductivity of 2.65 W·m-1·K-1, which were 2.24, 1.44, 3.16, 1.46, 1.15, and 3.90 times that of the pure GFs, respectively.Recent developments in two-dimensional liquid chromatography (2D-LC) now make separation and analysis of very complex mixtures achievable. Despite being such a powerful chromatographic tool, current 2D-LC technology requires a series of arduous method development activities poorly suited for a fast-paced industrial environment. Recent introductions of new technologies including active solvent modulation and a support for multicolumn 2D-LC are helping to overcome this stigma. However, many chromatography practitioners believe that the lack of a systematic way to effectively optimize 2D-LC separations is a missing link in securing the viability of 2D-LC as a mainstay for industrial applications. In this work, a computer-assisted modeling approach that dramatically simplifies both offline and online 2D-LC method developments is introduced. Our methodology is based on mapping the separation landscape of pharmaceutically relevant mixtures across both first (1D) and second (2D) dimensions using LC Simulator (ACD/Labs) software. Retention models for 1D and 2D conditions were built using a minimal number of multifactorial modeling experiments (2 × 2 or 3 × 3 parameters gradient slope, column temperature, and different column and mobile phase combinations). The approach was first applied to online 2D-LC analysis involving achiral and chiral separations of complex mixtures of enantiomeric species. In these experiments, the retention models proved to be quite accurate for both the 1D and 2D separations, with retention time differences between experiments and simulations of less than 3.5%. This software-based concept was also demonstrated for offline 2D-LC purification of drug substances.Obesity caused lipotoxicity, which results in insulin resistance. We studied whether benzyl isothiocyanate (BITC) improved insulin resistance in muscle. BITC was studied in vivo in mice fed a high-fat diet (HFD) and in vitro in C2C12 myotubes treated with palmitic acid (PA). In C2C12 cells, BITC mitigated PA inhibition of glucose uptake and phosphorylation of IRS-1, AKT, and TBC1D1 in response to insulin. BITC upregulated the expression of HO-1, GSTP, and GCLM mRNA and protein as well as GSH contents, which suppressed oxidative damage. Knockdown of Nrf2 abrogated BITC enhancement of antioxidant defense and subsequently reversed BITC protection against PA-induced insulin resistance. Moreover, BITC upregulated the expression of GLUT4, PPARγ, and C/EBPα. In HFD-fed mice, plasma total cholesterol, nonesterified fatty acid, and glucose levels and HOMA-IR were dose-dependently decreased with 0.05 or 0.1% BITC administration. In gastrocnemius muscle, compared with the HFD group, BITC increased the phosphorylation of AKT and TBC1D1, GSH contents, and the expression of antioxidant enzymes as well as GLUT4. These results indicate that BITC ameliorates obesity-induced hyperglycemia by enhancing insulin sensitivity in muscle. Napabucasin mouse This is partly attributed to its inhibition of lipotoxicity-induced oxidative insult and upregulation of GLUT4 expression.Six rhenium(I) κ3N-dicarbonyl complexes with 4′-(4-substituted phenyl)terpyridine ligands were evaluated in their ground and excited states. These complexes, bearing substituents of different electron-donating strengths-from CN to NMe2-were studied by a combination of transient IR (TRIR), electrochemistry, and IR spectroelectrochemistry, as well as time-dependent density functional theory (TD-DFT). They exhibit panchromatic absorption and can act as stronger photoreductants than their tricarbonyl counterparts. The ground- and excited-state potentials, absorption maxima, and lifetimes (250-750 ps) of these complexes correlate well with the Hammett σp substituent constants, showing the systematic effect of remote substitution in the ligand framework. TRIR spectroscopy allowed us to assign the lowest singlet and triplet excited states to a metal-to-ligand charge-transfer (MLCT) character. This result contrasts our previous report on analogous κ2N-tricarbonyl complexes, where remote substitution switched the character from MLCT to intraligand charge transfer. With the help of TD-DFT calculations, we dissect the geometric and electronic effects of coordination of the third pyridine, local symmetries, and increasing conjugation length. These results give valuable insights for the design of complexes with long-lived triplet excited states and enhanced absorption throughout the visible spectrum, while showcasing the boundaries of the excited-state switching strategy via remote substitution.1,5-Pentanediol (1,5-PDO) is an important C5 building block for the synthesis of different value-added polyurethanes and polyesters. However, no natural metabolic pathway exists for the biosynthesis of 1,5-PDO. Herein we designed and constructed a promising nonnatural pathway for de novo production of 1,5-PDO from cheap carbohydrates. This biosynthesis route expands natural lysine pathways and employs two artificial metabolic modules to sequentially convert lysine into 5-hydroxyvalerate (5-HV) and 1,5-PDO via 5-hydroxyvaleryl-CoA. Theoretically, the 5-hydroxyvaleryl-CoA-based pathway is more energy-efficient than a recently published carboxylic acid reductase-based pathway for 1,5-PDO production. By combining strategies of systematic enzyme screening, pathway balancing, and transporter engineering, we successfully constructed a minimally engineered Escherichia coli strain capable of producing 3.19 g/L of 5-HV and 0.35 g/L of 1,5-PDO in a medium containing 20 g/L of glucose and 5 g/L lysine. Introducing the synthetic modules into a lysine producer and enhancing NADPH supply enabled the strain to accumulate 1.04 g/L of 5-HV and 0.12 g/L of 1,5-PDO using glucose as the main carbon source. This work lays the basis for the development of a biological route for 1,5-PDO production from renewable bioresources.Following a strong regain of interest over the past 20 years in the chemistry of allenes, this “forgotten” family of unsaturated molecules is undergoing a renaissance. In this context, the metal-catalyzed hydrofunctionalization of allenes is nowadays one of the most studied transformations. The latter is of great interest because it opens a way to produce selectively functionalized allylic structures. These motifs are important in synthesis, particularly for the formation of asymmetric centers. Hydrofunctionalization of allenes is also a totally atom economical strategy, avoiding generation of any waste, to produce allylic functionalized structures. Compared to the main pathway to obtain the latter (aka Tsuji-Trost allylic substitution), metal-catalyzed hydrofunctionalization does not require the prefunctionalization of starting material with a leaving group. This review presents a state of the art exploration of all existing transition metal-catalyzed methods allowing the selective intermolecular hydrofunctionalization of allenes with N-H, C-H, and O-H nucleophiles or electrophiles.