Direct Deoxygenation of α-Hydroxy and α,ß-Dihydroxy Ketones Using a Silyl Lithium Reagent.

A reliable method for the one-step direct deoxygenation of α-hydroxy ketones has been developed using a silyl lithium reagent and acetic anhydride. The method is metal-catalyst-free and does not require prefunctionalization of the hydroxy group prior to its removal. Deoxygenation of different primary, secondary, and tertiary alcohols was carried out with up to 98% isolated yield. Additionally, double deoxygenation was achieved when the present method was applied to α,ß-dihydroxy ketones to access the corresponding enones in a single step.

Lewis Acid Site Assisted Bifunctional Activity of Tin Doped Gallium Oxide and Its Application in Rechargeable Zn-Air Batteries.

The enhanced safety, superior energy, and power density of rechargeable metal-air batteries make them ideal energy storage systems for application in energy grids and electric vehicles. However, the absence of a cost-effective and stable bifunctional catalyst that can replace expensive platinum (Pt)-based catalyst to promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode hinders their broader adaptation. Here, it is demonstrated that Tin (Sn) doped ß-gallium oxide (ß-Ga2 O3 ) in the bulk form can efficiently catalyze ORR and OER and, hence, be applied as the cathode in Zn-air batteries. The Sn-doped ß-Ga2 O3 sample with 15% Sn (Snx =0.15 -Ga2 O3 ) displayed exceptional catalytic activity for a bulk, non-noble metal-based catalyst. When used as a cathode, the excellent electrocatalytic bifunctional activity of Snx =0.15 -Ga2 O3 leads to a prototype Zn-air battery with a high-power density of 138 mW cm-2 and improved cycling stability compared to devices with benchmark Pt-based cathode. The combined experimental and theoretical exploration revealed that the Lewis acid sites in ß-Ga2 O3 aid in regulating the electron density distribution on the Sn-doped sites, optimize the adsorption energies of reaction intermediates, and facilitate the formation of critical reaction intermediate (O*), leading to enhanced electrocatalytic activity.

Tuning of α-Silyl Carbocation Reactivity into Enone Transposition: Application to the Synthesis of Peribysin D, E-Volkendousin, and E-Guggulsterone.

A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and Z-selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision. Formal synthesis of E-guggulsterone and E-volkendousin was also claimed using a short sequence.

Interplay between Solubility Limit, Structure, and Optical Properties of Tungsten-Doped Ga2O3 Compounds Synthesized by a Two-Step Calcination Process.

This work unfolds the fundamental mechanisms and demonstrates the tunable optical properties derived via chemical composition tailoring in tungsten (W)-doped gallium oxide (Ga2O3) compounds. On the basis of the detailed investigation, the solubility limits of tungsten (W6+) ion and associated effects on the crystal structure, morphology, and optical properties of W-doped Ga2O3 (Ga2-2 xW xO3, 0.00 ≤ x ≤ 0.25, GWO) compounds are reported. GWO materials were synthesized via a conventional solid-state reaction route, where a two-step calcination is adopted to produce materials with a high structural and chemical quality. X-ray diffraction analyses of sintered GWO compounds reveal the formation of a solid solution of GWO compounds at lower concentrations W ( x ≤ 0.10), while unreacted WO3 secondary phase formation occurs at higher concentrations ( x>0.10). Insolubility of W at higher concentrations ( x ≥ 0.15) is attributed to the difference in formation enthalpies of respective oxides, i.e., Ga2O3 and WO3. GWO compounds exhibit an interesting trend in morphology evolution as a function of W content. While intrinsic Ga2O3 exhibits rod-shaped morphology, W-doped Ga2O3 compounds exhibit nearly spherical-shaped grain morphology. Increasing W content ( x ≥ 0.10) induces morphology transformation from spherical to faceted grains with different facets (square and hexagonal). Relatively larger grain sizes in GWO compounds might be attributed to vacancy assisted enhanced mass transport due to W incorporation and/or WO3 induced liquid phase sintering. Our findings demonstrate a substantial red shift in band gap ( Eg), which is evident from the optical absorption spectra, enabling the wide spectral selectivity of GWO compounds. W 5d orbitals induced sp- d exchange interaction between valence band and conduction band electrons accounts for the substantial red shift in Eg of GWO compounds. Also, with increasing W, Eg decreases linearly, obeying Vegard law up to x = 0.15 and, at this point, an abrupt Eg drop prevails. The nonlinearity ( bowing effect) behavior in Eg beyond x = 0.15 is due to insolubility of W at higher concentrations. The fundamental scientific understanding of the interdependence of synthetic conditions, structure, chemistry, and band gap could be useful to optimize GWO materials for optical, optoelectronic, and photocatalytic device applications.

Interfacial chemical bonding-mediated ionic resistive switching.

In this paper, we present a unique resistive switching (RS) mechanism study of Pt/TiO2/Pt cell, one of the most widely studied RS system, by focusing on the role of interfacial bonding at the active TiO2-Pt interface, as opposed to a physico-chemical change within the RS film. This study was enabled by the use of a non-conventional scanning probe-based setup. The nanoscale cell is formed by bringing a Pt/TiO2-coated atomic force microscope tip into contact with a flat substrate coated with Pt. The study reveals that electrical resistance and interfacial bonding status are highly coupled together. An oxygen-mediated chemical bonding at the active interface between TiO2 and Pt is a necessary condition for a non-polar low-resistance state, and a reset switching process disconnects the chemical bonding. Bipolar switching mode did not involve the chemical bonding. The nature of chemical bonding at the TiO2-metal interface is further studied by density functional theory calculations.