Synthesis of peroxide‐curable butyl rubber via suzuki–miyaura coupling of halogenated butyl rubber with 4‐vinylphenylboronic acid

The Suzuki–Miyaura coupling reaction of brominated butyl rubber (BIIR) and/or chlorinated butyl rubber with a mixture of 4‐vinylphenylboronic acid and phenylboronic acid was carried out in THF under various conditions using a di‐μ‐chlorobis [5‐hydroxy‐2‐[1‐(hydroxyimino‐κN)ethyl]phenylκC] palladium(II) dimer, which is a type of cyclopalladated complex, as a catalyst. When BIIR and a small amount (Pd/Br ≈ 1/1000) of complex were used as the substrate and catalyst, respectively, a 4‐vinylphenyl and phenyl group could be introduced to butyl rubber in a high yield. Isomerization of the exo carbon–carbon double bond in BIIR was observed during the coupling reaction to give a cis and trans endo structure. The peroxide curing behavior of the resulting polymer at 170 °C indicated that the polymer could be cured by dicumyl peroxide, and the maximum torque of the resulting material, which reflects the crosslink density, was controllable by the composition of the boronic acids used. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Intracellular in vitro probe acylcarnitine assay for identifying deficiencies of carnitine transporter and carnitine palmitoyltransferase-1

Mitochondrial fatty acid oxidation (FAO) disorders are caused by defects in one of the FAO enzymes that regulates cellular uptake of fatty acids and free carnitine. An in vitro probe acylcarnitine (IVP) assay using cultured cells and tandem mass spectrometry is a tool to diagnose enzyme defects linked to most FAO disorders. Extracellular acylcarnitine (AC) profiling detects carnitine palmitoyltransferase-2, carnitine acylcarnitine translocase, and other FAO deficiencies. However, the diagnosis of primary carnitine deficiency (PCD) or carnitine palmitoyltransferase-1 (CPT1) deficiency using the conventional IVP assay has been hampered by the presence of a large amount of free carnitine (C0), a key molecule deregulated by these deficiencies. In the present study, we developed a novel IVP assay for the diagnosis of PCD and CPT1 deficiency by analyzing intracellular ACs. When exogenous C0 was reduced, intracellular C0 and total AC in these deficiencies showed specific profiles clearly distinguishable from other FAO disorders and control cells. Also, the ratio of intracellular to extracellular C0 levels showed a significant difference in cells with these deficiencies compared with control. Hence, intracellular AC profiling using the IVP assay under reduced C0 conditions is a useful method for diagnosing PCD or CPT1 deficiency.     

HCC-to-liver contrast on arterial-dominant phase images of EOB-enhanced MRI: comparison with dynamic CT

The purpose of this study was to assess the efficacy of arterial-dominant phase images of gadolinium–ethoxybenzyl–diethylenetriamine pentaacetic acid (EOB)-enhanced magnetic resonance imaging (MRI) for evaluation of arterial blood supply in hepatocellular carcinoma (HCC) in comparison with that of multiphasic dynamic computed tomography (CT). This study comprised 30 patients (22 men and 8 women, mean age: 68.0 years) with 40 pathologically proven HCCs (well differentiated: 3, moderately differentiated: 30, poorly differentiated: 7, mean diameter: 45.1 mm), all of whom underwent EOB-enhanced MRI and dynamic CT preoperative assessment. Regions of interest were placed over HCCs and the adjacent normal liver, and signal intensities or CT values were measured by two experienced abdominal radiologists on the arterial-dominant phase images of EOB-enhanced MRI and dynamic CT images. HCC-to-liver contrasts [Michelson's contrast: C_M=(S_HCC− S_Liver)/(S_HCC+ S_Liver)] were calculated and compared among the modalities. HCC-to-liver contrasts were also visually scored on a 5-point scale and compared. The mean C_M and visual score for dynamic CT were significantly higher than those for EOB-enhanced MRI. Good agreements were obtained among the two observers. Dynamic CT is a more suitable modality than EOB-enhanced MRI for evaluation of arterial blood supply in HCC. This should be taken into account for diagnosis and management of HCC.     

Hydrotalcite-bound ruthenium as a multifunctional heterogeneous catalyst for one-pot synthesis of α-alkylated nitriles and quinolines

This article reviews our recent progress in one-pot syntheses of α-alkylated nitriles and quinolines by heterogeneous catalysis with hydrotalcite-bound ruthenium based on cooperative action between cationic Ru species and the base sites of the hydrotalcite surface.     

Elucidation of the redox behavior of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) at poly(3,4-ethylenedioxythiophene) (PEDOT)-modified electrodes and application of the DMcT-PEDOT composite cathodes to lithium/lithium ion batteries

The redox reactions of DMcT at PEDOT-modified glassy carbon electrodes (GCEs) in acetonitrile (AN) have been investigated via cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM) in order to elucidate the redox reaction mechanism. A redox couple at -0.29 V versus Ag/Ag+ was assigned to the dimerization process of singly protonated DMcT (DMcT-1H), and a second couple observed at +0.42 V was assigned to the polymerization process of the protonated DMcT dimer. Our investigations revealed further that the anodic current response at +0.55 V (polymerization process) has a shoulder at +0.38 V ascribed to the dimerization process of doubly protonated DMcT (DMcT-2H), indicating that the redox couple at +0.42 V is the overlapping response of the polymerization of the protonated DMcT dimer and the dimerization of the DMcT-2H monomer. It was also confirmed that the dimerization process of DMcT-1H at -0.29 V proceeded not only at the surface of a PEDOT film but also inside the film as previously suggested. Moreover, the thermodynamics of these redox reactions at PEDOT-modified GCEs are dependent on the basicity (or acidity) of the solution, as anticipated and previously shown at unmodified GCEs. The oxidation of DMcT occurs at less positive potentials and the reduction occurs at more negative potentials in the presence of base. On the basis of the results obtained, the full redox reaction scheme for DMcT at a PEDOT-modified GCE is proposed.     

Reconstructed hydrotalcite as a highly active heterogeneous base catalyst for carbon-carbon bond formations in the presence of water

The aldol reaction of carbonyl compounds is efficiently catalyzed by reconstructed hydrotalcites, obtained by treating the Mg-Al mixed oxide with water, as solid base catalysts in the presence of water. The catalysis of the reconstructed hydrotalcites is attributable to the surface base sites, created during the organization of the layered structure, with uniformly distributed strength. Furthermore, the reconstructed hydrotalcites provide a unique acid-base bifunctional surface capable of promoting the Knoevenagel and Michael reactions of nitriles with carbonyl compounds.     

A review of parametric acoustic array in air

In this review paper, we examine some of the recent advances in the parametric acoustic array (PAA) since it was first applied in air in 1983 by Yoneyama. These advances include numerical modelling for nonlinear acoustics, theoretical analysis and experimentation, signal processing techniques, implementation issues, applications of the parametric acoustic array, and some safety concerns in using the PAA in air. We also give a glimpse on some of the new work on the PAA and its new applications. This review paper gives a tutorial overview on some of the foundation work in the PAA, and serves as a prelude to the recent works that are reported by different research groups in this special issue.