Well‐defined,environment‐friendly synthesis of polypeptides based on phosgene‐free transformation of amino acids into urethane derivatives and their applications

In this study, both naturally occurring and artificial amino acids were successfully transformed into the corresponding urethane derivatives using diphenyl carbonate. The urethanes thus prepared could be efficiently cyclized into amino acid N‐carboxyanhydrides (NCAs) without the requirement of phosgene. In addition, the presence of primary amines converted the urethane derivatives into NCAs and initiated the ring‐opening polymerization of the in situ formed NCAs, allowing for the well‐defined synthesis of polypeptides. These polypeptides contained initiating ends functionalized by an amine‐derived residue and propagating ends bearing the reactive amino group. By precise control of the structures of the polypeptides, various polypeptide conjugates such as block copolymers and graft copolymers were successfully synthesized as designed, and their applications in antifouling coatings against proteins, drug delivery systems and biosensors were demonstrated. © 2019 Society of Chemical Industry     

Estimation of anisotropic properties of nano-structured arrays by modal vibration control at microscale

Nano-structured arrays are engineered to meet the requirements of a variety of applications such as microfilters, sensors, and structural interface due to their unique mechanical characteristics, which cannot be achieved by conventional solid materials. However, it is hard to evaluate the elastic properties of nano-structured arrays owing to the discrete structure, sample size, and availability of suitable techniques. To facilitate this, we develop an advanced three-dimensional microscale vibration testing process. In the test, a specially designed three-dimensional microspecimen with tuned mass is excited by a piezoelectric actuator, and the resonance frequencies are detected by a laser device successfully. The anisotropic elastic moduli of nano-structured array composed of helical nano-springs are identified from a single spectrum. This array shows so strong characteristic anisotropy that the solid one hardly can attain. The microscale testing technique can be extended to other materials and microstructures.     

Application results of a prototype ultrasonic liquid film sensor to a 7 MPa steam–water two-phase flow experiment

A prototype ultrasonic liquid film sensor was applied to a high-temperature steam–water two-phase flow experiment. The liquid film sensor was vertically installed in a loop which was connected to HUSTLE, a multi-purpose steam source test facility. The hydraulic diameter of the measurement section was 9.4 mm. The output waveforms of the sensor were acquired with a digital oscilloscope. The fluid temperature and system pressure were kept at 288 °C and 7.2 MPa, respectively, during the experiment. The pulse-echo method was used to calculate the liquid film thickness. The cross-correlation calculation was utilized to determine the time difference between the pulse reflected at the sensor surface and the pulse reflected at the liquid film surface. The time-averaged liquid film thicknesses were less than 0.055 mm in the annular flow condition. The increase of the time-averaged thickness was small with the change of the gas momentum flux. The film thicknesses measured with the sensor were compared with the past experimental results; the former were smaller than one-fourth of the thickness estimated as the mean film thickness. The comparison results suggested that the continuous liquid sublayer thickness was measured with the liquid film sensor.     

Thermodynamic Properties of Ionic Semiclathrate Hydrate Formed with Tetrabutylammonium Propionate

The phase equilibrium temperature and dissociation heat of tetrabutylammonium propionate (TBAPr) hydrate are reported. TBAPr hydrate is a type of ionic semiclathrate hydrates and also could potentially be used as thermal energy storage material. The temperature‐composition phase diagram of the TBAPr hydrate was determined in a defined range of mass fractions. Considering the dissociation heat of differential scanning calorimetry (DSC) measurements, multiple peaks of heat flow were observed in the TBAPr‐water system at the TBAPr mass fraction lower than 0.35, and there was a single peak at the mass fraction higher than 0.37.     

A Method for Reducing the Dead‐Time Voltage and Impedance Voltage in a Series Voltage Compensator

Many research groups are developing series voltage compensators. In a series converter, since a transformer is used in series in the power system, the power system current flows into the voltage source inverter through the transformer. The inverter current, which is determined by the transformation ratio, gives rise to an error voltage that consists of a dead‐time voltage and an impedance voltage. The error voltage is generated even when the reference voltage is zero. This paper describes the mechanism by which the error voltage occurs and proposes a method for reducing the error voltage. © 2013 Wiley Periodicals, Inc. Electr Eng Jpn, 186(3): 85–93, 2014; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.22333     

Density-Functional Theoretical Study on the Role of Lewis and Brønsted Acid Sites on CeO2(110) Surfaces for Nitrile Hydration

Hydration of cyanopyridine on CeO₂(110) surfaces was studied using periodic DFT+U calculations. One of two adsorption modes of 2-cyanopyridine occurs with two-point interaction which causes substrate specificity. A catalytic cycle for the hydration of 2-cyanopyridine was proposed. Cooperativity of Lewis and Brønsted acid sites was found to stabilize the intermediates for the hydration.     

Effect of annealing on photovoltaic properties and microstructure of conventional and inverted organic solar cells using active bilayer based on liquid‐crystal semiconducting polymer and fullerene

Conventional and inverted organic solar cells of poly[9,9‐dioctyl‐fluorene‐co‐bithiophene] (F8T2) as liquid‐crystal semiconducting polymer and fullerene as electron acceptor were fabricated and characterized. An effect of thermal treatment of the films on annealing condition near glass transition was investigated for tuning optimization and improving the photovoltaic and optical properties. Annealing treatment below the glass transition improved the photovoltaic performance and carrier diffusion in crystal growth of active layer. The X‐ray diffraction patterns indicate a crystalline structure with molecular order of F8T2 in crystal index, 100 as a layer distance between sheets of F8T2 chains. The photovoltaic properties were based on molecular interactions with molecular ordering in active layer at crystal state. As the photovoltaic mechanisms, the F8T2 thin film as p‐type semiconducting polymer worked for electron‐donor layer to support light‐induced generation, carrier diffusion and charge transfer near interface in active layer. Copyright © 2014 John Wiley & Sons, Ltd.     

Epitaxial p-type SiC as a self-driven photocathode for water splitting

Solar-to-hydrogen conversion efficiencies of water-splitting photochathodes using epitaxially grown p-type 4H-, 6H- and 3C-SiC were estimated in a two-electrode system without applying any external bias. By using electrode materials with small oxygen overpotentials as counter electrodes, the photocurrent became comparable to that observed in a three-electrode system with a suitable bias. Estimated efficiencies seem to depend on the bandgap of the SiC polytypes. For the 3C-SiC, the obtained efficiency was 0.38%, which is so far the highest value reported for SiC. We confirmed that the hydrogen volumes estimated from the photocurrent were almost the same as actual volumes observed by gas chromatography.     

Impact of Dynamic Interlayer Interactions on Thermal Conductivity of Ca3Co4O9

The phonon thermal conductivity of misfit-layered Ca₃Co₄O₉ has been calculated by perturbed molecular dynamics using a classical force field. Detailed numerical analyses reveal that, in spite of its smaller cross-sectional area, the CoO₂ layer transports more heat than the thicker rock salt (RS) layer, although its local thermal conduction is more suppressed than in another layered cobaltite, Na _x CoO₂. The origins of these differences have been elucidated through careful examination of the atomic arrangements in each layer. Since thermal conduction in the RS layer can be reduced without deteriorating electronic properties for which the CoO₂ layer is responsible, it is suggested that the RS layer should be modified to further suppress the overall in-plane thermal conductivity. Computational experiments with increasing number of Ca–O planes in the RS layer showed the opposite trend to what can be predicted based on the misfit between two dissimilar layers. Further analyses to reveal the origin of these unexpected results provide yet another strategy to further decrease the thermal conductivity, namely to control the dynamic interference between atoms across the interface between two layers.     

Magnetovolume effects in manganese nitrides with antiperovskite structure

Magnetostructural correlations in antiperovskite manganese nitrides were investigated systematically for stoichiometric and solid solution Mn₃Cu_1?xA_xN (A = Co, Ni, Zn, Ga, Ge, Rh, Pd, Ag, In, Sn or Sb). This class of nitrides is attracting great attention because of their giant negative thermal expansion, which is achieved by doping Ge or Sn into the A site as a relaxant of the sharp volume contraction on heating (spontaneous volume magnetostriction ω_s) because of the magnetovolume effects. The physical background of large ω_s and mechanism of how the volume contraction becomes gradual with temperature are central concerns for the physics and applications of these nitrides. An entire dataset of thermal expansion, crystal structure and magnetization demonstrates that the cubic triangular antiferromagnetic state is crucial for large ω_s. The intimate relationship between ω_s and the magnetic structure is discussed in terms of geometrical frustration related to the Mn₆N octahedron and magnetic stress concept. The results presented herein also show that ω_s depends on the number of d electrons in the A atom, suggesting the important role of the d orbitals of the A atom. Not all the dopants in the A site, but the elements that disturb the cubic triangular antiferromagnetic state, are effective in broadening the volume change. This fact suggests that instability neighboring the phase boundary is related to the broadening. The relation between the gradual volume change and the local structure anomaly is suggested by recent microprobe studies.