Protein-Protein Recognition Involved in the Intermodular Transacylation Reaction in Modular Polyketide Synthase in the Biosynthesis of Vicenistatin

The ketosynthase (KS) domain is a core domain found in modular polyketide synthases (PKSs). To maintain the polyketide biosynthetic fidelity, the KS domain must only accept an acyl group from the acyl carrier protein (ACP) domain of the immediate upstream module even when they are separated into different polypeptides. Although it was reported that both the docking domain-based interactions and KS-ACP compatibility are important for the interpolypeptide transacylation reaction in 6-deoxyerythronolide B synthase, it is not clear whether these findings are broadly applied to other modular PKSs. Herein, we describe the importance of protein-protein recognition in the intermodular transacylation between VinP1 module 3 and VinP2 module 4 in vicenistatin biosynthesis. We compared the transacylation activity and crosslinking efficiency of VinP2 KS₄ against the cognate VinP1 ACP₃ with the noncognate one. As a result, it appeared that VinP2 KS₄ distinguishes the cognate ACP₃ from other ACPs.     

Biomolecule-recognition gating membrane using biomolecular cross-linking and polymer phase transition

We present for the first time a biomolecule-recognition gating system that responds to small signals of biomolecules by the cooperation of biorecognition cross-linking and polymer phase transition in nanosized pores. The biomolecule-recognition gating membrane immobilizes the stimuli-responsive polymer, including the biomolecule-recognition receptor, onto the pore surface of a porous membrane. The pore state (open/closed) of this gating membrane depends on the formation of specific biorecognition cross-linking in the pores: a specific biomolecule having multibinding sites can be recognized by several receptors and acts as the cross-linker of the grafted polymer, whereas a nonspecific molecule cannot. The pore state can be distinguished by a volume phase transition of the grafted polymer. In the present study, the principle of the proposed system is demonstrated using poly(N-isopropylacrylamide) as the stimuli-responsive polymer and avidin-biotin as a multibindable biomolecule-specific receptor. As a result of the selective response to the specific biomolecule, a clear permeability change of an order of magnitude was achieved. The principle is versatile and can be applied to many combinations of multibindable analyte-specific receptors, including antibody-antigen and lectin-sugar analogues. The new gating system can find wide application in the bioanalytical field and aid the design of novel biodevices.     

Low methanol crossover and high performance of DMFCs achieved with a pore-filling polymer electrolyte membrane

We compared the performance of the membrane electrode assembly for direct methanol fuel cells (DMFCs) composed of a pore-filling polymer electrolyte membrane (PF membrane) with that composed of a commercial Nafion-117 membrane. In DMFC tests, the methanol crossover flux was 23% lower in the PF membrane than in the Nafion-117 membrane even though the thickness of the PF membrane was 43% that of Nafion-117. This led to a higher DMFC performance and the lower overpotential of the cathode of the PF membrane. Feeding an aqueous 10 M methanol solution at 50 °C produced a low cathode overpotential, as low as 0.40 V at 0.2 A in the PF membrane, whereas the potential was 0.65 V at 0.2 A in the Nafion-117 membrane. In contrast, the ohmic loss and anode overpotential were almost the same in the two membranes. We confirmed that a reduction in methanol crossover using the PF membrane results in lower cathode overpotential and higher DMFC performance. In addition, the electro-osmotic coefficient was estimated as 1.3 in the PF membrane and 2.6 in Nafion-117, based on a water mass-balance model and values showing that the PF membrane prevents the flooding of the cathode at a low gas flow rate using. A highly concentrated methanol solution can be applied as a fuel without decreasing DMFC performance using PF membranes.     

Development of a Peristaltic Crawling Robot Using Planar Link Mechanisms

The field of bio‐mechanisms, which develops new machines that use motion and control of organisms as a model, is attracting attention. We examined the peristaltic crawling of an earthworm as a transport function in place of wheels or ambulation, and have developed a robot running inside a tube. In this robot, a joint corresponding to the earthworm's segment is driven by a DC motor. This paper presents the experimental result of the peristaltic crawling of an actual earthworm and the evaluation result of the transport mechanism of a prototype robot. Copyright © 2007 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Synthesis of Substituted 2,2′‐Bipyridines and 2,2′:6′,2′′‐Terpyridines by Cobalt‐Catalyzed Cycloaddition Reactions of Nitriles and α,ω‐Diynes with Exclusive Regioselectivity

A variety of substituted 2,2′‐bipyridines were synthesized by a 1,2‐bis(diphenylphosphino)ethane (dppe)/cobalt chloride hexahydrate (CoCl₂⋅6 H₂O)/zinc‐catalyzed [2+2+2] cycloaddition reaction of diynes and nitriles, with all reactions exhibiting exclusive regioselectivity. Thus, symmetrical and unsymmetrical 1,6‐diynes and 2‐cyanopyridine reacted in the presence of 5 mol % of dppe, 5 mol % of CoCl₂⋅6 H₂O and 10 mol % of zinc powder to provide the corresponding 2,2′‐bipyridines. Under identical reaction conditions, 1‐(2‐pyridyl)‐1,6‐diynes and nitriles reacted smoothly with exclusive regioselectivity to produce 2,2′‐bipyridines in good yield. 2,2′‐Bipyridines were also obtained by the double [2+2+2] cycloaddition reaction of 1,6,8,13‐tetraynes with nitriles. Similarly, 2,2′:6′,2′′‐terpyridines were synthesized from 1‐(2‐pyridyl)‐1,6‐diyne and 2‐cyanopyridine. The regiochemistry observed can be explained by considering the electronic nature of cobaltacyclopentadiene intermediates and nitriles. A survey of the exclusive regiochemical trend gives reasonable credence to the synthetic potential of the present method.     

Electrochromic Solid-State Devices Using Organic-Metallic Hybrid Polymers

Organic-metallic hybrid polymers are formed by the complexation of metal ions with organic modules bearing two coordination sites. The hybrid polymers consisting of bis-terpyridines and metal ions such as Fe(II) or Ru(II) have a specific color based on the metal-to-ligand charge transfer (MLCT) absorption. Cyclic voltammograms of the polymers exhibit a reversible redox wave according to the redox reaction of the metal ions. Interestingly, a polymer film cast on an indium tin oxide (ITO) electrode exhibits excellent electrochromic properties; the color of the film disappears when a higher potential as compares to the redox potential of the metal ions is applied to the polymer film. In addition, multicolor electrochromic changes appear on introducing two types of metal ions to the polymer. Electrochromic solid-state devices are successfully fabricated by using these polymers. This paper is dedicated to Professor Takakazu Yamamoto in honor of his pioneering research efforts and accomplishments in the fields of organometallics and π-conjugated polymers.     

Development of event-specific quantitation method for GA21 maize, which is a gm event without CaMV35S promoter

A real-time PCR detection method was developed for event-specific quantitation of Roundup Ready maize, GA21. The developed PCR method was designed to amplify an artificial junction site between the native maize genome DNA and the recombinant DNA of GA21 maize, which provides only one target sequence per haploid of GA21 genome. Thus, the amplification efficiency of the event-specific target for GA21 became closely similar to the amplification of SSIIb, and the conversion factor (Cf) for the quantitation method was similar to the theoretical value. The developed method demonstrated better performance than the existing construct-specific method that has been used as a Japanese official method. The developed method can easily be combined with the real-time PCR targeting of the CaMV35S promoter, and the multiplexed method should be an effective screening method for GM maize.     

Proposal of a high‐performance solid oxide fuel cell combined power generation system with carbon dioxide recovery

A new fossil‐fuel‐utilized high‐performance combined power generation system with liquefaction recovery of carbon dioxide is proposed. In the system, pure oxygen is used as the oxidant gas to prevent the mixture of nitrogen in the exhaust gas and to make the liquefaction recovery of carbon dioxide possible. Solid oxide fuel cell is selected as the topping cycle. The exhaust fuel gas of the solid oxide fuel cell is afterburned with its exhaust oxidant gas of pure oxygen and the heat of the combustion gas is utilized in the bottoming cycle. Nonequilibrium MHD/noble gas turbine cycle is selected as the bottoming cycle because the temperature of the combustion gas reaches about 2300 K. It is made clear through detailed examination of energy balance that the total thermal efficiency of the system using natural gas (methane) as the fuel reaches 63.24% (HHV) or 70.18% (LHV). This efficiency is very high as for the system with carbon dioxide recovery. The proposed system, therefore, has excellent performance, and further research and development is warranted. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 143(4): 12–21, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10146     

Thermal decomposition of uranium peroxide hydrates

The thermal decomposition of uranium peroxide hydrates, UO₄·4H₂O and UO₄·2H₂O, has been investigated by thermal analyses, X-ray diffraction study and infrared spectroscopy. As a result, it is concluded that the thermal decomposition of uranium peroxide hydrates proceeds in the following sequence:     

On the asymptotic distribution of the least-squares estimators in unidentifiable models

In order to analyze the stochastic property of multilayered perceptrons or other learning machines, we deal with simpler models and derive the asymptotic distribution of the least-squares estimators of their parameters. In the case where a model is unidentified, we show different results from traditional linear models: the well-known property of asymptotic normality never holds for the estimates of redundant parameters.