Anatase nanotubes as support for platinum nanocrystals

Anatase nanotubes were successfully produced via the sol–gel process involving organic titanium precursors and multi-walled carbon nanotubes as template. Controlled heat treatments were carried out in order to remove any solvents and to crystallise the initial amorphous titania coating into anatase. In order to use these structures for catalyst support, platinum particles were formed by the impregnation with hexachloroplatinic acid and subsequent calcination and reduction to obtain a final loading of 4 wt% platinum. This impregnation step was carried out either with the carbon nanotube former still present with subsequent heat treatment to remove the carbonaceous template (sample A) or with the carbon nanotube former already removed (sample B). The materials were characterised by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.     

Adhesion of viscoelastic materials to rigid substrates. III. Energy criterion for failure

Measurements are described of the strength of a model adhesive joint subjected to (1) tensile rupture, with the interface containing a small unbonded region of varying size, and (2) pure shear deformation, in the form of a partly unbonded sheet. These, and previous measurements of resistance to peeling separation, are all shown to be consistent with an energy criterion for adhesive failure. The characteristic failure energy per unit area of interface has been determined for the model adhesive material as a function of the effective rate of detachment, over a wide range covering almost the entire spectrum of viscoelastic response. The values obtained are found to increase from levels only slightly higher than thermodynamic considerations would predict, i.e., 10²?10³ ergs/cm², at low rates of crack propagation, up to a value of about 10⁶ ergs/cm² at high rates when the material responds in a glasslike manner. These results suggest that the failure energy has two components: the (reversible) work of adsorption and the (irreversible) work of deformation of the adhesive in effecting separation.     

Crystal structure and growth mechanism of unusually long fullerene (C60) nanowires

Exceptionally long C60 nanowires, with a length to width aspect ratio as large as 3000, are grown from a 1,2,4-trimethylbenzene solution of C60. They have been formed to possess a highly unusual morphology, with each nanowire being composed of two nanobelts joined along the growth direction to give a V-shaped cross section. The crystal structure of these nanowires is found to be orthorhombic, with the unit cell dimensions of a = 10.2 A, b = 20.5 A, and c = 25.6 A. Structural and compositional analyses enable us to explain the observed geometry with an anisotropic molecular packing mechanism that has not been observed previously in C60 crystal studies. The nanowires have been observed to be able to transform into carbon nanofibers following high-temperature treatment, but the original V-shaped morphology can be kept unchanged in the transition. A model for the nanowire morphology based upon the solvent-C60 interactions and preferential growth directions is proposed, and potentially it could be extended for use to grow different types of fullerene nanowires.     

Evaluation of electron-withdrawing group effects on heme binding in designed proteins: implications for heme a in cytochrome c oxidase

Heme a, the metalloporphyrin cofactor unique to cytochrome c oxidases, differs from the more common heme b by two chemical modifications, a C-2 hydroxyethylfarnesyl group and a C-8 formyl group. To elucidate a role of the C-8 formyl group, we compare the heme affinity, spectroscopy, and electrochemistry of a heme a mimic, Fe(diacetyldeuterioporphyrin IX) or Fe(DADPIX), with heme b, Fe(protoporphryrin IX) or Fe(PPIX), incorporated into a designed heme protein. The [Delta7-H3m]2 protein ligand, or maquette, selected for this study contains two equivalent bis-(3-methyl-L-histidine) heme binding sites within a four-alpha-helix bundle scaffold. The spectroscopic data on Fe(PPIX) and Fe(DADPIX) bound to [Delta7-H3m]2 demonstrate that these complexes are excellent synthetic analogues for natural cytochromes b and a, respectively. Comparison of the spectroscopic, electrochemical, and equilibrium thermodynamic data measured for the Fe(PPIX)-[Delta7-H3m]2 maquette with the previously reported Fe(PPIX)-[Delta7-His]2 complex demonstrates that changing the heme axial ligands to 3-methyl-L-histidine from L-histidine does not alter the resulting heme protein properties significantly in either oxidation state. Heme binding studies demonstrate that [Delta7-H3m]2 binds two ferrous Fe(DADPIX) or Fe(PPIX) moieties with similar dissociation constant values. However, in the ferric state, the data show that [Delta7-H3m]2 only binds a single Fe(DADPIX) and that one 2500-fold weaker than oxidized Fe(PPIX). The data demonstrate that the 4.6 kcal mol(-1) weakened affinity of [Delta7-H3m]2 for oxidized Fe(DADPIX) results in the majority of the 160 mV, 3.7 kcal mol(-1), positive shift in the heme reduction potential relative to Fe(PPIX). These data indicate that a role of the formyl group on heme a is to raise the iron reduction potential, thus making it a better electron acceptor, but that it does so by destabilizing the affinity of bis-imidazole sites for the ferric state.     

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd.     

The parameter space for the direct spinning of fibres and films of carbon nanotubes

We have recently introduced a method for the continuous spinning of carbon nanotube fibres and films directly from the gas phase of a chemical vapour deposition furnace [Y. Li, et al., Science 304 (2004) 276]. In this work the effect of the process parameters on the ability to spin continuously is studied, with particular focus on the carrier gas and feedstock flow rates. Catalyst dilution by high carrier gas flow rates led to smaller diameter nanotubes but these conditions are found the hardest to spin.     

Self-organization of carbon nanotubes in evaporating droplets

Here, we report a simple and efficient way for organizing carbon nanotubes, in particular, single-wall carbon nanotubes (SWNTs) into ordered structures from their dilute solutions. It was found that drying a droplet of carbon nanotube solution at room temperature on a wettable surface such as glass or silica wafer led to redistribution, accumulation, and organization of carbon nanotubes along the perimeter of the droplet. Unlike the aggregation behaviors of colloid nanoparticles, anistropic carbon nanotubes tended to show two orientations in a ring deposit: one parallel to the outer perimeter of the ring and the other normal to it in the interior. Drying droplets of SWNT solutions at high temperatures exhibited a long-range ordered structure. In addition, droplet drying may cause size separation of carbon nanotubes and pattern formation through interactions between droplets. This result helps us not only to further understand fluid dynamics during the drying process but also to provide a promising and simple strategy for either assembling carbon nanotubes on a surface or organizing them into well-aligned films and fibers.     

泥沙输运模拟综述——现状及其发展趋势

随着流体力学中数值方法的飞速发展,计算模型已经成为研究流体运动,泥沙输运和不同环境(诸如河流,湖泊及沿海地区)中相应污染物归趋过程等方面非常有吸引力的工具,在过去的30多年里,发展了许多计算水动力学/泥沙输运模型.文章追溯当前具有代表性的(一维、二维、三维)模型的发展历程,描述他们各自的特点,优势及局限,力图作为对模型方面感兴趣读者的第一指南,同时也为大家讨论模型的局限性,未来的发展趋势和研究需求方面搭建一个平台.给出了模型的表达,时空特性,水动力学和沉积物的耦合方式,处理非恒定流,推移质和悬移质,泥沙交换过程,泥沙类型(粘性或非粘性)及非均匀泥沙输运的能力.总结了不同模型的应用实例,读者可以运用这些例子作为研究模型设置,模型率定及模型验证的参考.给出了选择泥沙输运模型应遵循的原则,模型输入及率定方面存在的问题及改进的途径.探讨了现有水动力学/泥沙输运模型在处理复杂湍流,泥沙携带,流动与输沙耦合,非均匀泥沙,离散和扩散系数,河岸来沙处理等方面的局限性及改进的方向.最后,对基于多相流思想的泥沙输运模型及其它一些交叉性问题作了评述与展望.