Directed Evolution of a Cp*RhIII-Linked Biohybrid Catalyst Based on a Screening Platform with Affinity Purification

Directed evolution of Cp*Rh^III-linked nitrobindin (NB), a biohybrid catalyst, was performed based on an in vitro screening approach. A key aspect of this effort was the establishment of a high-throughput screening (HTS) platform that involves an affinity purification step employing a starch-agarose resin for a maltose binding protein (MBP) tag. The HTS platform enables efficient preparation of the purified MBP-tagged biohybrid catalysts in a 96-well format and eliminates background influence of the host E. coli cells. Three rounds of directed evolution and screening of more than 4000 clones yielded a Cp*Rh^III-linked NB(T98H/L100K/K127E) variant with a 4.9-fold enhanced activity for the cycloaddition of acetophenone oximes with alkynes. It is confirmed that this HTS platform for directed evolution provides an efficient strategy for generating highly active biohybrid catalysts incorporating a synthetic metal cofactor.     

Development of gap sensing system for narrow gap laser welding

Narrow gap welding with an oscillation laser beam is one of the effective processes for thick plate welding. To put this welding process into practical manufacturing, a groove-sensing system using image processing for narrow gap welding with an oscillation laser beam is used. This developed system uses still images of the weld zone taken by a coaxial CMOS camera. It can recognize the position of the groove wall by analysing the brightness distribution in the still image. It can then control the oscillation width and the laser-irradiated area by calculating the groove width and the groove centre position. Some narrow gap welding experiments were performed to evaluate the performance of the developed system. The results revealed that the developed system is effective for narrow gap welding with an oscillation laser beam. Using this system, the narrow gap groove can be welded even if the groove width has changed during the welding process.     

Self‐consistent electrical parameter extraction from bias dependent spectral response measurements of III‐V multi‐junction solar cells

Spectral response of multi‐junction solar cell is complicated because of the interplay between external measurement conditions such as bias light intensity, monochromatic light intensity, bias voltage, and intrinsic electrical properties of series interconnected subcells. In this paper, we report an experimental study on the bias voltage‐dependent spectral response (SR) for multi‐junction solar cell. A self‐consistent iteration loop was developed from a nonlinear least square Powell hybrid algorithm that was used for curve fitting the experimental SR versus bias voltage data of each subcell. We demonstrated for the first time that this approach enabled us to derive the electrical parameters such as dark saturation currents (J₀), shunt resistance (R_sh), series resistance (R_s), and spectra response (J_photo) for each subcell of a Ga_0.99In_0.01As/Ge dual junction solar cell with stable convergence. The accuracies of the fitting results were confirmed by the agreement between the J–V curves calculated on the basis of these parameters and the experimental J–V curve of multi‐junction solar cell measured under AM1.5 and 1 sun condition. Copyright © 2013 John Wiley & Sons, Ltd.     

Transient current mapping obtained from silicon photodiodes using focused ion microbeams with several hundreds of MeV

Single Event Effects (SEEs) triggered by energetic heavy ions traversing a sensitive parts of electric devices have been studied using high-energy heavy ion microbeams connected with Transient Ion Beam Induced Current (TIBIC) measuring system at the Japan Atomic Energy Agency (JAEA) Takasaki Ion Accelerators for Advanced Radiation Applications (TIARA) facility. In the TIBIC system, SEE for semiconductor device, that is fast charge collection, has been observed in timescales of the order of picoseconds. In this paper, we show successful demonstration of the performance of the system, in which clear images of TIBIC map have been observed for Si pin photodiodes irradiated by 260 MeV ²⁰Ne⁷⁺ and also by 520 MeV ⁴⁰Ar¹⁴⁺ microbeams.     

Influence of a fiber-network microstructure of paper-structured catalyst on methanol reforming behavior

A novel microstructured catalyst that consists of Cu/ZnO catalyst powders and ceramic fibers was successfully prepared using pulp fibers as a tentative matrix by a papermaking technique. As-prepared material, called a paper-structured catalyst, possessed porous microstructure with layered ceramic fiber networks (average pore size ca. 20 μm, porosity ca. 50%). In the process of methanol autothermal reforming (ATR) to produce hydrogen, paper-structured catalysts demonstrated both high methanol conversion and low concentration of undesirable carbon monoxide as compared with catalyst powders and pellets. The catalytic performance of paper-structured catalysts depended on the use of pulp fibers, which were added in the paper-forming process and finally removed by thermal treatment before ATR performance tests. Confocal laser scanning microscopy and mercury intrusion analysis suggested that the tentative pulp fiber matrix played a significant role in regulating the fiber-network microstructure inside paper composites. Various metallic filters with different average pore sizes, used as supports for Cu/ZnO catalysts, were subjected to ATR performance tests for elucidating the pore effects. The tests indicated that the pore sizes of catalyst support had critical effects on the catalytic efficiency: the maximum hydrogen production was achieved by metallic filters with an average pore size of 20 μm. These results suggested that the paper-specific microstructures contributed to form a suitable catalytic reaction environment, possibly by promoting efficient diffusion of heat and reactants. The paper-structured catalyst with a regular pore microstructure is expected to be a promising catalytic material to provide both practical utility and high efficiency in the catalytic gas-reforming process.     

Decay of material properties of degraded MEA caused by repeated cold starts under subzero conditions in polymer electrolyte fuel cells

This study investigated the characteristics of cell performance degradation, decline of component performance, and changes in the properties of membrane electrode assembly materials caused by repeated cold starts under a subzero condition of ?30 °C. It was made clear that functional decay appeared mainly at the cathode due to increased proton conductive impedance and reduction of reactivity of the electrode catalyst. Among the cathode components, an increase in proton conductive impedance in the cathode electrolyte was dominant. Furthermore, the application of ion chromatography and a newly developed proton‐induced gamma‐ray emission method to measure fluorine in the off‐gas drain revealed that decomposition of the electrolyte was dominant in the cathode catalyst layer. A decrease in fluorine in the cathode electrolyte measured by fluorine‐19 nuclear magnetic resonance confirmed this decomposition. A hypothesis is also presented concerning the cause of the performance degradation. © 2012 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20394     

Preparation of Lanthanum Nickel Oxide-Coated Ni Sheet Anodes and Their Application to Electrolytic Production of (CF3)3N in (CH3)4NF·4.0HF Melt

A new process for electrolytic production of a perfluorinated compound, (CF₃)₃N, using lanthanum nickel oxide-coated Ni sheet anode in the (CH₃)₄NF·4.0HF melt at room temperature, was developed. Thin films of the lanthanum nickel oxides were prepared on Ni sheets by sol-gel coating method using polyvinlylpyrrolidone(PVP). The main components of the thin films were La₂O₃, LaNiO₃, and La₂NiO₄ at 500, 750 and 1000 °C, respectively. The anode performance in the (CH₃)₄NF·4.0HF melt depends greatly on the main component of the thin film, and the LaNiO₃-coated Ni sheet anode gives the best anode performance. The potential of LaNiO₃-coated Ni sheet anode remains constant at 5.9 V during electrolysis at 20 mA·cm⁻² in the (CH₃)4NF·4.0HF melt for 100 h. This is because LaNiO₃ and NiF₃, and/or Ni₂F₅, the latter of which was formed during electrolysis, in the film give a high electronic conductivity to the surface film during electrolysis. The maximum mole fraction of (CF₃)₃N (21.4%) was obtained at 20 mA·cm⁻² in (CH₃)₄NF·4.0HF melt using the LaNiO₃-coated Ni sheet.     

DRYING OF OPTICALLY SEMITRANSPARENT MATERIALS BY COMBINED RADIATIVE-CONVECTIVE HEATING

The objective of this work has been to basically elucidate the drying characteristics of an optically semitransparent material by combined radiative and convective heating. The experiments were conducted for a graphite suspension, a slurry of surplus activated sludge and a wet silica sand. The time-change of the drying rate as well as of the surface temperature of the brimfully wet material layer were measured under the step heating conditions using an infrared lamp bundle and a blast of hot air heated by an electric heater.

The experimental data obtained show satisfactory agreement with the calculated results from unsteady heat and mass transfer equations derived on the basis of a semitransparent drying model during the preheating and the constant drying rate periods.     

Soft Margins for AdaBoost

Recently ensemble methods like ADABOOST have been applied successfully in many problems, while seemingly defying the problems of overfitting.ADABOOST rarely overfits in the low noise regime, however, we show that it clearly does so for higher noise levels. Central to the understanding of this fact is the margin distribution. ADABOOST can be viewed as a constraint gradient descent in an error function with respect to the margin. We find that ADABOOST asymptotically achieves a hard margin distribution, i.e. the algorithm concentrates its resources on a few hard-to-learn patterns that are interestingly very similar to Support Vectors. A hard margin is clearly a sub-optimal strategy in the noisy case, and regularization, in our case a mistrust in the data, must be introduced in the algorithm to alleviate the distortions that single difficult patterns (e.g. outliers) can cause to the margin distribution. We propose several regularization methods and generalizations of the original ADABOOST algorithm to achieve a soft margin. In particular we suggest (1) regularized ADABOOST_REG where the gradient decent is done directly with respect to the soft margin and (2) regularized linear and quadratic programming (LP/QP-) ADABOOST, where the soft margin is attained by introducing slack variables.Extensive simulations demonstrate that the proposed regularized ADABOOST-type algorithms are useful and yield competitive results for noisy data.