Haaningrees6402

Diabetes mellitus (DM) can cause systemic metabolic disorders, but the impact of gender on DM-related metabolic changes is rarely reported. Herein, we analyzed metabolic alterations in the heart, liver, and kidney of male and female mice from normal to diabetes via a 1H NMR-based metabolomics method and aimed to investigate sex-specific metabolic mechanisms underlying the onset and development of diabetes and its complications. Our results demonstrate that male mice had more significant metabolic disorders from normal to diabetes than female mice. Moreover, the kidney was found as the major organ of metabolic disorders during the development of diabetes, followed by the liver and heart. These altered metabolites were mainly implicated in energy metabolism as well as amino acid, choline, and nucleotide metabolism. Therefore, this study suggests that the kidney is the primary organ affected by diabetes in a sex-specific manner, which provides a metabolic view on the pathogenesis of diabetic kidney diseases between genders.Gadolinium-doped ceria or gadolinium-stabilized ceria (GDC) is an important technical material due to its ability to conduct O2- ions, e.g., used in solid oxide fuel cells operated at intermediate temperature as an electrolyte, diffusion barrier, and electrode component. We have synthesized Ce1-xGdxO2-yEu3+ (0 ≤ x ≤ 0.4) nanoparticles (11-15 nm) using a scalable spray pyrolysis method, which allows the continuous large-scale technical production of such materials. Introducing Eu3+ ions in small amounts into ceria and GDC as spectroscopic probes can provide detailed information about the atomic structure and local environments and allows us to monitor small structural changes. This study presents a novel approach to structurally elucidate europium-doped Ce1-xGdxO2-yEu3+ nanoparticles by way of Eu3+ spectroscopy, processing the spectroscopic data with the multiway decomposition method parallel factor (PARAFAC) analysis. In order to perform the deconvolution of spectra, data sets of excitation wavelength, emissi environments. The data of the Gd3+-containing samples indicates that the average charge density around the Eu3+ ions in the lattice is decreased with increasing Gd3+ and oxygen vacancy concentration. For reference, the Judd-Ofelt parameters of all spectra were calculated. PARAFAC proves to be a powerful tool to analyze lanthanide spectra in crystalline solid materials, which are characterized by numerous Stark transitions and where measurements usually yield a superposition of different contributions to any given spectrum.The mechanism of Pd-catalyzed desymmetric monoarylation of dihydrosilanes with aryl iodides in the presence of chiral TADDOL-derived phosphoramidite ligand toward deeper understanding of the stereoselectivity has been investigated using hybrid density functional theory (DFT) methodology. The full catalytic cycle for the favorable reaction pathway, which is initiated by the oxidative addition of aryl iodide to monoligated Pd0 leading to the silylation product, was calculated. The DFT calculation results indicate that the enantio-discriminating transmetalation between Pd-Ar bond of the Pd(II) aryl iodide complex and Si-H bond of the prochiral dihydrosilane was the enantioselectivity-determining step. On the basis of the structure of the transition state, the attractive aryl-aryl interactions between the aryl group of ligand, aryl iodide, and dihydrosilane were found to play an important role for the chiral transference from the chiral ligand to asymmetric cleavage of the Si-H bond of the prochiral dihydrosilane.Expanded helicenes are large, structurally flexible π-frameworks that can be viewed as building blocks for more complex chiral nanocarbons. Here we report a gram-scale synthesis of an alkyne-functionalized expanded [11]helicene and its single-step transformation into two structurally and functionally distinct types of macrocyclic derivatives (1) a figure-eight dimer via alkyne metathesis (also gram scale) and (2) two arylene-bridged expanded helicenes via Zr-mediated, formal [2+2+n] cycloadditions. HDAC inhibitor The phenylene-bridged helicene displays a substantially higher enantiomerization barrier (22.1 kcal/mol) than its helicene precursor ( less then 11.9 kcal/mol), which makes this a promising strategy to access configurationally stable expanded helicenes. In contrast, the topologically distinct figure-eight retains the configurational lability of the helicene precursor. Despite its lability in solution, this compound forms homochiral single crystals. Here, the configuration is stabilized by an intricate network of two distinct yet interconnected helical superstructures. The enantiomerization mechanisms for all new compounds were probed using density functional theory, providing insight into the flexibility of the figure-eight and guidance for future synthetic modifications in pursuit of non-racemic macrocycles.Cleavage of the triple N≡N bond by metal clusters is of fundamental interest and practical importance in nitrogen fixation. Previous studies of N≡N bond cleavage by gas-phase metal clusters emphasized the importance of the dinuclear metal centers. Herein, the dissociative adsorption of N2 and subsequent C-N coupling on trinuclear carbide cluster anions V3C4- under thermal collision conditions have been characterized by employing mass spectrometry (collision induced dissociation), cryogenic photoelectron imaging spectroscopy, and quantum chemistry calculations. A theoretical analysis identified a crucial adsorption intermediate with N2 bonded with the V3 metal core in the end-on/side-on/side-on (ESS) mode, which most likely enables the facile cleavage of the N≡N bond. Such a vital N2 coordination in the ESS mode is a result of symmetry-matched interactions between the occupied orbitals of the metal core and both of the two empty π* orbitals of N2. Furthermore, carbon ligands also play a considerable role in enhancing the reactivity of the metal core toward N2. This study strongly suggests a new mechanism of N≡N bond cleavage by gas-phase metal clusters.Aliphatic primary amines are prevalent in natural products, pharmaceuticals, and functional materials. While a plethora of processes are reported for their synthesis, methods that directly install a free amine group into C(sp3)-H bonds remain unprecedented. Here, we report a set of new-to-nature enzymes that catalyze the direct primary amination of C(sp3)-H bonds with excellent chemo-, regio-, and enantioselectivity, using a readily available hydroxylamine derivative as the nitrogen source. Directed evolution of genetically encoded cytochrome P411 enzymes (P450s whose Cys axial ligand to the heme iron has been replaced with Ser) generated variants that selectively functionalize benzylic and allylic C-H bonds, affording a broad scope of enantioenriched primary amines. This biocatalytic process is efficient and selective (up to 3930 TTN and 96% ee), and can be performed on preparative scale.