Design and characterization of ferrocene-peptide-oligoaniline conjugates

Ferrocene-peptide-oligoaniline conjugates were designed by the introduction of two ferrocene-peptide conjugates into a π-conjugated phenylenediamine spacer to demonstrate the luminescent switching by changing the redox states of the π-conjugated phenylenediamine moiety, wherein the self-aggregation of the π-conjugated moiety was achieved in a higher concentration to induce the chirality organization with a red shift of the maximum emission wavelength.     

Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior

Anionic polymerizations of three 1,3‐butadiene derivatives containing different N,N‐dialkyl amide functions, N,N‐diisopropylamide (DiPA), piperidineamide (PiA), and cis‐2,6‐dimethylpiperidineamide (DMPA) were performed under various conditions, and their polymerization behavior was compared with that of N,N‐diethylamide analogue (DEA), which was previously reported. When polymerization of DiPA was performed at ?78 °C with potassium counter ion, only trace amounts of oligomers were formed, whereas polymers with a narrow molecular weight distribution were obtained in moderate yield when DiPA was polymerized at 0 °C in the presence of LiCl. Decrease in molecular weight and broadening of molecular weight distribution were observed when polymerization was performed at a higher temperature of 20 °C, presumably because of the effect of ceiling temperature. In the case of DMPA, no polymer was formed at 0 °C and polymers with relatively broad molecular weight distributions (M_w/M_n = 1.2) were obtained at 20 °C. The polymerization rate of PiA was much faster than that of the other monomers, and poly(PiA) was obtained in high yield even at ?78 °C in 24 h. The microstructure of the resulting polymers were exclusively 1,4‐ for poly(DMPA), whereas 20–30% of the 1,2‐structure was contained in poly(DiPA) and poly(PiA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3714–3721, 2010     

Spatial resolution improvement of scanning microscopy based on thermal lens spectroscopy with a total-internal-reflection arrangement.

In scanning microscopy by total internal reflection with thermal lens spectroscopy, its spatial resolution depends on the distance between the sample and a converging lens, which corresponds to the objective lens in an ordinary optical microscope. It was found that the resolution was best when the signal induced by the thermal lens effect was maximum. The distance was precisely adjusted by monitoring the signal intensity, and the resolution became twice better than that previously reported. Using a shorter focal-length lens, a resolution of 1.9 microm was attained.     

Estimation of Stochastic Frontier Cost Function Using Data Envelopment Analysis: an Application to the AT&T Divestiture

This study develops a new use of data envelopment analysis for estimating a stochastic frontier cost function that is assumed to have two different error components: a one-sided disturbance (representing technical and allocative inefficiencies) and a two-sided disturbance (representing an observational error). The two error components are handled by data envelopment analysis in combination with goal programming/constrained regression. The approach proposed in this study can avoid several statistical assumptions used in conventional methods for estimating a stochastic frontier function. As an important application, this study uses the estimation technique to obtain an AT&T stochastic frontier cost function. As a result, this study measures technical and allocative efficiencies of AT&T production process and review its natural monopoly issue. The estimated stochastic frontier cost function is also compared with the other cost function models used for previous studies concerning the divestiture of the telephone industry.     

Concentration-dependence of faradaic currents and conductivity in a polystyrene sulfonic latex suspension

The conductivity, κ, in a suspension of polystyrene sulfonic latex without supporting electrolyte showed a linear dependence on the volume fraction, v_f, of the latex for v_f<0.03 with a finite intercept. In contrast, this deviated upward from the linear line for v_f>0.03. These variations were qualitatively consistent with the dependence of the voltammetric reduction current of H⁺ on v_f without supporting electrolyte. The current values were only a few percent of the theoretical diffusion-controlled current that could be observed in the suspension with supporting electrolyte. This fact indicates the electrostatic immobilization of the hydrogen ions by sulfonic latex particles. A plot of the current against κ at common values of v_f showed that the current for v_f>0.07 was smaller than the value predicted from the conductivity. This can be explained in terms of a combination of the increase in electrostatically unbounded H⁺ estimated by conductance measurements and electric migration in which the electrochemical depletion of [H⁺] also causes the depletion of the latex.     

High-temperature continuous counter-current gas-liquid chromatography

In continuous counter-current gas-liquid chromatography, which has a high resolving power and is suitable for the large-scale purification of organic solvents, it is very important that the samples that can be applied extend from easily separable to more difficult to separate, such as azeotropes, low-volatility compounds and stereoisomers. A system was designed and constructed for high-temperature operation up to 200°C, and was applied to the separation of dimethyl and diethyl phthalate, trans- and cis-decahydronaphthalene and cis-decahydronaphthalene and tetrahydronaphthalene. It was confirmed that over 99% of purity could be achieved for dimethyl and diethyl phthalate, trans-decahydronaphthalene, and tetrahydronaphthalene.     

In VivoLongitudinally Detected ESR Measurements at Microwave Regions of 300, 700, and 900 MHz in Rats Treated with a Nitroxide Radical

A signal detector of longitudinally detected ESR (LODESR) is independent of the resonant frequency. We developed anin vivoLODESR spectrometer operating in the regions of 300, 700, and 900 MHz. Using this apparatus, we estimated signal intensities at different operating frequencies obtained from non- or high-dielectric loss phantoms that contained nitroxide radical solutions and from live rats that had received a nitroxide radical. Our result, higher signal intensities in the high-dielectric loss samples (such as physiological saline solution and animals) at a lower frequency, shows that the influence of a decrease in dielectric loss dominates over the signal reduction caused by smaller Zeeman splitting. We believe that this finding strongly supports anin vivoESR resonant frequency that tends to be low.     

A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State

Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor.     

A Study of the Solvation Structure of l‐Leucine in Alcohol–Water Binary Solvents through Molecular Dynamics Simulations and FTIR and NMR Spectroscopy

The solvation structures of l ‐leucine (Leu) in aliphatic‐alcohol–water and fluorinated‐alcohol–water solvents are elucidated for various alcohol contents by using molecular dynamics (MD) simulations and IR, and ¹H and ¹³C NMR spectroscopy. The aliphatic alcohols included methanol, ethanol, and 2‐propanol, whereas the fluorinated alcohols were 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol. The MD results show that the hydrophobic alkyl moiety of Leu is surrounded by the alkyl or fluoroalkyl groups of the alcohol molecules. In particular, TFE and HFIP significantly solvate the alkyl group of Leu. IR spectra reveal that the Leu C?H stretching vibration blueshifts in fluorinated alcohol solutions with increasing alcohol content, whereas the vibration redshifts in aliphatic alcohol solutions. When the C?H stretching vibration blueshifts in the fluorinated alcohol solutions, the hydrogen and carbon atoms of the Leu alkyl group are magnetically shielded. Consequently, TFE and HFIP molecules may solvate the Leu alkyl group through the blue‐shifting hydrogen bonds.     

Polyaniline‐Induced CH Arylation of Arenes with Arenediazonium Salts

A reduced form of polyaniline has been shown to induce direct arylation of an arenediazonium salt with an arene (Gomberg–Bachmann reaction) to give the cross‐coupling product in moderate to good yields under mild conditions. Various arenediazonium salts and arenes, including heteroarenes such as furans, thiophenes, and pyrroles, are employed for the reaction. The most favorable combination of substrates is an electron‐poor arenediazonium salt with an electron‐rich heteroarene. Investigation of the mechanism by reactions with radical scavengers and experiments on kinetic isotope effects indicated the occurrence of a radical chain reaction initiated by one‐electron reduction of an arenediazonium salt by the polyaniline. Only 1 mol % (based on aniline tetramer) of the polyaniline is required for the cross‐coupling reaction to occur. This reaction proceeds under metal‐free conditions and with no need for photonic activation.