The mechanism of the copolymerization of CO(2) and epoxides to afford the corresponding polycarbonates catalyzed by a highly active and thermally stable cobalt(III) complex with 1,5,7-triabicyclo[4,4,0] dec-5-ene (designated as TBD, a sterically hindered organic base) anchored on the ligand framework has been studied by means of electrospray ionization mass spectrometry (ESI-MS) and Fourier transform infrared spectroscopy (FTIR). The single-site, cobalt-based catalyst exhibited excellent activity and selectivity for polymer formation during CO(2)/propylene oxide (PO) copolymerization even at temperatures up to 100 degrees C and high [epoxide]/[catalyst] ratios, and/or low CO(2) pressures. The anchored TBD on the ligand framework plays an important role in maintaining thermal stability and high activity of the catalyst. ESI-MS and FTIR studies, in combination with some control experiments, confirmed the formation of the carboxylate intermediate with regard to the anchored TBD on the catalyst ligand framework. This analysis demonstrated that the formed carboxylate intermediate helped to stabilize the active Co(III) species against decomposition to inactive Co(II) by reversibly intramolecular Co-O bond formation and dissociation. Previous studies of binary catalyst systems based on Co(III)-Salen complexes did not address the role of these nucleophilic cocatalysts in stabilizing active Co(III) species during the copolymerization. The present study provides a new mechanistic understanding of these binary catalyst systems in which alternating chain-growth and dissociation of propagating carboxylate species derived from the nucleophilic axial anion and the nucleophilic cocatalyst take turns at both sides of the Co(III)-Salen center. This significantly increases the reaction rate and also helps to stabilize the active SalenCo(III) against decomposition to inactive SalenCo(II) even at low CO(2) pressures and/or relatively high temperatures.

A series of fluorinated analogues of AOT, the sodium salt of bis(3,

DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst.

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Reduced graphite oxide-NiFe 2 O 4 (RGO-NiFe 2 O 4 ) composites were synthesized by adding different amounts of NH 3 $H 2 O into a mixed aqueous solution of graphite oxide, Ni(NO 3 ) 2 and Fe(NO 3 ) 3 at room temperature. NH 3 $H 2 O was used to adjust the synthesis system's pH value. The morphology and the microstructure of the as-prepared composites were characterized by X-ray diffraction (XRD), BrunauerEmmett-Teller (BET) and transmission electron microscope (TEM) techniques. The structure characterizations indicate that NiFe 2 O 4 successfully deposited on the surface of the RGO and the morphologies of RGO-NiFe 2 O 4 show a transparent structure with NiFe 2 O 4 homogeneously distributed on the RGO surfaces. Capacitive properties of the synthesized electrodes were studied using cyclic voltammetry and electrochemical impedance spectroscopy in a three-electrode experimental setup using 1 M Na 2 SO 4 aqueous solution as electrolyte. It is found that the pH value plays an important role in controlling the electrochemical properties of these electrodes. Among the synthesized electrodes, RGONiFe 10 (pH ¼ 10) shows the best capacitive properties because of its suitable particle size and good dispersion property. It could be anticipated that the synthesized electrodes will gain promising applications as novel electrode materials in supercapacitors and other devices by virtue of their outstanding characteristics of controllable capacitance and facile synthesis.

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An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.

A new design for photoresponsive shape memory hydrogels and their possible applications are demonstrated in the present study. We show that the photodissociable Fe3+-carboxylate coordination can be utilized as a molecular switch to realize photocontrol of shape memory on both macroscopic and microscopic scales and enable a number of functions. Indeed, Fe3+-carboxylate coordination can fix a large tensile strain (up to 680%) of the sodium alginate/polyacrylamide hydrogel through cross-linking of sodium alginate chains, and subsequent UV irradiation allows strain energy release in spatially selected regions through reduction of Fe3+ to Fe2+. By manipulating light irradiation, complex 3D structures are obtained from 2D hydrogel sheets, and they exhibit complex solvent-driven actuation behaviors due to a light-changeable modulus and cross-linking density in the hydrogel. Based on the same approach, micropatterns can be inscribed on the hydrogel surface using mask-assisted irradiation, and they exhibit chain orientation-mediated anisotropic topography change upon solvent exchange. Moreover, light-controlled strain energy release also enables changing hydrogel surface wettability by solvent replacement. The demonstrated mechanism for photoresponsive hydrogels is highly efficient and applicable to many systems, which offers new perspectives in developing hydrogels with multiple photoresponsive functions.