A visible-light-promoted transfer hydrogenation of azobenzenes has been developed. In the presence of B2pin2 and upon visible-light irradiation, the reactions proceeded smoothly in methanol at ambient temperature. The azobenzenes with diverse functional groups have been reduced to the corresponding hydrazobenzenes with a yield of up to 96%. Preliminary mechanistic studies indicated that the hydrogen atom comes from the solvent and the transformation is achieved through a radical pathway.Honey maturity is an important factor in evaluating the quality of honey; however, there are few studies on the molecular mechanism of the formation of mature honey (MH). In this study, the different metabolites of stomach honey (SH), immature honey (IMH), and MH samples during the same rapeseed flower season were analyzed by an UPLC-QTOF-MS-based metabolomics approach. MH was found to have a distinct metabolic profile to IMH, and a total of 9 different metabolites were obtained, 3 of which, including decenedioic acid, were accumulated in MH. Decenedioic acid as a bee-originated fatty acid (FA) was further verified in rape, acacia, and jujube honey by GC-MS, making it a potential marker to discriminate IMH and MH (P less then 0.01). Besides, MH showed higher FAs concentrations; in particular, 3 FAs were significantly richer in MH than IMH (P less then 0.05). This study reveals the molecular mechanism from IMH to MH from a FA perspective.Low-nuclearity nitrides of the late transition metals are rare and reactive molecular species, with little experimental precedent. selleck chemicals The first putative examples of dicobalt bridging nitrides, [( n PDI2)Co2(μ-N)(PMe3)2][OTf]3 ( n [Co 2 N] 3+ ; PDI = pyridyldiimine; n = 2 or 3, representing the length of the aliphatic chain linking PDI imino groups), were reported recently and shown to undergo a range of intramolecular reaction pathways, including N-H bond formation, C-H bond insertion, and P═N bond formation at the bridging nitride. The specific mode of reactivity changed with the phase of the reaction and the size of the macrocycle used to support the transient species. The present contribution offers a computational investigation into both the geometric and electronic structures of these nitrides as well as the factors governing their reaction selectivity. The compounds n [Co 2 N] 3+ exhibit μ-N-based lowest unoccupied molecular orbitals (LUMOs) that are consistent with subvalent, electrophilic nitrides. The specific orientations of the LUMOs induce ring-size-dependent stereoelectronic effects, thereby causing the product selectivity observed experimentally. Notably, the nitrides also exhibit a degree of nucleophilicity at μ-N by way of a high-energy, μ-N-based lone pair. This ambiphilic character appears to be a direct result of the constrained environment imposed by the folded-ligand geometries of n [Co 2 N] 3+ . When combined with the experimental findings, these data led to the conclusion that the folded-ligand isomers are the reactive species and that the constrained geometry imposed by the macrocyclic ligand plays an important role in controlling the reaction outcome.Two-dimensional (2D) semiconductors are attractive candidates for a variety of optoelectronic applications owing to the unique electronic properties that arise from quantum confinement along a single dimension. Incorporating nonradiative mechanisms that enable directed migration of bound charge carriers, such as Förster resonance energy transfer (FRET), could boost device efficiencies provided that FRET rates outpace undesired relaxation pathways. However, predictive models for FRET between distinct 2D states are lacking, particularly with respect to the distance d between a donor and acceptor. We approach FRET in systems with binary mixtures of donor and acceptor 2D perovskite quantum wells (PQWs), and we synthetically tune distances between donor and acceptor by varying alkylammonium spacer cation lengths. FRET rates are monitored using transient absorption spectroscopy and ultrafast photoluminescence, revealing rapid picosecond lifetimes that scale with spacer cation length. We theoretically model these binary mixtures of PQWs, describing the emitters as classical oscillating dipoles. We find agreement with our empirical lifetimes and then determine the effects of lateral extent and layer thickness, establishing fundamental principles for FRET in 2D materials.Moisture penetration into active biomedical implants such as the bionic ear and eye is a major problem in healthcare since surgery is required to replace devices affected by corrosion. Existing methods for measuring moisture leak rates such as the commercially available dynamic relative humidity method are not sufficiently sensitive to guarantee security against moisture penetration. Helium leak detection is highly sensitive but is challenged by the unknown relation to the moisture leak rate because of mixed flow modes involving liquid water. A standard moisture leak traceable to fundamental units is not currently available, preventing direct comparison of moisture and helium leak rates in the same device. Here, we demonstrate a practical calibrated moisture leak based on the stable polymer poly(ether-ether-ketone), for calibrating heavy water mass spectrometry. Using biomedical test structures from manufactured encapsulations, we show that in the majority of cases, calibrated measurements of molar moisture leak rates exceed the helium leak rate, especially for very small and large leaks. Comparison with theory shows that LaPlace pressure is the driving force for the enhanced moisture flows. We recommend that the compliance limit for helium testing in biomedical devices be reduced by one order of magnitude.Polyferrocenylsilane (PFS)-based polymers are an attractive family of organometallic polymers with unique redox-active properties. Herein, we report a novel amphiphilic redox-active PFS-based homopolymer, poly(ferrocenylmethylethylthiocarboxypropylsilane) (PFC), with a hydrophobic backbone chain and hydrophilic carboxylic acid side groups in each repeating unit. Self-assembly was induced by addition of water to a molecularly dispersed solution of PFC in DMSO. Spherical PFC micelles with controllable hydrodynamic diameters (60-180 nm) were obtained under various conditions. These PFC micelles could be readily endocytosed by A549 cells and HUVEC cells and show no significant cytotoxicity toward them at the concentration of 200 μg/mL. On this basis, Au nanoparticles (AuNPs) were prepared through in situ reduction of HAuCl4 by PFC micelles as nanoreactors without requiring any other reductants. The PFC/Au nanocomposites (NCs) were found to exhibit significant photothermal behavior. Moreover, PFC micelles could also act as nanoreactors for other noble metals such as Ag, Pd, and Pt.