In situ monitoring of the H concentration change near an electrode surface through electrolysis using slab optical waveguide pH sensor

The H⁺ concentration change was monitored near an electrode surface through an electrolysis using a slab optical waveguide technique. Indium tin oxide transparent electrode modified by porous insulating polymer to which methyl red was covalently immobilized was used as a guiding layer, and the absorbance change of the polymer film was monitored. H⁺ generation at the vicinity of the electrode through the oxidation of ascorbic acid could be monitored by this technique.     

Test compounds for detecting the silanol effect on the elution of ionized amines in reversed‐phase LC

The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC.     

Noncovalent Modification of Cycloparaphenylene by Catenane Formation Using an Active Metal Template Strategy**

The active metal template (AMT) strategy is a powerful tool for the formation of mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes, allowing the synthesis of a variety of MIMs, including π-conjugated and multicomponent macrocycles. Cycloparaphenylene (CPP) is an emerging molecule characterized by its cyclic π-conjugated structure and unique properties. Therefore, diverse modifications of CPPs are necessary for its wide application. However, most CPP modifications require early stage functionalization and the direct modification of CPPs is very limited. Herein, we report the synthesis of a catenane consisting of [9]CPP and a 2,2′-bipyridine macrocycle as a new CPP analogue that contains a reliable synthetic scaffold enabling diverse and concise post-modification. Following the AMT strategy, the [9]CPP-bipyridine catenane was successfully synthesized through Ni-mediated aryl-aryl coupling. Catalytic C−H borylation/cross-coupling and metal complexation of the bipyridine macrocycle moiety, an effective post-functionalization method, were also demonstrated with the [9]CPP-bipyridine catenane. Single-crystal X-ray structural analysis revealed that the [9]CPP-bipyridine catenane forms a tridentated complex with an Ag ion inside the CPP ring. This interaction significantly enhances the phosphorescence lifetime through improved intermolecular interactions.     

Observation of nonlinear coupling between small-poloidal wave-number potential fluctuations and turbulent potential fluctuations in Ohmically heated plasmas in the JFT-2M tokamak

Two types of electrostatic modes with small-poloidal wave numbers (approximately 1 and 10-15 kHz) are observed in the edge region of Ohmically heated plasmas in the JFT-2M tokamak. The envelope of the higher frequency coherent mode is modulated at the frequency of the lower frequency mode. A bispectral analysis revealed that a significant nonlinear coupling among the two types of fluctuations and the broadband background turbulent potential fluctuations occurs inside the last closed magnetic flux surface, suggesting that a nonlinear process such as the parametric-modulational instability is involved.     

Redox reaction in two-dimensional porous coordination polymers based on ferrocenedicarboxylates

A series of 1,1'-ferrocenedicarboxylate-based two-dimensional porous coordination polymers were synthesized by incorporating different diamine co-ligands. These compounds immobilized on electrodes, exhibited reversible redox reactions, arising from ferrocenyl moiety.     

GdAlO3 perovskite

Flux‐grown gadolinium aluminate perovskite, GdAlO₃, was examined using single‐crystal 0.7 Å‐wavelength synchrotron X‐ray diffraction. In the context of other well categorized rare earth aluminate (RAlO₃) perovskite phases, the orthorhombic Pnma symmetry determined for the current compound is unsurprising. Corner‐linked AlO₆ octahedra form the structural backbone of RAlO₃ perovskites and distort to accommodate the various rare earth ions in the structural voids. For GdAlO₃, the octahedral distortion, characterized by tilting of the octahedra about the shortest R—Al—R vectors, and octahedral deformation, characterized by strain of the octahedra along those axes, are in accordance with trends in the RAlO₃ series.     

Optical properties of molecular aggregates of oxazine dyes in dispersions of clay minerals

The molecular aggregation of oxazine 1 (Ox1) and oxazine 4 (Ox4) in reduced charge montmorillonite (RCM) colloids was investigated by absorption and fluorescence spectroscopies. The aggregation was significantly influenced by the structure of dye cations. Presence of four hydrophobic ethyl groups attached to the ammonium substituents in Ox1 cation prevented formation of closely packed sandwich-type assemblies (H-aggregates). Significant effect of the layer charge was observed for Ox4/RCMs dispersions. Large amounts of the Ox4 H-aggregates were formed in the systems with RCMs of the highest layer charge and reflected in quenched fluorescence. The presence of J-aggregates was proven by absorption spectra for the systems with Ox4 and low-charge RCMs. The flocculation of the lowest charge RCM colloids led to an extensive reduction of the luminescence. The trends and effects of the dye molecular structure and RCM properties are compared with the results previously published for other types of dyes.     

Analysis of Cu segregation to oxide–metal interface of Ni‐based alloy in a metal‐dusting environment

Hard X‐ray photoelectron spectroscopy (HX‐PES) has been realized using high‐brilliance synchrotron radiation. High‐energy photon excitation enables us to probe photoelectrons with larger escape depth compared to conventional PES. This allows us to conduct, without destruction, a study of the embedded interface of materials as the oxide‐ metal interface. We apply HX‐PES to investigate for Cu segregation in the oxide–metal interface during metal‐dusting corrosion. The effective concentration of Cu in the segregation was estimated a few times higher than the bulk concentration. These results on the interface layer can explain the variation in the corrosion resistance. Copyright © 2008 John Wiley & Sons, Ltd.