Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Palladium(I) Complexes

The dinuclear palladium(I) complexes [L(Ar₂HGe)Pd(μ‐GeAr₂)₂Pd(GeHAr₂)L] (Ar=Ph, p‐Tol; L=PMe₃, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge???Ge bond lengths of 2.8263(4) Å (L=PMe₃) and 2.928(1) Å (L=tBuNC), which are close to the longest Ge? Ge bond reported to date [2.714(1) Å]. Significant Ge???Ge interactions between the germylene and germyl ligands (PMe₃ complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe₃ ligands increases the Ge???Ge interaction, and simultaneously activates two Pd? Ge bonds. Adding the chelating diphosphine 1,2‐bis(diethylphosphino)ethane (depe) to the PMe₃ complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.     

Development of a scanning microscopy by total internal reflection coupled with thermal lens spectroscopy

Non-destructive measurement of a small region on a solid/liquid interface is of great importance in physical chemistry and biochemistry, especially in the research of thin films and cell membranes. Optical methods for surface analysis with high lateral resolution are suitable methods for monitoring them. We now report a new scanning optical microscopic method to which total internal reflection coupled with a thermal lens technique was introduced. Its lateral resolution was estimated both experimentally and theoretically. To experimentally estimate the resolution, the grid patterns of thin photoresist films with well-defined lateral structures were measured. The experimental resolution was about 45 microm, which was almost same as the diameter of the excitation beam at a glass/sample interface. From this result, it was verified that this new scanning microscopy ideally worked.     

A reduced mechanism for primary reactions of coal volatiles in a plug flow reactor

In the present paper, the authors study the primary reactions of coal volatiles and a detailed mechanism has been made for three different environments: thermal decomposition (pyrolysis), partial oxidation (O₂) and O₂/CO₂ gasification in a plug flow reactor to analyze the combustion component. The computed results have similar trend for three different environments with the experimental data. A systematically reduced mechanism for O₂/CO₂ gasification has also been derived by examination of Rate of Production (ROP) analysis from the detailed mechanism (255 species and 1095 reactions). The reduced mechanism shows similar result and has been validated by comparing the calculated concentrations of H₂, CH₄, H₂O, CO, CO₂ and polycyclic aromatic hydrocarbon (PAH) with those of the detailed mechanism in a wide range of operating conditions. The authors also predicted the concentration profiles of H₂, CO, CO₂ and PAH at high temperature and high pressure.     

The size and mass distribution of firebrands collected from ignited building components exposed to wind

Wildfires that spread into communities, commonly referred to as Wildland-Urban Interface fires (WUI), are a significant international problem. Post-fire damage studies have suggested for some time that firebrands are a significant cause of structure ignition in WUI fires, yet little research has been conducted to investigate firebrand production from burning vegetation and structures. To this end, firebrand production from real-scale building components under well-controlled laboratory conditions was investigated. Specifically, wall and re-entrant corner assemblies were ignited and during the combustion process, firebrands were collected to determine the size/mass distribution generated from such real-scale building components under varying wind speed. Finally, the size and mass distributions of firebrands collected in this study were compared with the data from an actual full-scale structure burn to determine if simple component tests such as these can provide insights into firebrand generation data from full-scale structures. The results are presented and discussed.     

Organic thin‐film transistor fabricated between flexible films by thermal lamination

We propose a novel and complementary method for fabrication of flexible electronics. This method is not based on conventional printing using inks, but is based on the application of a toner‐based method such as Xerox or laser printing, followed by a lamination process. The lamination method is a solvent‐free and material‐saving process that simultaneously seals the devices, and the fabricated flexible devices have structural durability against bending. We have also shown that thermal lamination has an oriented growth effect, and the electrical characteristics of flexible organic field‐effect transistors did not degrade under a bending radius of 1 mm.

     

Highly transparent and flexible field electron emitters based on hybrid carbon nanostructure

We demonstrate a unique strategy to fabricate highly transparent and flexible field electron emitters (FEEs) based on combined carbon nanostructures, i.e., conical nanocarbon structures (CNCSs) and single‐walled carbon nanotubes (SWNTs). The combined structure was prepared by spray coating of 1,2‐dichloroethane (DCE) dispersed SWNTs onto neon ion (Ne⁺) irradiation induced CNCSs on nafion substrate. The field emission (FE) property of SWCNTs on both flat nafion and CNCSs surfaces increased with increasing the SWCNTs amount. The best FE result was attained for the highest amount of SWCNTs on the CNCSs substrate. This kind of collective structures is found to be effective emitters on transparent and flexible ion‐irradiated nafion substrate. Moreover, the combined carbon nanostructures showed improved transparency and emission performance compared to the individual nanostructures. The FE properties of 0.5 ml SWCNTs solution on CNCSs surfaces were equal to those of 1.5 ml SWCNTs solution on flat nafion surface. The hybrid structure based emitters (CNCSs and SWCNTs) produced by this method are lower‐cost cathode materials than hybrid structures of SWCNTs and flat nafion. Thus the combined nanostructures of SWCNTs/CNCSs might have huge prospects for the fabrication of efficient transparent and flexible FEEs and their broad application in next‐generation portable display devices. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temporal diet changes recorded by stable isotopes in Asiatic black bear (Ursus thibetanus) hair

Carbon and nitrogen stable isotope ratios were measured in hair samples of the Asiatic black bear (Ursus thibetanus) inhabiting the Northern Japanese Alps (NJA) (n?=?20) and the periphery of Nagano City (NC) (n?=?6), in Nagano Prefecture, Japan. The hair of NJA bears, which did not have access to anthropogenic foods, showed lower values of δ¹³C and δ¹⁵N than that of NC bears which had access to garbage and corn fields, especially during the summer. These results reflect somewhat differing diets between the NJA and NC bears. We attempted to assess the feeding history during the hair growth cycle using the growth section analysis method. Each hair sample had been cut into 3?mm lengths from root to tip, labeled, and analyzed along the hair growth. We measured the carbon and nitrogen stable isotope ratios of each 3?mm length of hair sample from one NC bear which had been killed while raiding a corn field. The sections showed wide ranges of isotope ratios, from ?23.2‰ to ?14.6‰ for δ¹³C, and from 0.3‰ to 4.6‰ for δ¹⁵N. It was shown that the diet of this bear shifted dramatically from principally C₃ plants to more C₄ plants and to foods of animal origin. An analysis of the whole hair reflects just the average feeding habit during hair growth, but the present method can trace its diet history. This method can contribute to obtain precise ecological information of wildlife.     

Synthesis of directly connected BODIPY oligomers through Suzuki-Miyaura coupling

Treatment of a meso-arylboron dipyrrin (BODIPY) with NBS provides mono- and dibrominated BODIPYs at the 2- and 6-positions in excellent yields with high regioselectivity. Brominated products can be employed as a nice building block for the synthesis of a variety of BODIPY derivatives through Suzuki-Miyaura coupling. Because of a lack of substituents at the 1,3,5,7-positions, a directly β-β-linked BODIPY dimer exhibits a completely coplanar conformation of BODIPY units, offering effective π-conjugation.     

Field-angle dependence of the quasiparticle scattering inside a vortex core in unconventional superconductors

We theoretically investigate the quasiparticle scattering rate Γ inside a vortex core in the existence of non-magnetic impurities distributed randomly in a superconductor. We show that the dependence of Γ on the magnetic field direction is sensitive to the sign of the pair potential. The behavior of Γ is quite different between an s-wave and a d-wave pair potential, where these are assumed to have the same amplitude anisotropy, but a sign change only for the d-wave one. It is suggested that measurements of the microwave surface impedance with changing applied-field directions would be used for the phase-sensitive identification of pairing symmetry.     

Fe-site substitution effect on the structural and magnetic properties in SrFeO2

We investigated the Fe-site substitution effect on the structural and magnetic properties of the infinite layer iron oxide Sr(Fe(1-x)M(x))O(2) (M = Co, Mn) using synchrotron X-ray diffraction, neutron diffraction, and (57)Fe Mo?ssbauer spectroscopy. Both systems have a similar solubility limit of x ≈ 0.3, retaining the ideal infinite layer structure with a space group of P4/mmm. For the Fe-Co system, both in-plane and out-of-plane axes decrease linearly and only slightly with x, reflecting the ionic radius difference between Fe(2+) and Co(2+). For the Fe-Mn system the lattice evolution also follows Vegard's law but is anisotropic: the in-plane axis increases, while the out-of-plane decreases prominently. The magnetic properties are little influenced by Co substitution. On the contrary, Mn substitution drastically destabilizes the G-type magnetic order, featured by a significant reduction and a large distribution of the hyperfine field in the Mo?ssbauer spectra, which suggests the presence of magnetic frustration induced presumably by a ferromagnetic out-of-plane Mn-Fe interaction.