Generation of Aryl(2‐lithiophenyl)methanone O‐Methyl Oximes and Their Use for the Synthesis of N‐(3‐Alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines via the Reaction with Nitriles

An efficient two‐step procedure for the preparation of a new type of 1H‐isoindoles, i.e., N‐(3‐alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines 5 , from readily available aryl(2‐bromophenyl)methanones 1 has been developed. Aryl(2‐bromophenyl)methanone O‐methyloximes 2 , derived from the corresponding ketones, were treated with BuLi in Et₂O at 0° to generate novel lithium compounds, aryl(2‐lithiophenyl)methanone O‐methyloximes 3 , which were allowed to react with nitriles to give the desired products 5 in moderate‐to‐fair yields.     

Labelless impedance immunosensor based on polypyrrole-pyrolecarboxylic acid copolymer for hCG detection

In this work, a sensitive label-free impedimetric hCG-immunosensor was constructed by using a commercial screen-printing carbon ink electrode (namely disposable electrochemical printed chip) as the basis. The carbon ink electrode of DEP chip is modified first by deposition of polypyrrole-pyrole-2-carboxylic acid copolymer and thence hCG antibody immobilization via the COOH groups of pyrrole-2-carboxylic acid, which can serve as a linker for covalent biomolecular immobilization. The experimental results exposed that the designed immunosensor is more sensitive than other previously reported immunosensors, in the case of detection limit and linear range for antigen detection. With optimal fabrication parameters, the detection limit for α-hCG was 2.3 pg/mL in 10 mM phosphate buffer saline (PBS) solution containing 1% bovine serum albumine (BSA). Moreover, the use of inexpensive DEP chip as a basis for these immunosensors will allow for simple instrumentation, disposable and portable at low cost. This work also demonstrates a new approach to develop a sensitive and label-free impedimetric immunosensor based on screen-printed electrode for applications in clinical diagnosis.     

Photochemical activation of ruthenium(II)-pyridylamine complexes having a pyridine-N-oxide pendant toward oxygenation of organic substrates

Ruthenium(II)-acetonitrile complexes having η(3)-tris(2-pyridylmethyl)amine (TPA) with an uncoordinated pyridine ring and diimine such as 2,2'-bipyridine (bpy) and 2,2'-bipyrimidine (bpm), [Ru(II)(η(3)-TPA)(diimine)(CH(3)CN)](2+), reacted with m-chloroperbenzoic acid to afford corresponding Ru(II)-acetonitrile complexes having an uncoordinated pyridine-N-oxide arm, [Ru(II)(η(3)-TPA-O)(diimine)(CH(3)CN)](2+), with retention of the coordination environment. Photoirradiation of the acetonitrile complexes having diimine and the η(3)-TPA with the uncoordinated pyridine-N-oxide arm afforded a mixture of [Ru(II)(TPA)(diimine)](2+), intermediate-spin (S = 1) Ru(IV)-oxo complex with uncoordinated pyridine arm, and intermediate-spin Ru(IV)-oxo complex with uncoordinated pyridine-N-oxide arm. A Ru(II) complex bearing an oxygen-bound pyridine-N-oxide as a ligand and bpm as a diimine ligand was also obtained, and its crystal structure was determined by X-ray crystallography. Femtosecond laser flash photolysis of the isolated O-coordinated Ru(II)-pyridine-N-oxide complex has been investigated to reveal the photodynamics. The Ru(IV)-oxo complex with an uncoordinated pyridine moiety was alternatively prepared by reaction of the corresponding acetonitrile complex with 2,6-dichloropyridine-N-oxide (Cl(2)py-O) to identify the Ru(IV)-oxo species. The formation of Ru(IV)-oxo complexes was concluded to proceed via intermolecular oxygen atom transfer from the uncoordinated pyridine-N-oxide to a Ru(II) center on the basis of the results of the reaction with Cl(2)py-O and the concentration dependence of the consumption of the starting Ru(II) complexes having the uncoordinated pyridine-N-oxide moiety. Oxygenation reactions of organic substrates by [Ru(II)(η(3)-TPA-O)(diimine)(CH(3)CN)](2+) were examined under irradiation (at 420 ± 5 nm) and showed selective allylic oxygenation of cyclohexene to give cyclohexen-1-ol and cyclohexen-1-one and cumene oxygenation to afford cumyl alcohol and acetophenone.     

Catalytic silicon-mediated carbon-carbon bond-forming reactions of unactivated amides

In the presence of catalytic amounts of trialkylsilyl triflate and triethylamine, unactivated amides react with imines to afford the corresponding Mannich-type adducts in high yields with high anti selectivities. While silicon enolates have been widely used in organic synthesis for four decades, this is the first example of the catalytic use of the silicon species, to the best of our knowledge. Moreover, it is noteworthy that unactivated simple amides bearing α-protons that are less acidic than those of ketones and aldehydes can be successfully used in catalytic direct-type addition reactions. Finally, a preliminary trial of an asymmetric catalytic version was conducted and showed promising enantioselectivity of the desired product.     

Physicochemical properties and plastic crystal structures of phosphonium fluorohydrogenate salts

Fluorohydrogenate salts of quaternary phosphonium cations with alkyl and methoxy groups (tetraethylphosphonium (P(2222)(+)), triethyl-n-pentylphosphonium (P(2225)(+)), triethyl-n-octylphosphonium (P(2228)(+)), and triethylmethoxymethylphosphonium (P(222(101))(+))) have been synthesized by the metatheses of anhydrous hydrogen fluoride and the corresponding phosphonium bromide or chloride precursors. The three salts with asymmetric cations, P(222m)(FH)(2.1)F (m = 5, 8, and 101), are room temperature ionic liquids (ILs) and are characterized by differential scanning calorimetry, density, viscosity, and conductivity measurements. Linear sweep voltammetry using a glassy carbon working electrode shows these phosphonium fluorohydrogenate ILs have wide electrochemical windows (>4.9 V) with the lowest viscosity and highest conductivity in the known phosphonium-based ILs. Thermogravimetry shows their thermal stabilities are also improved compared to previously reported alkylammonium cation-based fluorohydrogenate salts. Differential scanning calorimetry and X-ray diffraction revealed that tetraethylphosphonium fluorohydrogenate salt, P(2222)(FH)(2)F, exhibits two plastic crystal phases. The high temperature phase has a hexagonal lattice, which is the first example of a plastic crystal phase with an inverse nickel arsenide-type structure, and the low-temperature phase has an orthorhombic lattice. The high-temperature plastic crystal phase exhibits a conductivity of 5 mS cm(-1) at 50 °C, which is the highest value for the neat plastic crystals.     

Effects of sub-millimeter-bubble injection on transition to turbulence in natural convection boundary layer along a vertical plate in water

Temperature and velocity measurements are performed to clarify the effects of sub-millimeter-bubble injection on the transition to turbulence in the natural convection boundary layer along a vertical plate in water. In particular, we focus on the relationship between the bubble injection position L and the transition to turbulence in the natural convection boundary layer. The bubble injection positions used in our experiments are L = 1.6 and 3.6 mm. Bubble injection at L = 1.6 mm delays the transition to turbulence in the natural convection boundary layer, while that at L = 3.6 mm accelerates the transition to turbulence in the boundary layer. In the case of L = 1.6 mm, the appearance region of the liquid velocity fluctuation in the bubble-induced upward flow in the upstream unheated section is restricted to near the wall, although the peak of the liquid velocity fluctuation is high. In contrast, in the case of L = 3.6 mm, the relatively large liquid velocity fluctuation is distributed widely over the laminar boundary layer width. These results suggest that the effect of the liquid velocity fluctuation on the laminar boundary layer is quite different between L = 1.6 and 3.6 mm. It is therefore expected that the transition to turbulence in the natural convection boundary layer for the case with bubble injection is dependent on the magnitude and appearance region of the liquid velocity fluctuation in the bubble-induced upward flow in the upstream unheated section.     

Preparation of telechelic oligomers by thermal degradation of propylene copolymers

The reactive end groups of nonvolatile oligomers obtained by controlled thermal degradation of poly(propylene-ran-ethylene) and poly(propylene-ran-1-butene) were determined by ¹H and ¹³C NMR spectroscopy. The molar ratio of unsaturated to saturated end groups was found to be about 9:1. The average number of unsaturated end groups per molecule was between 1.6 and 1.8, indicating that 60–80 mol% of the oligomer molecules were telechelic, having two terminal unsaturated end groups. These oligomers had a lower polydispersity than the raw material, despite their lower molecular weight and melting temperature. Although the end groups resulting from each monomer unit could be detected by ¹³C NMR, the end group composition differed from that of the main chains of the raw materials. The end group composition was satisfactorily explained by the differences in bond dissociation energy and activation energy of elementary reactions that occurred during thermal degradation, based on the monomer composition of the raw materials.     

Influence of the loading rate on liquid‐crystalline epoxy resin systems

The fracture toughness of liquid‐crystalline epoxy systems, which had a nematic polydomain structure (domain size about 40 μm), with an increasing loading rate was evaluated. In this system, the fracture toughness dramatically decreased from 1.96 to 0.22 MN/m^3/2 with an increasing loading rate (0.1–5 mm/min). The network orientation near the fracture surface of different loading rate systems was investigated with polarized optical microscopy and polarized infrared spectroscopy. As a result, a large oriented region of mesogenic groups was observed near the fracture surface in the relatively low loading rate (0.1 and 0.5 mm/min) systems, but such a phenomenon was not observed in the high loading rate (2 and 5 mm/min) systems. These results showed that the high fracture toughness of the system at the low loading rate was due to the magnitude and region of the reorientation of the mesogenic groups in the fracture process and that high toughness could not be achieved at a high loading rate because the loading rate was too fast to allow orientation of the networks containing the mesogenic groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1296–1302, 2005