Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes

Stoichiometric reactions between mesityl azide (MesN(3), Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3) (2)(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)(2); Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-(C6H3Pr2)-Pr-i))(2)(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN(3))]Ln[(MesN(3))-(CH2SiMe3)](2) (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)] Lu[NH(2,6-C6H3 Pr-i(2))](2) (4), and bis(alkynyl) complex (5) (L(MesN(3))Lu (C CPh)(2))(2), respectively. The triazenyl group in 3 coordinates to the metal ion in a rare eta(2)-mode via N-beta and N-gamma atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN(3)), in 3, 4 and 5 chelates to the metal ion in a eta(3)-mode via N-alpha and N-gamma atoms. In the presence of excess phenylacetylene, complex 3a isomerized to 3', where the triazenyl group coordinates to the metal ion in a eta(3) mode via Na and Ng atoms.

Raspberry-like Hierarchical Au/Pt Nanoparticle Assembling Hollow Spheres with Nanochannels: An Advanced Nanoelectrocatalyst for the Oxygen Reduction Reaction

In this contribution, we for the first time report the synthesis of raspberry-like hierarchical Au/Pt nanoparticle (NP) assembling hollow spheres (RHAHS) with pore structure and complex morphology through one in situ sacrificial template approach without any post-treatment procedure. This method has some clear advantages including simplicity, quickness, high quality, good reproducibility, and no need of a complex post-treatment process (removing templating). Furthermore, the present method could be extended to other metal-based NP assembling hollow spheres. Most importantly, the as-prepared RHAHS exhibited excellent electrocatalytic activity for oxygen reduction reaction (ORR). For instance, the present RHAHS-modified electrode exhibited more positive potential (the half-wave potential at about 0.6 V), higher specific activity, and higher mass activity for ORR than that of commercial platinum black (CPB). Rotating ring-disk electrode (RRDE) voltarnmetry demonstrated that the RHAHS-modified electrode could almost catalyze a four-electron reduction of O-2 to H2O in a 0.5 M air-saturated H2SO4 solution.

Construction of metal nanoparticle/multiwalled carbon nanotube hybrid nanostructures providing the most accessible reaction sites

Functionalized multiwalled carbon nanotubes (MWNTs) were selected as cross-linkers to construct three-dimensional (3D) porous nanoparticle/MWNT hybrid nanostructures by "bottom-up'' self-assembly. The resultant 3D hybrid nanostructure was different from that of metal nanoparticle multilayer assemblies prepared by traditional routes using small molecules or polymers as cross-linkers. The rigidity of the MWNTs resulted in only partial coverage of the nanoparticle surfaces between the linkers during the growth of multilayer film, providing more accessible surfaces to allow target molecules to adsorb on to and react with. HRP was used as a simple model to study the porosity of this assembly.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.

Motion of integrated CdS nanoparticles by phase separation of block copolymer brushes

A new method of reversibly moving US nanoparticles in the perpendicular direction was developed on the basis of the phase separation of block copolymer brushes. Polystyrene-b-(poly(methyl methaerylate)-co-poly(cadmium dimethacrylate)) (PS-b-(PMMA-co-PCdMA)) brushes were grafted from the silicon wafer by surface-initiated atom transfer radical polymerization (ATRP). By exposing the polymer brushes to H2S gas, PS-b-(PMNlA-co-PCdNlA) brushes were converted to polystyrene-b-(poly(methyl methacrylate) -co-poly(methacrylic acid)(CdS)) (PS-b-(PMMA-co-PMAA(CdS))) brushes, in which US nanoparticles were chemically bonded by the carboxylic groups of PMAA segment. Alternating treatment of the PS-b-(PMMA-co-PMAA(CdS)) brushes by selective solvents for the outer block (a mixed solvent of acetone and ethanol) and the inner PS block (toluene) induced perpendicular phase separation of polymer brushes, which resulted in the reversible lifting and lowering of US nanoparticles in the perpendicular direction. The extent of movement can be adjusted by the relative thickness of two blocks of the polymer brushes.

Efficient one-pot synthesis of highly substituted pyridin-2(1H)-ones via the Vilsmeier-Haack reaction of 1-acetyl,1-carbamoyl cyclopropanes

A facile and efficient one-pot synthesis of highly substituted pyridin-2(1H)-ones is developed via the Vilsmeier-Haack reaction of readily available 1-acetyl,1-carbamoyl cyclopropanes, and a mechanism involving sequential ring-opening, haloformylation, and intramolecular nucleophilic cyclization reactions is proposed.

Synthesis of novel functional polyolefin containing carboxylic acid via Friedel-Crafts acylation reaction

The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via Friedel-Crafts (F-C) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in order to optimize the acylation process. In the optimum reaction conditions, almost all of the phenyls can be acylated with any anhydride. The microstructure of acylated copolymer was characterized by Fr-IR, H-1 NMR and H-1-H-1 COSY. All the peaks of acylated copolymers can be accurately attributed, which indicates that all the acylation reactions occur only at the para-positions of the substituent of the aromatic rings. The thermal behavior was studied by differential scanning calorimetry (DSC), showing that the melting temperatures (T(m)s) of acylated copolymers with GA firstly decrease slowly and then increase significantly with the increase of the amount of carboxyl acid groups.

The real role of carbon in Pt/C catalysts for oxygen reduction reaction

A new electrocatalysis of carbon materials for oxygen reduction reaction (ORR) on Pt/C catalysts was discovered. It was found that there exist two kinds of electroactive sites on these supports of carbon materials, which can effectively electrocatalyze the reduction of peroxide intermediated from oxygen reduction on Pt, as this provides continuous driving force to move the equilibrium toward the production of peroxide from ORR.

Sugars-grafted aliphatic biodegradable poly(L-lactide-co-carbonate)s by click reaction and their specific interaction with lectin molecules

A novel biodegradable aliphatic poly(L-lactide-co-carbonate) bearing pendant acetylene groups was successfully prepared by ring-opening copolymerization of L-lactide (LA) with 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (PC) in the presence of benzyl alcohol as initiator with ZnEt2 as catalyst in bulk at 100 degrees C and subsequently used for grafting 2-azidoethyl beta-D-glucopyranoside and 2-azidoethyl beta-lactoside by the typical "click reaction," that is Cu(I)-catalyzed cycloaddition of azide and alkyne. The density of acetylene groups in the copolymer can be tailored by the molar ratio of PC to LA during the copolymerization. The aliphatic copolymers grafted with sugars showed low cytotoxicity to L929 cells, improved hydrophilic properties and specific recognition and binding ability with lectins, that is Concanavalin A (Con A) and Ricinus communis agglutinin (RCA). Therefore, this kind of sugar-grafted copolymer could be a good candidate in variety of biomedical applications.