Ruthenium‐catalyzed synthesis of quinolines via reductive heteroannulation of nitroarenes with 3‐amino‐1‐propanols

Nitroarenes are reductively cyclized with 3‐amino‐1‐propanols in dioxane/H₂O in the presence of a ruthenium catalyst and tin(II) chloride dihydrate together with isopropanol to afford the corresponding quinolines. A reaction pathway involving initial reduction of nitroarenes to anilines, propanol group transfer from 3‐amino‐1‐propanols to anilines, N‐alkylation of anilines by 3‐anilino‐1‐propanols and heteroannulation of 1,3‐dianilinopropanes is proposed.     

Interfacial Characteristics and Fracture Toughness of Electrolytically Ni-Plated Carbon Fiber-Reinforced Phenolic Resin Matrix Composites

The electrolytic plating of metallic nickel on a carbon fiber surface has been carried out in order to improve the interfacial adhesion and the mechanical properties in carbon fiber/phenolic matrix composite systems. The surface and the mechanical interfacial properties of composites are characterized by X-ray photoelectron spectrometry (XPS), surface free energy, and the critical stress intensity factor (K(IC)). From the experimental results, it is clearly revealed that the oxygen functional groups and the metallic nickel on fibers largely affect the mechanical interfacial behavior of the composites, resulting in increased surface polarity, whereas the nitrogen functional groups have no effect. Also, a good correlation between surface oxygen functional groups and mechanical interfacial properties and between wettability and K(IC) is established and it is found that a 10 A m(-2) current density is the optimum condition for this system. Copyright 2001 Academic Press.     

Nanophase segregation and water dynamics in the dendrion diblock copolymer formed from the Fréchet polyaryl ethereal dendrimer and linear PTFE

We propose a new material consisting of a dendrion copolymer formed from (a) a water-soluble dendritic polymer and (b) a hydrophobic backbone. Using molecular dynamics simulations techniques, we determine the structure and dynamics of the dendrion formed by second-generation Fréchet polyaryl ethereal dendrimer as the hydrophilic component and linear polytetrafluoroethylene (PTFE) as the hydrophobic polymer, with 5 and 10 wt % of water. We find that this material produces a well-developed nanoscale structure in which water forms a continuous nanophase, making this new family of compounds promising candidates for applications in fuel cell membranes. We find that the water molecules are incorporated into the dendrimer block of the copolymer to form a nanophase-segregated structure. The well-developed nanophase-segregated structures rendered by this material have characteristic dimensions of segregation ( approximately 30 Angstrom) and dendrimer conformational properties that are independent of water content. Calculations of water dynamics and proton transport in these nanophase-segregated structures indicate that the dendrion copolymer membrane with 10 wt % of water content has a water structure and transport properties equivalent to that of the hydrated Nafion membrane with 20 wt % of water content.     

Comparative studies of various run buffers for chiral capillary electrophoresis using chiral crown ether as a chiral selector

In the capillary electrophoretic separation of primary amine enantiomers using (+)-(18-crown-6)-tetracarboxylic acid (18C6H4) as a chiral selector, the presence of run buffer constituents such as tris(hydroxymethyl)aminomethane (Tris) or Na+ competing with analytes for 18C6H4, diminishes the effectiveness of 18C6H4. In order to determine appropriate buffer systems for 18C6H4, various run buffer cationic components including Tris, 1,3-bis[tris(hydroxymethyl)methylamino]propane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, triethanolamine, tetramethylammonium, and Na+ were compared. Quantitative studies of the effects of the competitive constituents were carried out by measuring the electrophoretic mobilities of histidine as a function of the 18C6H4 concentration. We also derived a simple equation to estimate the optimal chiral selector concentration for a maximum mobility difference in the presence of a competitive inhibitor.     

Catalytic degradation of polystyrene using HUSY catalysts

Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1&gt;C3&gt;C2&gt;C4&gt;C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities.     

Supramolecular reactor from self-assembly of rod-coil molecule in aqueous environment

We synthesized an amphiphilic coil-rod-coil triblock molecule consisting of hexa-p-phenylene as a rod block and poly(ethylene oxide) with the number of repeating units of 17 as coil blocks and investigated aggregation behavior in aqueous environment. The rod-coil molecule was observed to aggregate into discrete micelles consisting of hydrophobic disklike rod bundles encapsulated by hydrophilic poly(ethylene oxide) coils. The aromatic bundles of the micelles were demonstrated to be used as an efficient supramolecular reactor for the room temperature Suzuki cross-coupling reaction of a wide range of aryl halides, including even aryl chlorides with phenylboronic acids in aqueous environment. These results demonstrate that self-assembly of amphiphilic rod-coil molecules can provide a useful strategy to construct an efficient supramolecular reactor for aromatic coupling reaction.     

Unusually stable molecular capsule formation of a tetraphenyleneurea cavitand

An unusually stable molecular capsule was formed by heating phenyleneurea-spanned resorcinarene cavitand with 4-methyl-N-p-tolylbenzamide. The molecular capsule behaved as a discrete molecular entity showing a cylindrical D(4d) structure and showed no guest exchange in toluene-d(8) even at 100 degrees C. [structure: see text]     

A facile synthesis of polypyrrole nanotubes using a template-mediated vapor deposition polymerization and the conversion to carbon nanotubes

Polypyrrole (PPy) nanotubes with highly uniform surface and tunable wall thickness were fabricated by one-step vapor deposition polymerization (VDP) using anodic aluminium oxide (AAO) template membranes, and transformed into carbon nanotubes through a carbonization process.     

Degradation of polystyrene using montmorillonite clay catalysts

Summary The performance of acid-treated montmorillonite catalysts in the degradation of polystyrene (PS) was investigated in this study. The degradation was carried out in a semi-batch reactor with a mixture of PS and catalyst at 400-450^oC. The commercial Süd Chemie acid-treated montmorillonite clays (K-series) showed good catalytic activity for the degradation of PS. The styrene monomer and ethylbenzene were major liquid products. The increase of surface acidity enhanced further cracking of styrene dimer and trimer to produce styrene monomer. Higher production of ethylbenzene for K30 may be related to its bigger pore volume and surface area compared to those of K5. High degradation temperature favored styrene monomer production.     

Phase separation behavior of epoxy resin modified with crosslinked rubber

Low molecular weight liquid rubber (ATBN = amine terminated butadiene acrylonitrile copolymer or CTBN = carboxyl terminated butadiene acrylonitrile copolymer)–DGEBA (diglycidyl ether of bisphenol A) blends indicated upper critical solution temperature (UCST) behavior. The phase separation behavior of the neat and crosslinked rubber (ATBN, CTBN)–epoxy blends was analyzed by a laser light scattering experiment. Lauryl peroxide (LPO) was employed to crosslink the rubber during the initial annealing stage. The onset point of the phase separation in the crosslinked ATBN–epoxy system occurred later than in the case of the neat ATBN–epoxy system. However, the onset point of the phase separation process started earlier in the case of the crosslinked CTBN–epoxy system. The domain correlation length of the crosslinked rubber-added system was smaller than that of the neat rubber-added system.