Effect of temperature on the stereoselectivity of phospholipase D toward glycerol in the transphosphatidylation of phosphatidylcholine to phosphatidylglycerol

In this study, the effect of temperature on the stereoselectivity of phospholipase D (PLD) toward the two primary hydroxyl groups of glycerol in the transphosphatidylation reaction of phosphatidylcholine to phosphatidylglycerol (PtdGro) was investigated. For this purpose, PLD from bacteria (Streptomyces septatus TH-2, S. halstedii subsp. scabies K6, and Actinomadura sp.) and cabbage were tested. At the reaction temperatures employed (0–60°C), the proportions of the two PtdGro diastereomers, namely, 1,2-dioleoyl-sn-glycero-3-phospho-3′-sn-glycerol (R,R configuration) and 1,2-dioleoyl-sn-glycero-3-phosphol-1′-sn-glycerol (R,S configuration), which were produced with PLD from Streptomyces TH-2 and Actinomadura sp., changed gradually from 50% R,R and 50% R,S at 50–60°C to 70% R,R and 30% R,S at O°C. These alterations suggested that the stereoselectivity of the bacterial PLD toward the two primary hydroxyl groups of prochiral glycerol was significantly influenced by reaction temperature. PLD from Streptomyces K6 showed relatively little effect of temperature on stereoselectivity, giving 65–69% R,R in the temperature range of 60–10°C examined. The plots of In ([R,R]/[R,S]) vs. 1/T gave good linear fits for these three bacterial PLD. No temperature effect was observed for cabbage PLD, which gave an almost equimolar mixture of the R,R and R,S diastereomers in the range from 0 to 40°C. The temperature-dependent change in enantiomeric selectivity of the bacterial PLD promises potentially profitable commercial exploitation.     

Generation of single-walled carbon nanotubes from alcohol and generation mechanism by molecular dynamics simulations

Recent advances in high-purity and high-yield catalytic chemical vapor deposition (CVD) generation of single-walled carbon nanotubes (SWNTs) from alcohol are comprehensively presented and discussed on the basis of results obtained from both experimental and numerical investigations. We have uniquely adopted alcohol as a carbon feedstock, and this has resulted in high-quality, low-temperature synthesis of SWNTs. This technique can produce SWNTs even at a very low temperature of 550 degrees C, which is about 300 degrees C lower than the conventional CVD methods in which methane or acetylene is typically used. We demonstrate the excellence of the proposed alcohol catalytic CVD method for high-yield production of SWNTs when Fe-Co on USY-zeolite powder was used as a catalyst. At optimum CVD conditions, a SWNT yield of more than 40 wt % was achieved over the weight of the catalytic powder within the reaction time of 120 min. In addition to the advantages for mass production, this method is also suitable for the direct synthesis of high-quality SWNTs on Si and quartz substrates when combined with the newly developed liquid-based "dip-coat" technique to mount catalytic metals on the surface of substrates. This method allows easy and costless loading of catalytic metals without the need for any support or underlayer materials that were usually required in previous studies for the generation of a sufficient quantity of SWNTs on an Si surface. Finally, the result of molecular dynamics simulation for the SWNT growth process is presented to obtain a fundamental insight into the initial growth mechanism on the catalytic particles.     

Observation of polarization property in near-field optical imaging by a polarization-maintaining fiber probe

We fabricated an original near-field scanning optical microscopy (NSOM) fiber probe made of polarization-maintaining and attenuation-reducing (PANDA)-type polarization-maintaining optical fiber, and observed the polarization property of propagation light in a polymer optical waveguide. The distribution of the transmission coefficient in polarization angles through this NSOM probe showed that the linear polarization is maintained in the two crossing directions: the fast and slow axes. The polarization degree parallel to the slow axis decreases from 1000:1 to 2:1 by bending the fiber probe and the decrease is independent of the bending direction. Using this PANDA-type NSOM probe, we investigated the polarization property of periodic intensity modulation. It was found that the intensity modulation was observed clearly with the electric vector parallel to the radius direction of the waveguide, but was observed vaguely with the electric vector perpendicular to the radius direction.     

Behaviour of the spin-spin relaxation time for natural rubber vulcanizates under large deformation

The spin-spin relaxation time, T₂, for DCP-cured natural rubber with various crosslink densities, v_e, has been measured under various deformation. T₂ is separated into two components: one is the long T₂ component, T_2L, for the mobility of amorphous network chains, the other is the short one, T_2S, for that of the strain-induced crystalline chains. T_2L decreased exponentially with increasing extension ratio,α, and the decreasing rate was more remarkable with increasing v_e. The α and v_e dependence of T_2L has been quantitatively explained by the equation experimentally derived by Nishi et al.T_2L under various extension increased and became almost constant with increasing temperature, while the corrected fraction of T_2S, T_2S (%), gradually decreased. The apparent melting point, T_m, at which the corrected T_2S (%) was zero under various deformation was determined. The α dependence of T_m, has been discussed by using Flory's equation.     

Novel gene assay by probe-regulated simultaneous separation using capillary electrophoresis (CE-PRESS)

A novel methodology, a probe-regulated simultaneous separation using capillary electrophoresis (CE-PRESS), was developed for simultaneous assay of multiple genes. The single-stranded (ss) DNA-polymer conjugate-probes were placed in a capillary, and then a mixture of target ssDNAs was injected. These ssDNAs were hybridized with corresponding complementary ssDNA-polymer conjugate-probes after charging the capillary. Two resulting double-stranded (ds) complexes of ssDNAs and ssDNA-polymer conjugate-probes were detected at different migration times. We found that the electrophoretic mobilities of two ssDNA-poly(acrylamide) conjugate-probes [-(5'-GCCACCAGC-3')m-AAm(n)- and -(5'-ACCTTCACT-3')p-AAm(q)-; AAm, acrylamide] obtained by copolymerizing 5'-methacryloyl-modified ssDNA and AAm were different, depending on their molar fraction of ssDNA, although the ssDNAs chain lengths were the same. Two ssDNAs (5'-GCTGGTGGC-3' and 5'-AGTGAAGGT-3') having the same chain length were successfully separated with our novel system, although the separation of these ssDNAs is impossible in conventional capillary electrophoresis systems.     

Characterization of polymer-adhesive interfaces on a nanometre scale by elemental mapping and image EELS using EFTEM

Energy-filtering transmission electron microscopy (EFTEM) was applied for investigating interfaces between a polymer and an adhesive. The sample employed in this work is polybutylene terephtharate (PBT) sheets laminated with an epoxy adhesive. It was found that heat aging of the PBT at 180 degrees C in air for > 9 h prior to adhesion decreases the adhesion strength drastically. To investigate this unfavourable aging effect on the adhesion strength, we performed elemental mapping and image EELS using EFTEM. A weak boundary layer with a thickness of < 50 nm was visualized at the PBT-adhesive interface by elemental mapping in the sample subjected to the heat aging and image EELS revealed the origin of this layer. Thus, we clearly correlated the nanoscale interfacial structure with the adhesion strength by EFTEM.     

Chemiluminescence detection for a microchip capillary electrophoresis system fabricated in poly(dimethylsiloxane)

Chemiluminescence (CL) detection integrated with a microchip capillary electrophoresis (MCE) system that was fabricated in poly(dimethylsiloxane) was demonstrated for chemical and biochemical analyses. Two model CL systems were involved here: metal ion-catalyzed luminol-peroxide reaction and dansyl species conjugated peroxalate-peroxide reaction. Different strategies based on three chip patterns (cross, cross combining with Y, and cross combining with V) to perform on-line CL detection for MCE were evaluated and compared in terms of sensitivity, reproducibility, and peak symmetry. The chip pattern of cross combining with Y proved to be promising for the luminol-peroxide CL system, while the chip pattern of cross combining with V was preferred for the peroxalate-peroxide system where CL reagent could not be effectively transported by electroosmotic flow. A detection limit down to submicromolar concentrations (midattomole) was achieved with good reproducibility and symmetric peak shape. Successful separation of three metal cations such as Cr(III), Co(II), and Cu(II) and chiral recognition of dansyl phenylalanine enantiomers within 1 min revealed distinct advantages of combining MCE with CL detection for rapid and sensitive analyses.     

Observations of vibration shape of AT-cut quartz resonator including electric twins

Quartz crystal resonators, including electric twins, are investigated. Electric twins are artificially formed in the usual AT-cut quartz crystal resonantor before the deposition of electrodes. We have directly observed that vibrations generated at electrodes propagate into the outside region isotropically, but cannot propagate into the region of electric twin.     

Magnetic Properties of Superconducting and Nonsuperconducting (Nd0.33Eu0.33Gd0.33)Ba2Cu3Oy

The temperature dependence of the DC susceptibility (T) is measured between 1.7 and 350 K on superconducting and nonsuperconducting bulk melt-processed (Nd_0.33Eu_0.33Gd_0.33)Ba₂Cu₃O_y by means of SQUID magnetometry. A strong superconducting contribution is found to coexist with a large paramagnetic moment provided by the Nd and Gd ions. The paramagnetic contributions measured on both types of samples follow a Curie–Weiss law; however, an antiferromagnetic ordering is not observed down to 1.7 K.