Preparation and Photophysical and Photoelectrochemical Properties of a Covalently Fixed Porphyrin–Chemically Converted Graphene Composite

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl‐functionalized CCG and porphyrin boronic ester. The covalently linked CCG–porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady‐state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin‐linked CCG revealed a short‐lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO₂ electrode coated with the porphyrin‐linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π‐conjugated systems in the excited and ground states.     

Effects of dihydronaphthyl-based [60]fullerene bisadduct regioisomers on polymer solar cell performance

The effects of fullerene bisadduct regioisomers on solar cell performance have been examined for the first time and the two substituent positions on C(60) have been found to have a large impact on the solar cell performance.     

Formation of "fuzzy" phases with high proton conductivities in the composites of polyphosphoric acid and metal oxide nanoparticles

A high proton-conducting phase appears in the composites of zirconium- and titanium-oxide nanoparticles and polyphosphoric acid (HPO(3)). Metal oxide nanoparticles (ZrO(2) and TiO(2)) react with HPO(3) and form composite electrolytes containing pyrophosphates (ZrP(2)O(7) or TiP(2)O(7)) and shortened HPO(3) chains. The ZrO(2)-HPO(3) composite exhibits eleven times higher conductivity than sole HPO(3) at the maximum. A formed layer of shortened HPO(3) chains surrounding the pyrophosphates enhances the proton conductivities of the composite electrolytes and reduces the activation energies for the proton conductivities from 50 to 30 kJ mol(-1).     

Magnetic resonance elastography using an air ball-actuator

The purpose of this study was to develop a new technique for a powerful compact MR elastography (MRE) actuator based on a pneumatic ball-vibrator. This is a compact actuator that generates powerful centrifugal force vibrations via high speed revolutions of an internal ball using compressed air. This equipment is easy to handle due to its simple principles and structure. Vibration frequency and centrifugal force are freely adjustable via air pressure changes (air flow volume), and replacement of the internal ball. In order to achieve MRI compatibility, all parts were constructed from non-ferromagnetic materials. Vibration amplitudes (displacements) were measured optically by a laser displacement sensor. From a bench test of displacement, even though the vibration frequency increased, the amount of displacement did not decrease. An essential step in MRE is the generation of mechanical waves within tissue via an actuator, and MRE sequences are synchronized to several phase offsets of vibration. In this system, the phase offset was detected by a four-channel optical-fiber sensor, and it was used as an MRI trigger signal. In an agarose gel phantom experiment, this actuator was used to make an MR elastogram. This study shows that the use of a ball actuator for MRE is feasible.     

SVG+Ajax+R: a new framework for WebGIS

This paper first proposes a method of establishing a Web-based system that can visualize statistical data that are accompanied by geographical information and analyze it interactively using dynamic graphics. In terms of the graphics format, our proposed system uses XML-based 2D vector graphics, known as Scalable Vector Graphics (SVG). To install an enhanced interactive function, we adopted a technique of server–client asynchronous communication using JavaScript, called Asynchronous JavaScript and XML (Ajax) and R, which perform statistical analysis on the server side. This enables Web developers to construct a lightweight system including statistical computing rapidly. Furthermore, many users get possible to utilize such data effectively and efficiently anywhere anytime. The latter half of this paper introduces the WebGIS realized by this framework. We then discuss the possibility and advantages of applying this new method to the dynamic graphics proposed previously.     

Radical copolymerization of cyclic diarsine with vinyl monomers

1,2,4,5‐Tetramethyltetrahydrodiarsenine ( 1 ), a cyclic diarsine compound, was stirred with styrene and a catalytic amount of 2,2′‐azobisisobutyronitrile (AIBN) as a radical initiator at 80 °C for 8 h in toluene to give a copolymer containing arsenic atoms in the backbone. The gel permeation chromatography (GPC) chromatogram of the copolymer showed a single peak. The number‐average molecular weight of the copolymer was estimated to be more than 10,000 by GPC analysis (CHCl₃, polystyrene standards). The structure of the copolymer was confirmed by the ¹H NMR and ¹³C NMR spectra. According to the integral ratio of peaks in the ¹H‐NMR spectrum, the content of 1 in the copolymer was smaller compared to the monomer feed ratio of 1 . Radical copolymerization of 1 with methyl methacrylate also provided the corresponding copolymer in the presence of AIBN, whereas copolymerization with vinyl acetate yielded no polymeric material. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3023–3028, 2004     

Determination of some physical constants of cyclodextrin complexes by electrochemical methods

The characterization of cyclodextrin(CD) systems by electrochemical methods, mainly by cyclic voltammetry, is discussed. The addition of CD to the electrolyte solution causes a decrease in the peak current and also a shift in the apparent half-wave potential in cyclic voltammetry. Quantitative analysis in the both phenomena affords the formation constants of CD complexes. The formation or dissociation rate constants can be evaluated from the cyclic voltammetric data at high scan rates. Adsorption of CD on the electrode surface is also mentioned.     

Preparation and Characterization of Titania Thin Films from Aqueous Solutions

Dip- or spin-coating and characterization of titania (TiO₂) thin films from various aqueous solutions have been studied. The aqueous titanium solutions mainly used in this study were halogen- and chelate-free solutions with the concentrations up to 1.4 M derived from titanium isopropoxide (TIP) with tetramethylammonium hydroxide (TMAOH) or some alkylamines, while aqueous and alcoholic solutions containing titanium atoms stabilized chelating ligands were examined for comparison. The TiO₂ films prepared from the TIP-TMAOH solution were already crystallized at 350°C to anatase form and those formed at 600°C had high transparency and refractive indices of 2.40. No carbon residue in the film prepared at 400°C was detected by XPS. The pure anatase form was sustained up to 850°C. Interestingly, it was found that the (004) preferentially oriented anatase films were obtained from TIP-lactic acid (LA) system until 700°C. The solutions containing citric acid (CA) or alkanolamines yielded anatase and rutile form fired at the temperatures equal to or higher than 600°C. Carbon residue was detected in the film fired at 400°C. The film thickness monotonically decreased from the upper to the bottom ends of the substrate. However, it was found that the thickness uniformity was drastically improved by an addition of sucrose to the aqueous solutions. The effects of the solution composition and polyhydroxy compounds on the crystal modifications of formed films and the film uniformity are discussed.