Ammonium Dinitramide as a Prospective N-NO Synthon: Electrochemical Synthesis of Nitro--Azoxy Compounds from Nitrosoarenes.

In this study, the electrochemical coupling of nitrosoarenes with ammonium dinitramide is discovered, leading to the facile construction of the nitro--azoxy group, which represents an important motif in the design of energetic materials. Compared to known approaches to nitro--azoxy compounds involving two chemical steps (formation of azoxy group containing a leaving group and its nitration) and demanding expensive, corrosive, and hygroscopic nitronium salts, the presented electrochemical method consists of a single step and is based solely on nitrosoarenes and ammonium dinitramide. The dinitramide salt plays the roles of both the electrolyte and reactant for the coupling.

Three-Dimensional Model Analysis Revealed Differential Cytotoxic Effects of the NK-92 Cell Line and Primary NK Cells on Breast and Ovarian Carcinoma Cell Lines Mediated by Variations in Receptor-Ligand Interactions and Soluble Factor Profiles.

The functional activity of a certain tumor determines the effectiveness of primary NK cells and NK-92 cell line-based cancer therapy; their therapeutic effectiveness against different tumors can vary. This work provides a direct simultaneous comparison of the cytotoxic effects of in vitro-activated peripheral NK (pNK) cells and NK-92 cells in spheroid models of BT-474, MCF7 and SKOV-3 carcinomas and uncovers the reasons for the differential effectiveness of NK cells against tumors. Tumor spheroids of similar size and shape, obtained from agarose molds, were incubated with NK-92 or pNK cells for 24 h.

Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and -oxyl radicals.

Radical ring-opening oxyimidation of cyclobutanols and cyclopropanols with the formation of ω-functionalized ketones was discovered. The oxidative C-O coupling proceeds the interception of a primary alkyl radical generated from a cyclic alcohol with a reactive radical generated , which is an electron-deficient -oxyl radical. The developed conditions allow for the balanced generation rates of carbon- and -oxyl radicals, which are necessary for their selective cross-recombination.

4-Halomethyl-Substituted Imidazolium Salts: A Versatile Platform for the Synthesis of Functionalized NHC Precursors.

N,N'-Diarylimidazolium salts containing haloalkyl functional groups that are reactive with various nucleophiles are considered to be promising reagents for the preparation of functionalized N-heterocyclic carbene (NHC) ligands, which are in demand in catalysis, materials science, and biomedical research. Recently, 4-chloromethyl-functionalized N,N'-diarylimidazolium salts became readily available via the condensation of N,N'-diaryl-2-methyl-1,4-diaza-1,3-butadienes with ethyl orthoformate and MeSiCl, but these compounds were found to have insufficient reactivity in reactions with many nucleophiles. These chloromethyl salts were studied as precursors in the synthesis of bromo- and iodomethyl-functionalized imidazolium salts by halide anion exchange.