Observation of the solid-state formation of a TTF–CA complex by terahertz spectroscopy

The solid-state synthesis of a tetrathiafulvalene–chloranil (TTF–CA) complex was demonstrated, and progress in the formation of the complex was monitored using a GaP Raman terahertz (THz) spectrometer. Clear transitions in the THz absorption spectra indicated that the mixture of TTF and CA became the black phase TTF–CA complex. The results of X-ray diffraction, Raman scattering, and FTIR spectra are presented as supporting evidence.     

Geometric control and tuneable pore size distribution of buckypaper and buckydiscs

The fabrication of buckypaper from unfunctionalised multi-walled carbon nanotubes (MWCNTs) without the aid of surfactants or surface modification techniques is accomplished through a novel and quick frit compression method. The dimensions can be controlled through the size of the syringe housing and the through the mass of carbon nanotubes added. Their thicknesses are typically much larger than surfactant-cast buckypaper and range from 120 μm up to 650 μm; buckypaper with thicknesses larger than 500 μm we call buckydiscs. Buckypaper and buckydiscs are mechanically robust to handle, flexible, stable in solvents and possess larger porosities than Triton-X100 cast buckypaper. They also exhibit a memory effect when bending wetted samples, returning to their former geometry on drying. Buckypaper and buckydiscs were studied by mercury intrusion porosimetry to reveal a defined distribution of mesopores and small macropores that is, along with their density and apparent free volume, dependant on the casting solvent and therefore tuneable. Moreover, the frit compression system also allows control over the 3-dimensional geometry of the buckydiscs during the casting process.     

Study on dominant mechanism of high-cycle fatigue life in 6061-T6 aluminum alloy through microanalyses of microstructurally small cracks

The mechanism controlling the fatigue life of a precipitation-hardened Al–Mg–Si alloy (6061-T6) at a high-cycle fatigue (HCF) regime of over 10⁷ cycles was investigated in detail. It was found that over 90% of the total fatigue life was occupied by the growth process of a microstructurally small crack at relatively low stress amplitude. The small crack was often found to be arrested and halted for a long period (more than 10⁶ cycles) before it began to grow again, which resulted in a significantly slow growth process. The small crack was then analyzed not only by the conventional fractography but also by the cross-sectional observation of the crack tip region using a focused ion beam and transmission electron microscopy. These observations, supplemented also by a grain orientation analysis using electron backscattered diffraction, explicitly revealed the following points: (i) the small crack growth observed on the specimen surface is primarily related to facet-type cracking that occurs exclusively at the specimen surface; (ii) the growth direction of the small crack has strong anisotropy (i.e. surface-induced growth); (iii) the facet-type cracking is related to the formation of persistent fine slip bands that accompany no structural change of the matrix. On the basis of these results, the micromechanism of small crack growth and its relation to the concept of fatigue limit at the HCF regime is discussed in detail.     

Crystal growth of MgAlB14-type compounds using metal salts and some properties

LEAlB₁₄ (orthorhombic, Imam) (LE = Li, Mg) crystals were grown using metal salts (Li₂CO₃, LiF, LiI, MgO, MgF₂, MgI₂) and crystalline boron from a high-temperature aluminium metal flux. The growth conditions for growing LEAlB₁₄ were established using the starting mixtures of B/LE = 2.0, and Al metal was added to each mixture at a mass ratio of 1:15–20. LEAlB₁₄ crystals from the Al-self flux using metal salts could be obtained from all the different salts. The maximum dimensions of LiAlB₁₄ and MgAlB₁₄ crystals were approximately 18 and 12 mm for the crystals obtained from LiF and MgF₂. The unit-cell parameters of as-grown LEAlB₁₄ are as follows: for LiAlB₁₄, obtained from LiF, a = 0.5846 (2) nm, b = 0.8144 (2) nm, c = 1.0355 (3) nm, V = 0.4930 (2) nm³: for MgAlB₁₄, obtained from MgF₂, a = 0.5845 (2) nm, b = 0.8114 (2) nm, c = 1.0330 (3) nm, V = 0.4899 (3) nm³. Microhardness, oxidation resistance and magnetic susceptibility of these materials are described in detail.     

Development of fabrication process for Ag/polydiacetylene (core/shell) hybridized nanocrystals

Core/shell hybridized nanocrystals composed of Ag nanoparticle core and polydiacetylene shell were fabricated successfully by means of “co-reprecipitation/microwave irradiation method”. The hybridized nanocrystals were characterized using transmission electron microscopy (TEM) observation and UV–vis absorption spectroscopy. UV–vis spectral measurements revealed that polydiacetylene shell was the red phase while π-conjugated backbone is distorted. Detailed mechanism of formation of the red phase was discussed.     

Synthesis of soluble poly(9,10-dihydrophenanthrene-2,7-diyl)s. A new class of luminescent poly(p-phenylene)s with ethylene type bridges

Poly(9,10-dihydrophenanthrene-2,7-diyl)s with -OSi(R)₂(R′) groups at the 9,10-positions were synthesized by dehalogenative polycondensation of the corresponding monomers by using a zerovalent nickel complex. They showed number average molecular weights (M_n's) of 9800-69,000 and high quantum yields (62%-quantitative) in photoluminescence. Palladium catalyzed copolymerization of 2,7-dibromo-9,10-dihydrophenanthrene having -OCH₃ or -OSi(R)₂(R′) groups at the 9,10-positions with diethynyl- or diboronic-aromatic compounds also gave photoluminescent polymers with high quantum yields.     

Development of a new loading test apparatus for microfocus X-ray CT and its application to the investigation of soil behavior surrounding driven open-section piles

In recent years, X-ray CT scanners with task-specific modifications, such as microfocus and/or a synchrotron, have been widely implemented in a variety of fields, including medical and industrial fields. Since microfocus X-ray CT systems enable the visualization of whole samples, and also yield a relatively high resolution of the region of interest in the sample, they are commonly utilized in the fields of soil mechanics and geotechnical engineering. This paper describes a novel loading test apparatus that is specifically designed for microfocus X-ray CT systems capable of performing loading tests to investigate soil behavior during the installation of driven open-section piles. The loading tests were designed to take the micro-level spatial resolution of microfocus X-ray CT systems into account. Digital image correlation (DIC) is subsequently implemented to analyze the obtained CT images, making it possible for measurements to be taken of the displacement fields in the ground following installation of the model pile. Finally, the versatility of this novel test apparatus is proof of its high potential for application in different types of loading tests.     

Liposome‐Based in Vitro Evolution of Aminoacyl‐tRNA Synthetase for Enhanced Pyrrolysine Derivative Incorporation

Methanosarcina species pyrrolysyl‐tRNA synthetase (PylRS) attaches Pyl to its cognate amber suppressor tRNA. The introduction of two mutations (Y384F and Y306A) into PylRS was previously shown to generate a mutant, designated LysZ‐RS, that was able to attach N‐benzyloxycarbonyl‐L ‐lysine (LysZ) to its cognate tRNA. Despite the potential of LysZ derivatives, further LysZ‐RS engineering has not been performed; consequently, we aimed to generate LysZ‐RS mutants with improved LysZ incorporation activity through in vitro directed evolution. Using a liposome‐based in vitro compartmentalization (IVC) approach, we screened a randomly mutagenized gene library of LysZ‐RS and obtained a mutant that showed increased LysZ incorporation activity both in vitro and in vivo. The ease and high flexibility of liposome‐based IVC should enable the evolution of not only LysZ‐RS that can attach various LysZ derivatives but also of other enzymes involved in protein translation.     

Improving the photovoltaic performance of co‐evaporated Cu2ZnSnS4 thin‐film solar cells by incorporation of sodium from NaF layers

We have investigated the influence of sodium (Na) on the properties of co‐evaporated Cu₂ZnSnS₄ (CZTS) layer microstructures and solar cells. The photovoltaic performance and diode properties were improved by incorporating Na from NaF layers into the CZTS layers, while Na had a negligible effect on the microstructural properties of the layer. The best cell fabricated by using an optimal CZTS layer (Cu/(Zn + Sn) = 0.70, Zn/Sn = 1.8) yielded an active area efficiency of 5.23%. The analysis of device properties suggests that charge‐carrier recombination at CZTS/CdS interface is suppressed by intentional Na incorporation from NaF layers. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and photoinduced surface relief grating formation of novel photo-responsive amorphous molecular materials, 4-[bis(9,9-dimethylfluoren-2-yl)amino]-4′-cyanoazobenzene and 4-[bis(9,9-dimethylfluoren-2-yl)-amino]-4′-nitroazobenzene

Novel azobenzene-based photo-responsive amorphous molecular materials, 4-[bis(9,9-dimethylfluoren-2-yl)amino]-4′-cyanoazobenzene and 4-[bis(9,9-dimethylfluoren-2-yl)amino]-4′-nitroazobenzene, have been synthesized and the formation of surface relief grating on their amorphous films has been investigated. It was found that a relatively large surface relief grating could be inscribed on both amorphous films upon interference exposure to the writing laser beams. The modulation depth of the surface relief grating inscribed on the amorphous film of the cyano-substituted material was found to be larger than that inscribed on the film of the nitro-substituted one and seemed to be comparable to that inscribed on the amorphous film of the parent material, 4-[bis(9,9-dimethylfluoren-2-yl)amino]azobenzene. These results were discussed from the viewpoint of their trans–cis photoisomerizations as amorphous films and glass-transition temperatures.