Morphology,interfacial interaction,and thermal degradation of polycarbonate/MCM-41 (nano)composites

This article reports on the morphology, interfacial interaction, thermal stability, and thermal degradation kinetics of polycarbonate (PC)/mesoporous silica (MCM-41) composites with various MCM-41 contents, prepared by melt compounding. The composites with low filler loadings (<0.3?wt%) maintained their transparency because of the well dispersed MCM-41 particles, but at higher filler loadings the composites lost their transparency due to the presence of agglomerates. The presence of agglomerates decreased the thermal stability of PC due to the reduced effectiveness of the particles to immobilize the polymer chains, free radicals, and volatile degradation products.     

Preparation and properties of polyhedral oligomeric silsesquioxane polymers

Polyhedral oligomeric silsesquioxane (POSS) polymers were synthesized by the dehydrogenative condensation of (HSiO_3/2)₈ with water in the presence of diethylhydroxylamine followed by trimethylsilylation. Coating films were prepared by spin‐coating of the coating solution prepared by the dehydrogenative condensation of POSS. The hardness of the coating films was evaluated using a pencil‐hardness test and was found to increase up to 8H with increases in the curing temperature. Free‐standing film and silica gel powder were prepared by aging the coating solution at room temperature. The silica gel powder was subjected to heat treatment under air atmosphere to show a specific surface area of 440 m² g⁻¹ at 100 °C, which showed a maximum at 400 °C as 550 m² g⁻¹. Copyright © 2011 John Wiley & Sons, Ltd.     

Mesoporous silica supported ytterbium as catalyst for synthesis of 1,2‐disubstituted benzimidazoles and 2‐substituted benzimidazoles

The benzimidazole ring is an important pharmacophore in contemporary drug discovery. Thus, effort to identifying new compounds containing benzimidazole scaffolds have gained much attention in recent years. In the present study, MCM‐41 type mesoporous silica with large pore (l‐MSN) supported ytterbium was successfully prepared by wet impregnation method. Among rare earth metal salts, ytterbium triflate has already been widely investigated as a catalyst in organic synthesis but less toxic ytterbium oxide has yet to be explored. Relatively high abundance and low cost of ytterbium with respect to many catalytically active metals (e.g. Pd, Au, Ru, Ir, Pt) offer an opportunity to develop sustainable catalysts for organic conversions. The catalyst has been characterized by various techniques including nitrogen adsorption, FT‐IR, TEM, SEM, EDX technique and elemental mapping. The obtained materials exhibit high surface area and a narrow distribution of mesoporosity. The catalytic performance of the Yb@l–MSNs was tested by synthesis of 1,2‐disubstituted benzimidazoles and 2‐substituted benzimidazoles through the coupling of aldehydes with o‐phenylenediamine. The catalyst resulted in excellent yields in short reaction times and the reaction showed tolerance toward both electron‐donating and electron‐withdrawing functional groups at room temperature. A particularly interesting finding was the solvent selectivity of this reaction; namely, 1,2‐disubstituted benzimidazoles generated as major product in water‐ethanol, while the 2‐substituted benzimidazoles was generated exclusively in non‐polar solvents like toluene.     

Synthesis,characterization and solid‐phase extraction properties of novel bis(diazo‐azomethine) ligands supported on mesoporous silica

The novel mesoporous silica‐supported bis(diazo‐azomethine) compounds have been synthesized and characterized successively. In the first step, 1,3‐phenylenedimethanamine and 4,4′‐diaminodiphenylmethane were diazotized, and the obtained bis(diazonium) cations were coupled with 2,4‐dihydroxybenzaldehyde. The synthesized bis(diazo‐carbonyl) compounds, 5,5′‐((1,3‐phenylenebis(methylene))bis(diazene‐2,1‐diyl))bis(2,4‐dihydroxybenzaldehyde) (A1) and 5,5′‐((methylenebis(4,1‐phenylene))bis(diazene‐2,1‐diyl))bis(2,4‐dihydroxybenzaldehyde) (A2) were chemically supported on amino‐modified silica‐gel (as L1 and L2). Elemental analysis, liquid chromatography‐mass spectroscopy, liquid‐phase NMR (¹H and ¹³C) and solid‐phase NMR (CP‐MAS ²⁹Si and ¹³C), FT‐IR, TG/DTA, scanning electron microscopy and energy‐dispersive X‐ray spectroscopy techniques were used for characterizations of all the synthesized compounds. The syringe and batch techniques were applied for the solid‐phase extraction properties of Pb(II), Cu(II), Cd(II) and Cr(III) ions using an inductively coupled plasma‐atomic emission spectroscopy instrument. The recoveries of Pb(II), Cu(II), Cd(II) and Cr(III) ions have been achieved to 95–99% with the (RSDs) of ± 2–3% in optimum conditions.     

Palladium–quaternary phosphonium phase transfer catalyst brush assembly as reusable and environmentally benign catalyst for coupling of aryl halides and sodium tetraphenylborate in neat water

A first example of simultaneous covalent anchoring of a palladate anion–phosphonium cation matrix on the surface of silica nanoparticles and application in the Suzuki coupling reaction of a variety of different haloarenes and sodium tetraphenylborate in neat aqueous media without the addition of any organic co‐solvent are described. Copyright © 2015 John Wiley & Sons, Ltd.     

Syntheses of 5-Fluorouracil-Terminated Monomethqxypqly(Ethylene Glycol)S,Their Hydrolysis Behavior,and Their Antitumor Activities

The covalent attachments of 5-fluorouracil (5FU) units to poly(ethylene glycol) monomethoxy ether (MeO-PEG) attached through ester, amide, and ether bonds were carried out; three types of linkages were obtained through which 5FU units were attached to MeO-PEG. For the investigation of the release of the 5FU units, the homogeneous hydrolysis was investigated in vitro in the presence and absence of enzymes. Although the rate of release of l-β-carboxyethyl-5FU or 1-β-hydroxyethyl-5FU from the compounds was fast, the release of 5FU itself was slow. In addition, the antitumor activity of these three types of MeO-PEG-bound 5FU unit was tested in vivo by preliminary screening by the National Cancer Institute or by the Japanese Foundation for Cancer Research.     

H2SO4O2 AS AN EFFICIENT CATALYST FOR THE PREPARATION OF PHENYLHYDRAZONES AND 2,4-DINITROPHENYLHYDRAZONES UNDER SOLVENT-FREE CONDITIONS

HSO mixed with silica gel (1:1) by weight produces a white powder which is an effective catalyst for the conversion of carbonyl compounds to their corresponding phenylhydrazones and 2,4-dintrophenylhydrazones under solvent-free conditions.     

A VERSATILE METHOD FOR THE CONVERSION OF ALDOXIMES TO NITRILES USING SILICA GEL/THIONYL CHLORIDE

A simple convenient procedure for dehydration of aldoximes has been developed using silica gel/thionyl chloride in heterogeneous conditions. The method has been found to be effective for a wide range of aromatic oximes.