Synthesis and characterisation of bis(pentafluorophenyl)antimony(V) cations, [(C6F5)2SbL3]

Pentacoordinate complex cations of the general formula [(C₆F₅)₂SbL₃]³⁺ stabilized as solid salts in combination with tetraphenylborate (BPh₄), tetrafluorobroate (BF₄) anions, where L=DMSO, Ph₃AsO, PyO, DMF, α-, β- and γ-picoline have been isolated. The newly formed complexes were characterized by elemental analysis, molar conductance measurements, solid-state IR and and NMR. From these results, a five-fold coordination around antimony was required.     

The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

Molecular structure and spectral properties of thionaphthalimides

The molecular structure and absorption spectra of monothio- and dithio-naphthalimides were compared to their naphthalimide analogues using AM1, PM3 and ZINDO/S semiempirical quantum chemical methods. The substitution of the 4R-naphthalimide oxygen atoms by sulphur atoms resulted in a red-shift of the absorption spectra by Δλ_max60-65 and 100-140 nm, respectively. The thionated naphthalimide derivatives do not show observable fluorescence due to intersystem crossing to the triplet -states localised at the CS groups. The -absorption bands of monothioimides are located at 525-580 nm (ε=60-80) and those for dithioimides at 535-560 nm (ε=140-390) and 628-686 nm (ε=34-68). None of these transitions are solvent sensitive. The -transitions of N-phenylthioimides have also a small contribution from -states due to a partial conjugation between CS group and π-electronic system of the N-phenyl ring. As a result, the bands of aromatic substituted N-phenylthioimides are red-shifted as compared to those of the aliphatic N-methyl-thioimides.     

Modelling sediment transport over partially non‐erodible bottoms

In‐depth‐averaged and cross‐section‐averaged morphodynamic models, based on explicit time integration, it may happen that the computed bed level becomes lower than the top level of a non‐erodible layer (e.g. concrete, bedrock or armoured layer). This is a standard pitfall, which has been addressed in different ways. In this paper, we present an original approach for avoiding computation of non‐physical bed levels, using an iterative procedure to correct the outward sediment fluxes. The procedure is shown to be computationally efficient while it achieves a high accuracy in terms of mass conservation. We compare our original approach with the existing Struiksma's method and with a reformulation of the problem in terms of mathematical optimization of a linear or nonlinear objective function under linear constraints. The new procedure has been incorporated into an existing finite volume morphodynamic model. It has been validated with several 1D benchmarks leading to configurations with sediment transport over non‐erodible bottom. The computation time has been verified not to increase by more than 15% compared with runs without non‐erodible bottom. Copyright © 2011 John Wiley & Sons, Ltd.     

Tuning the phase transition of ZnO thin films through lithography: an integrated bottom‐up and top‐down processing

An innovative approach towards the physico‐chemical tailoring of zinc oxide thin films is reported. The films have been deposited by liquid phase using the sol–gel method and then exposed to hard X‐rays, provided by a synchrotron storage ring, for lithography. The use of surfactant and chelating agents in the sol allows easy‐to‐pattern films made by an organic–inorganic matrix to be deposited. The exposure to hard X‐rays strongly affects the nucleation and growth of crystalline ZnO, triggering the formation of two intermediate phases before obtaining a wurtzite‐like structure. At the same time, X‐ray lithography allows for a fast patterning of the coatings enabling microfabrication for sensing and arrays technology.     

Scalable bottom‐up assembly of suspended carbon nanotube and graphene devices by dielectrophoresis

Bottom‐up assembly by dielectrophoresis (DEP) has emerged in recent years as a viable alternative to conventional top–down fabrication of electronic devices from nanomaterials, particularly carbon nanotubes and graphene. Here, we demonstrate how this technique can be extended to fabricate devices containing carbon nanotubes and graphene suspended between two electrodes over a back‐gate electrode. The suspended device geometry is critical for the development of nano‐electromechanical devices and to extract maximum performance out of electronic and optoelectronic devices. This technique allows for parallel assembly of devices over large scale. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

渤黄东海底摩擦系数数值研究

使用伴随同化方法探讨了四种底摩擦系数处理方法并模拟了渤黄东海的M₂分潮.理想实验表明:伴随同化方法有很强的反演底摩擦系数的能力;为了得到较好的反演结果,反演策略必须与给定的分布一致;如果给定分布很复杂,则需要复杂的反演策略.实际实验表明,底摩擦效应与地形密切相关,而海洋地形十分复杂,故需要较多的独立的底摩擦系数才能得到较好的模拟结果.本文的第四种方法将每一点均作为独立的底摩擦系数,在实验中获得了成功,验证了这种方法的合理性和有效性.     

S-wave baryons in an equally mixed scalar-vector square root potential model of independent quarks

A relativistic model of independent quarks based on Dirac equation with an equally mixed scalar-vector square root confining potential is used to compute the quark core contributions to the static properties like magnetic moments, charge radii and axial vector coupling constant ratios of the baryon octet. The results obtained with appropriate corrections due to centre-of-mass motion agree fairly well with experimental values. The model is also extended to the study of magnetic moments of the quark core of baryons in the charmed andb-flavoured sectors and the overall predictions so obtained compare well with other model predictions.