Silica-supported Re−Pd bimetallic catalysts (Re−Pd/SiO 2 ) with a high molar ratio of Re/Pd, which were reported to be effective for selective hydrogenation of carboxylic acids to the corresponding fatty alcohols in 1,4-dioxane solvent, were characterized by means of X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and CO adsorption. Various kinds of Re species (hexagonal closed packing (HCP) and face-centered cubic (FCC) Re 0 metals, Re 3+ , Re 4+ , and Re 6+ ) were detected on the catalysts after reaction or reduction, and the ratio of these Re species was estimated by the combination of characterization results. The activity of these catalysts is sensitive to air because of the high oxophilicity of Re, and the catalysts must be handled without contact to air. Pd addition and catalyst activation method (liquid-phase reduction and gas-phase reduction) influenced the ratio of the Re species. Liquid-phase reduced Re−Pd/SiO 2 (Re/Pd = 8), which is the most effective catalyst, has Pd 0 , Re 0 , and Re n+ (Re 3+ and Re 4+ ) species on the catalyst, and the metal surface (Pd 0 , Re 0 (HCP), Re 0 (FCC)) is modified with Re n+ species. This structure will be responsible for the high hydrogenation activity. Combined with kinetic studies with Re−Pd/SiO 2 (Re/Pd = 8) and Re/SiO 2 catalysts, Pd plays a role in promoting the reduction and dispersion of Re species, as well as strengthening the interaction of stearic acid with the catalytic surface, and on the other hand, Re n+ plays a role in promoting the heterolytic dissociation of H 2 .

A theoretical equation of the reversible polarographic current-potential curves for the ion transfer across the aqueous/organic interface facilitated by the neutral macrocyclic ligand present in the o-phase is derived without any limitation on the magnitude of distribution constant of the ligand. In two limiting cases, which have been employed in common experimental practice, i.e., (A) the bulk concentration of cation, c*M, in the aqueous phase >> that of ligand, c*L, in the organic phase and (B) the reverse condition, c*M<<c*L, the equation of current-potential curves becomes the same in form as that of reversible D. C. polarographic waves. It is shown that the limiting current is controlled by diffusion of ligand in the organic phase for (A) and of cation in the aqueous phase for (B) and, on the other hand, the half-wave potential depends on c*M for (A) and on c*L for (B). Furthermore, an analysis method to determine the complex formation constants in the organic phase (and in the aqueous phase for favorable cases) from the concentration dependence of the half-wave potential is presented. The theoretical predictions are verified experimentally using dibenzo-18-crown-6 and 18-crown-6 as macrocyclic ligands and sodium, cesium, barium, and oxonium ions as transferred cations.

Mixtures of the protic ionic liquids trioctylammonium bis(trifluoromethanesulfonyl)amide ([TOAH][NTf 2 ]) and trioctylammonium nitrate ([TOAH][NO 3 ]) were investigated as extractants for platinum-group elements. The mixture of 10 wt % [TOAH][NO 3 ] in [TOAH][NTf 2 ] has low viscosity (274.2 mPa s) and low aqueous solubility (2.6 Â 10 À5 mol dm À3 as the cation). With the ionic liquid mixture, Pd(II) and Pt(IV) were extracted almost quantitatively from 0.10 mol dm À3 hydrochloric acid. Under the same conditions, Na(I), Mg(II), K(I), Ca(II), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(III), Rh(III), and Cd(II) were only slightly extracted. It was found that the extraction of Pd and Pt increases with increasing content of [TOAH][NO 3] in the mixture. The metals could be back-extracted from the ionic liquid mixture with nitric acid solution, and selective stripping of Pt was possible by controlling the concentration of nitric acid. The metal extractability of the ionic liquid mixture after the back-extraction was equivalent to that of the fresh mixture, indicating that the species composition of the mixture returned to the original state through the back-extraction process. This extraction system provides an efficient separation method for Pd and Pt in acidic chloride media using ionic liquid mixtures, which are recyclable, easy to handle, safe, and environmentally friendly.

ROS1 gene rearrangement was observed in around 1–2 % of NSCLC patients and in several other cancers such as cholangiocarcinoma, glioblastoma, or colorectal cancer. Crizotinib, an ALK/ROS1/MET inhibitor, is highly effective against ROS1 -rearranged lung cancer and is used in clinic. However, crizotinib resistance is an emerging issue, and several resistance mechanisms, such as secondary kinase-domain mutations (e.g., ROS1-G2032R) have been identified in crizotinib-refractory patients. Here we characterize a new selective ROS1/NTRK inhibitor, DS-6051b, in preclinical models of ROS1- or NTRK-rearranged cancers. DS-6051b induces dramatic growth inhibition of both wild type and G2032R mutant ROS1–rearranged cancers or NTRK-rearranged cancers in vitro and in vivo . Here we report that DS-6051b is effective in treating ROS1- or NTRK-rearranged cancer in preclinical models, including crizotinib-resistant ROS1 positive cancer with secondary kinase domain mutations especially G2032R mutation which is highly resistant to crizotinib as well as lorlatinib and entrectinib, next generation ROS1 inhibitors.

Higher fatty alcohols were synthesized in high yield (492%) by direct hydrogenation of fatty acids catalyzed by ReO x -Pd/SiO 2 . High catalytic performance of ReO x -Pd/SiO 2 can be generated by the synergy between ReO x and Pd. Preferential adsorption of the carboxylic acid to alcohols prohibited the overreaction of alcohols to alkanes.