Methanol vapor‐induced morphology and current–voltage characteristic changes in a cast‐coated nafion film/interdigitated microarray electrode

Methanol vapor‐induced membranous changes in a cast‐coated Nafion thin film were studied through current–voltage (I–V) characteristics with an interdigitated microarray (IDA) electrode and atomic force microscopy (AFM). The obtained I–V curves showed that the as‐prepared Nafion film was stable under humidified nitrogen gas; however, the I–V profile dramatically changed with exposure to methanol vapor. Next, the morphology of the film was compared before and after methanol exposure with AFM images. On the basis of our observations, we found that the as‐prepared film had an irregularly complicated microstructure, whereas the structure became homogeneous in appearance after 30 min of exposure to methanol gas. The alternating‐current conductivity data, showing almost the same magnitude before and after exposure, strongly suggested that the I–V profile shift was based on a change in an electrode reaction mechanism induced by a change in the junction at the Nafion/IDA electrode interface. Furthermore, the methanol vapor‐pre‐exposed Nafion was stable for further exposure to methanol vapor, water vapor, or both. With the stabilized film used in combination with the IDA electrode, a reversible change in the magnitude of the current was observed when the methanol/water vapor ratio was varied. This indicated that the electrode reaction had good reproducibility after the treatment. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1103–1109, 2002     

An Entropy-Based Tool to Help the Interpretation of Common-Factor Spaces in Factor Analysis

This paper proposes a method for deriving interpretable common factors based on canonical correlation analysis applied to the vectors of common factors and manifest variables in the factor analysis model. First, an entropy-based method for measuring factor contributions is reviewed. Second, the entropy-based contribution measure of the common-factor vector is decomposed into those of canonical common factors, and it is also shown that the importance order of factors is that of their canonical correlation coefficients. Third, the method is applied to derive interpretable common factors. Numerical examples are provided to demonstrate the usefulness of the present approach.     

Spectroscopic Properties of Amine‐substituted Analogues of Firefly Luciferin and Oxyluciferin

Spectroscopic and photophysical properties of firefly luciferin and oxyluciferin analogues with an amine substituent (NH₂, NHMe and NMe₂) at the C6' position were studied based on absorption and fluorescence measurements. Their π‐electronic properties were investigated by DFT and TD‐DFT calculations. These compounds showed fluorescence solvatochromism with good quantum yields. An increase in the electron‐donating strength of the substituent led to the bathochromic shift of the fluorescence maximum. The fluorescence maxima of the luciferin analogues and the corresponding oxyluciferin analogues in a solvent were well correlated with each other. Based on the obtained data, the polarity of a luciferase active site was explained. As a result, the maximum wavelength of bioluminescence for a luciferin analogue was readily predicted by measuring the photoluminescence of the luciferin analogue in place of that of the corresponding oxyluciferin analogue.     

Reaction of 2-propargylphenylcarbamates with diphenyliodonium salts via Meyer-Schuster rearrangement

The syntheses of 2,3-dihydro-4-quinolones from 2-propargylphenylcarbamates by one-pot tandem process that involves Meyer-Schuster rearrangement or arylative Meyer-Schuster rearrangement/Michael addition of carbamate nitrogen to the resulting vinyl ketones have been developed. Phenylcarbamates tethering tertiary propargyl alcohols underwent arylative Meyer-Schuster rearrangement/Friedel-Crafts alkylation to produce 2,3-dihydroindenones.     

Similarities and Differences of the Active Sites in Basic and Advanced MgCl2‐Supported Ziegler‐Natta Propylene Polymerization Catalysts

Though preparation procedures of heterogeneous Ziegler‐Natta catalysts for propylene polymerization are sophisticated, it is uncertain whether the nature of the active sites is similar or different for different preparation procedures. In this study, the effects of preparation procedures on the nature of the active sites were investigated by stopped‐flow polymerization in combination with microstructure analysis of polymers. Both basic and advanced types of catalysts showed the same two kinds of isospecific active site, which indicated little influence of the preparation method on the active site structure. On the contrary, the ratios of the two kinds of isospecific sites were not the same, resulting in variation of average polymer properties.

     

A Parabolic Approach to Martin Boundaries for Elliptic Equations in Skew Product Form

We consider positive solutions of elliptic partial differential equations on non-compact domains of Riemannian manifolds. We explicitly determine Martin compactifications and Martin kernels for a wide class of elliptic equations in skew product form by exploiting parabolic Martin kernels for associated parabolic equations.     

Addition of alkyl radicals, generated from carboxylic acids via photochemical decarboxylation, to glyoxylic oxime ether: a mild and efficient route to α-substituted α-aminoesters

Radical addition to a glyoxylic oxime ether was accomplished under mild conditions using an alkyl radical generated from a free carboxylic acid via photochemical decarboxylation. The photoreaction provided an efficient route to α-substituted α-aminoesters from carboxylic acids and oxime ether.     

Copper‐Catalyzed Ritter‐Type Reaction of Unactivated Alkenes with Dichloramine‐T

It was shown that dichloramine‐T ( 1 ) reacted with cyclohexene in acetonitrile to give N¹‐(2‐chlorocyclohexyl) amidine 2a and N‐(2‐chlorocyclohexyl)acetamide ( 3 ) via the competitive addition of acetonitrile and N‐chloro‐N‐tosylamino anion to cyclohexenechloronium ion. This reaction can be catalyzed by Cu(OAc)₂, primarily affording 2a . Furthermore, the resulting 2a can be cyclized to benzimidazol 14a in good yield by treating with KOH in dioxane.