Palladium-catalyzed cycloaddition of alkynyl aryl ethers with internal alkynes via selective ortho C-H activation

Alkynyl aryl ethers react with internal alkynes through selective ortho C-H activation by a palladium(0) catalyst to give substituted 2-methylidene-2H-chromenes. The alkynoxy group acts as a directing group to promote ortho C-H functionalization. Deuterium-labeling experiments indicated that the arylpalladium hydride complex is a key intermediate via oxidative addition. Various functional groups tolerate the present transformation to give the corresponding products.     

Photodegradation of toluene over TiO(2-x)N(x) under visible light irradiation

We report the photooxidation of toluene over nitrogen doped TiO(2) (TiO(2-x)N(x)) under visible light irradiation. The photocatalytic oxidation of toluene in air over TiO(2-x)N(x) powders was studied using diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), gas chromatography (GC), ion chromatography (IC), and gas chromatography mass spectrometry (GC-MS), focusing on the photocatalytic decomposition processes of toluene. Results obtained indicate that toluene, weakly adsorbed on the catalyst surface, is initially photooxidized to benzaldehyde which adsorbs onto the TiO(2-x)N(x) surface more strongly, leading to the formation of ring-opening products such as carboxylic acids and aldehydes. No gaseous intermediates were detected during the photooxidation. Major intermediates adsorbed at the catalyst surface were oxalic acid, (COOH)(2), acetic acid, CH(3)COOH, formic acid, HCOOH, and pyruvic acid, CH(3)COCOOH, whereas more complicated carboxylic species, including propionic acid, CH(3)CH(2)COOH, isovaleric acid, (CH(3))(2)CHCH(2)COOH, and succinic acid, (CH(2)COOH)(2), were also found in the early stage of the photooxidation. These intermediate products were gradually photodegraded to CO(2) and H(2)O under visible light irradiation.     

Microgel formation in emulsion copolymerization: II. Seeded polymerization

Microgel formation in seeded emulsion copolymerization of methyl methacrylate and ethylene glycol dimethacrylate is investigated both experimentally and theoretically. By introducing seed latex, the network structure development can be changed significantly. Even when the crosslinking density development takes a similar pattern as the crosslinking copolymerization in homogeneous media, the molecular weight development shows both types of behavior that is characteristic of emulsion polymerization without seed latex and of homogeneous polymerization, depending on the primary polymer chain length and the mole fraction of the divinyl monomer used. Once the microgels are formed, the weight-average molecular weight increases just linearly with conversion due to a very small locus of polymerization. The present investigation reveals important characteristics of gelation phenomena in a limited space. © 1996 John Wiley & Sons, Inc.     

LR Tests for Random-Coefficient Covariance Structures in an Extended Growth Curve Model

This paper is concerned with an extended growth curve model with two within-individual design matrices which are hierarchically related. For the model some random-coefficient covariance structures are reduced. LR tests for testing the adequacy of each of these random-coefficient structures and their asymptotic null distributions are derived.     

Gravitational Effects on Mixing and Growth Morphology of an In0.5Ga0.5 System

A mixing experiment of multicomponents melts was performed using a uniform temperature furnace in the Second International Microgravity Laboratories (IML-2) mission. Growth morphologies and Ga concentration profiles were analyzed for the samples with the compositional ratio of 0.5 In–0.5 Ga–1.0 Sb grown under microgravity and on earth. The sample with free surface grown under microgravity was nearly spherical in shape, except some parts with projections. Ga was dispersed homogeneously in the bulk because the mixing was enhanced by Marangoni convection due to the concentration gradient. On the other hand, the sample grown on earth was a double cylindrical shape with different diameters, and Ga concentration decreased from top to bottom, showing clearly the effect of gravity. Many needle crystals were formed in both space and earth samples due to rapid cooling. The average size of the needle crystals grown in space was larger than that of the earth sample.