Electron transfer reactions of glucose oxidase at Au111 electrodes modified with phenothiazine derivatives

The catalytic reaction of glucose oxidase (GOx) mediated by 3-(10-phenothiazyl)propionic acid (PT-PA) and phenothiazine-labeled poly(ethylene oxide) (PT-PEO1000) that are covalently bonded to Au(111) electrodes has been investigated. The PT-PA and PT-PEO1000 are reacted with 2-aminoethanethiol (AET), followed by the formation of a self-assembled monolayer (SAM) onto the Au surface. The PT group immobilized on the SAM of AET acts as an effective mediator for the electron transfer (ET) between the electrode and the FAD center of freely diffusing GOx in solution. The ET rate constant estimated from the catalytic current using a newly derived equation is larger by 1 order of magnitude for the PT-PA-modified system (1.1 x 10(5) dm(3) mol(-1) s(-1)) than for the PT-PEO1000 system (1.4 x 10(4) dm(3) mol(-1) s(-1)). The order of the magnitude of the ET rate constant clearly contrasts with the GOx hybrid systems that we previously investigated (Anal. Chem. 2003, 75, 910-917), in which the presence of the PEO spacer enhances the ET reaction rate. The reduction in the apparent PT concentration at the electrode interface due to the high mobility of the PEO chain, leading to low efficiency in the formation of an enzyme-mediator complex, is a possible reason for the lower mediation ability of PT-PEO1000 than that of PT-PA for the ET between the FAD group and PT(+) immobilized on the electrode. Inhibition of the penetration of GOx molecules into the monolayer and of the accessibility of some part of PT groups to GOx molecules could also be reasons for the lower mediation ability of PT-PEO1000 thickly modified on the electrode.     

New Class of High-TC Diluted Ferromagnetic Semiconductors Based on CaO without Transition Metal Elements

We propose new-type ferromagnetic semiconductors based on CaO and K₂S without any transition metal elements. These materials show transparent and half-metallic ferromagnetism if the deep-impurity-band width (W) induced by doping of C, N, Si, or Ge impurities, and the electron-correlation energy (U) satisfy the Stoners condition of highly correlated electron system (U>W). Based on our first-principles calculations, we demonstrate that these materials satisfy the Stoners condition, and could be new candidates for transparent and half-metallic DMSs.     

New Class of High-<Emphasis Type="Italic">T</Emphasis><Subscript>C</Subscript> Diluted Ferromagnetic Semiconductors Based on CaO without Transition Metal Elements

We propose new-type ferromagnetic semiconductors based on CaO and K₂S without any transition metal elements. These materials show transparent and half-metallic ferromagnetism if the deep-impurity-band width (W) induced by doping of C, N, Si, or Ge impurities, and the electron-correlation energy (U) satisfy the Stoner’s condition of highly correlated electron system (U>W). Based on our first-principles calculations, we demonstrate that these materials satisfy the Stoner’s condition, and could be new candidates for transparent and half-metallic DMSs.     

Direct imaging of molecular chains in a poly(p-xylylene) single crystal

Individual chains comprising a β-form poly(p-xylylene) (PPX) single crystal were resolved with a high resolution electron microscope (JEM-500). In a polymer crystal the important limiting factor for resolution is radiation damage. The total end point dose of a PPX crystal is about 0.5 coulomb cm^?2 for 500 kV electron irradiation which is more than 20 times greater than that for a polyethylene crystal. The high resolution image obtained was processed by optical filtering to reduce noise due to the granularity of film. The processed image, which corresponds to the ab-plane projection of polymer chains, shows clearly the mutual arrangement of each molecule in the crystal. This high resolution image is sufficient to provide a starting point for determining the unknown crystal structure of the β-modification of PPX.     

Heat capacity of metallic uranium and thorium from 80 to 1000 k

The heat capacities of metallic uranium and thorium from 80 to 1000 K have been determined by laser-flash calorimetry. The results on uranium agree very well with those in the literature over the temperature range investigated. The results on thorium are several percent lower than the heat-capacity values hitherto reported, while the enthalpy data at high temperatures in the literature are in good agreement with the present results. Shomate's analysis showed that the present results are the most consistent through the temperature range from 80 to 1000 K. On this, a revised table of thermodynamic functions of thorium from 80 to 1000 K is presented. The excess heat capacity on thorium has been found to be not appreciable up to 1000 K, in contrast with the large excess heat capacity above 300 K for uranium.     

Reduced‐order method for mathematical modeling of multiphase dc‐dc converter

A multiphase dc‐dc converter is effective for miniaturization and achieving high‐power density in a switching power supply. However, its mathematical modeling becomes complex as the phase number of the circuit increases. This study proposes a new modeling method to derive a reduced‐order method in a simple manner. The frequency characteristics of the reduced‐order model are fit to those of the original mathematical model of the multiphase dc‐dc converter. Therefore, the efficacy of the proposed method is validated.     

Facile Preparation of Nanosized MoP as Cocatalyst Coupled with TiO2 for Highly Efficient Photocatalytic H2 Production

Catalysis Letters - Presently, combining MoP as a co-catalyst and another subjective semiconductor into a composite catalyst often requires the use of various complex reduction methods. In this...     

Effect of CNTs on morphology and electromagnetic properties of non-firing CNTs/silica composite ceramics

Carbon composite ceramics have much attention for industry because of their excellent properties such as strong toughness, high electrical conductivity as well as low percolation threshold. Therefore, carbon nanotubes (CNTs) were used to incorporate with silica ceramics in order to improve their electromagnetic properties. The amount of CNTs in CNTs/silica composite ceramics was varied in order to investigate its effect on morphologies and electromagnetic properties of those. The composites were successfully fabricated by non-firing process. The results revealed that the obtained CNTs/silica composite ceramic have an electrical resistivity of 66.6?Ω·cm with a bending strength of 13.8?MPa. At the same time, the electromagnetic wave absorption ability achieved 70% over a wild frequency. This indicates that the CNTs in CNTs/silica composite ceramics may be potentially applied for an electromagnetic wave reflective material.     

Effect of silane modification on CNTs/silica composites fabricated by a non-firing process to enhance interfacial property and dispersibility

Carbon nanotube/ceramic composites have been in the spotlight thanks to their excellent properties. Sintering is the vital part of ceramics fabrication in terms of reliability, however sintering the carbon nanotube (CNT) based ceramic composites is a challenging task. In this study, interfacial bonding of silane functionalized CNT with silica ceramic is investigated by a non-firing sintering process. CNTs are first treated by a mixed acid with the aid of a silane 3-aminopropyl triethoxysilane (APTES), which improves the chemical bonding and dispersibility of CNT in ceramic bodies. The extent of APTES chemical functionalization and mechanical property of CNT/silica ceramic composites are characterized using Raman spectrometer, FT-IR analysis, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and three-point bending strength measurement. Results show that composites are successfully prepared without sintering with stable CNT-silica interface, superior dispersibility, and good mechanical properties.     

Manipulating the chemical affinity and kinetics of 3D silica particle network via the phase-separation technique

We developed a simple and versatile technique for a particle’s self-organizing-network based on a non-solvent induced micro-phase separation (NIPS). When a good solvent vaporizes from a particle dispersion in a ternary solution including the polymer, good solvent and non-solvent, the suspension is separated into the polymer network and non-solvent phase. If the affinity between the particles and polymer is sufficient enough, the particles are entrapped in the polymer network and particle network can be achieved. To expand this technique to particles with various physical properties, the surface of the particles was identified using the Hansen dispersibility parameter (HDP). From a comparison of the HDP of the unmodified and modified silica, an NH₂ group is suitable for entrapment of the silica by cellulose acetate as the polymer. However, with an increase in number of the silica particles, entrapment of the silica in the polymer was prevented. Control of the phase separation rate by the lowering temperature leaded to entrapment of silica particles in the polymer network. The proposed technique is effective not only for spherical oxide particles, but also for non-oxides, various shapes and structures. Depending on particle characteristics, functional films and bulk materials for thermal insulation, light diffusion, and electro conductivity can be obtained.