Temperature-dependent structural changes in hydrogen bonds in microcrystalline cellulose studied by infrared and near-infrared spectroscopy with perturbation-correlation moving-window two-dimensional correlation analysis

Temperature-dependent structural changes in hydrogen bonds (H-bonds) in microcrystalline cellulose (MCC) were investigated by infrared (IR) and near-infrared (NIR) spectroscopy. The O-H stretching fundamentals and their first overtone bands were employed to explore the structural changes. In order to analyze the overlapping OH bands due to various H-bonds, perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy was applied to the IR and NIR data. Typical spectral variation temperatures were visualized by the PCMW2D correlation analysis. Structural changes in the strong H-bonds in MCC gradually occur in the temperature region of 25-130 degrees C, and they become greater above 130 degrees C. Both OH groups with H-bonds of intermediate strength and very weak H-bonds arise from the structural change of strong H-bonds in the temperature region of 40-90 degrees C, whereas the appearance of the latter OH groups with very weak H-bonds gradually becomes dominant above 90 degrees C. It is revealed from the present study that the glass transition at 184 degrees C induces the changes in the H-bonds in the Ibeta and the O3-H3...O5 intrachain H-bonds. Band assignments for the O-H stretching first overtone vibration region are proposed based on the results of the PCMW2D correlation analyses.     

Establishment of long-term preservation for dimethyl sulfide by the solid-phase microextraction method

Dimethyl sulfide (DMS) derived from marine biological activity affects radiative forcing of the climate. The general analytical technique for DMS in seawater (purge and trap analytical method, P&T) is complex onboard ship. Thus it is difficult to obtain sufficient data for a comprehensive understanding of the spatiotemporal variability of DMS in the sea surface layer. On the other hand, a new analytical method for DMS using SPME (solid-phase microextraction) has recently been developed as an alternative method to P&T. This method is simpler than P&T because no special or complex apparatus is needed. If it is possible to preserve DMS for an extended period in excess of the duration of the cruise, the SPME method is a promising method for measuring DMS in seawater. We assessed an analytical method which can allow us to preserve DMS on the long-term scale using SPME. In liquid nitrogen (-196 degrees C), as preserved environment, for a period of 20 days after sampling, we found the preservation rate of DMS to be 94.7 +/- 4.4% (n = 6) in this study. Furthermore, estimating the distribution coefficient with respect to the effect of salinity on SPME, we found that DMS changed by 0.1 nM/% sal, suggesting that salinity has only a minor influence on oceanic DMS measurements in the open ocean because the minimal change of the open ocean salinity is within 2 %. Applying the SPME method to open ocean samples, we found that there were no significant differences in DMS between the unpreserved and preserved samples (r = 0.99, n = 26, SE = 0.01, p < 0.0001), showing the SPME method has potential for use for open ocean surveys.     

In situ Raman study on single- and double-walled carbon nanotubes as a function of lithium insertion

We investigated the electrochemical lithium ion (Li(+)) insertion/desertion behavior on highly pure and bundled single- and double-walled carbon nanotubes (SWNTs and DWNTs) using an in situ Raman technique. In general, two storage sites could host Li(+) in SWNT and DWNT bundles when varying an external potential: a) the outer surface sites, and b) the interstitial spaces within the bundles. The most sensitive changes in the tangential mode (TM) of the Raman spectra upon doping with Li(+) can be divided into two regions. The first region was found from 2.8 to 1.0 V (the coverage of Li(+) on the outer surface of a bundled nanotube) and was characterized by the loss of resonant conditions via partial charge transfer, where the G(+) line of the SWNT and the TM of the outer tube of DWNTs experienced a highly depressed intensity, but remained almost constant in frequency. The appearance of a Breit-Wigner-Fano (BWF) profile provided strong evidence of metallic inner tubes within DWNTs. The second region was observed when the applied potentials ranged from 0.9 to 0 V and was characterized by Li(+) diffusion into the interstitial sites of the bundled nanotube material. This phenomenon invoked a large downshift of the G(-) band in SWNTs, and a small downshift of the TM of the inner tube of DWNTs caused by expansion of the C--C bonds due to the charge transferred to the nanotubes, and the disappearance of the BWF profile through the screening effect of the interstitial Li(+) layers.     

Study of the differential theory of lamellar gratings made of highly conducting materials

Differential theory is said to be difficult to apply to surface-relief gratings made of metals with very high conductivity even though the formulation follows Li's Fourier factorization rules. Recently, Popov et al. [J. Opt. Soc. Am. 21, 199 (2004)] pointed out this difficulty and explained that its origin is related to the inversion of Toeplitz matrices constructed by the permittivity distribution inside the groove region. The current paper provides information about the differential theory for highly conducting gratings and considers the numerical instability problems. A stable calculation for lossless gratings is described, based on the extrapolation technique with the assumption of small losses.     

Estimation of heat generation rate in solid oxide fuel cell module from single cell performance and module performance based on impedance analysis

Heat generation rate in SOFC module was estimated under various thermal self-sustained conditions. SOFC module and system was designed to evaluate power generation property and temperature of module. Single cell was also evaluated the performance and electrode overpotential by impedance analysis under the similar condition to module power generation state. We estimated the heat generation rate with enthalpy calculation based on the actual module performance, and also with entropy calculation based on the impedance analysis of single cell. It was found that the heat generation rate calculated by enthalpy is approximately corresponded with that calculated by entropy. There still contains small error between heat generation rate calculated by enthalpy and that calculated by entropy. It was considered that these errors are originated from distribution in stack temperature and reforming gas temperature in the module. According to impedance analysis, it was found that the ohmic resistance is varied under operating condition and related with the current distribution which is calculated with the current path length in the cell. It was suggested that power generation state of module is affected by the current path length in the cell (in another word, distribution of power density) and distribution of overpotential; these phenomena is dominated by gas composition and thermal self-sustainable temperature.     

Synthesis and characterization of TiO2 powders by electrospray pyrolysis method

Electrospray pyrolysis, i.e. combination of electrospray and in-flight thermal treatment, has attracted much attention as a preparation method of functional ceramic particles. In this paper, we report the processing detail of spherical TiO₂ nano- and microparticles by the electrospray pyrolysis method as well as their photocatalytic activity for hydrogen evolution. Titanium(IV) bis(ammonium lactato)dihydroxide aqueous solutions (TALH aq., 0.2–20 wt%) were injected into a capillary nozzle by a syringe pump (0.15–0.59 mL/min), and were electrosprayed by using DC 4 kV voltage, followed by the pyrolysis at 300–500 °C. Spherical TiO₂ nano- and microparticles were successfully obtained. Effects of precursor-liquid concentration, liquid flow-rate, and pyrolysis temperature on the particle size, microstructure and functions were discussed.     

Single-molecule conductance of π-conjugated rotaxane: new method for measuring stipulated electric conductance of π-conjugated molecular wire using STM break junction

An electronic conductance with small fluctuations, which is stipulated in single-molecule junctions, is necessary for the precise control of single-molecule devices. However, the suppression of conductance fluctuations in conventional molecular junctions is intrinsically difficult because the fluctuations are related to the contact fluctuations and molecular motion. In the present study involving experimental and theoretical investigations, it is found that covering a single π-conjugated wire with an α-cyclodextrin molecule is a promising technique for suppressing conductance fluctuations. The conductance histogram of the covered molecular junction measured with the scanning tunneling microscope break-junction technique shows that the conductance peak for the covered junction is sharper than that of the uncovered junction. The covering technique thus has two prominent effects: the suppression of intramolecular motion, and the elimination of intermolecular interactions. Theoretical calculations of electronic conductance clearly support these experimental observations.     

A decentralized control scheme for orchestrating versatile arm movements in ophiuroid omnidirectional locomotion

Autonomous decentralized control is a key concept for understanding the mechanism underlying the adaptive and versatile behaviour of animals. Although the design methodology of decentralized control based on a dynamical system approach that can impart adaptability by using coupled oscillators has been proposed in previous studies, it cannot reproduce the versatility of animal behaviours comprehensively. Therefore, our objective is to understand behavioural versatility from the perspective of well-coordinated rhythmic and non-rhythmic movements. To this end, we focus on ophiuroids as a simple good model of living organisms that exhibit spontaneous role assignment of rhythmic and non-rhythmic arm movements, and we model such arm movements by using an active rotator model that can describe both oscillatory and excitatory properties. Simulation results show that the spontaneous role assignment of arm movements is successfully realized by using the proposed model, and the simulated locomotion is qualitatively equivalent to the locomotion of real ophiuroids. This fact can potentially facilitate a better understanding of the control mechanism responsible for the orchestration of versatile arm movements in ophiuroid omnidirectional locomotion.     

A numerical investigation of evaporation characteristics of a fuel droplet suspended from a thermocouple

Numerical simulations of combined natural convection–conduction in a droplet of n-dodecane suspended from a thermocouple were carried out, taking into consideration evaporation, and the effect of thermocouple diameter on the evaporation characteristics was investigated. The calculated temperature history of the droplet is in good agreement with experimental results; both show that the rate of heating decreases with increasing thermocouple diameter. The maximum error in temperature due to the thermocouple increases linearly with increasing thermocouple diameter. Thus, in investigations involving a droplet suspended from a thermocouple, it is preferable to use a thermocouple with the smallest possible diameter.