An innovative molybdenum column liner for oxygen and hydrogen stable isotope analysis by pyrolysis

The most widely used method for pyrolysing samples for hydrogen or oxygen isotopic analysis involves heating them to greater than 1300 degrees C in a helium stream passed through a glassy carbon tube in an alumina casing. There are a number of difficulties with this. Glassy carbon tubes are expensive and interaction between the carbon tube and the outer casing produces unwanted carbon monoxide by reduction of the alumina at high temperatures. The latter effect is overwhelming if temperatures of 1400 degrees C or greater are used for pyrolysis. We experimented with lining alumina casings with pure molybdenum sheet. It is relatively cheap, conforms well to the interior of the reactor tube (to avoid carrier and sample bypassing of the carbon pack), resists high temperatures and neither oxidises excessively nor absorbs the gases. The main disadvantages are that silver sample cups must be used and that the molybdenum degrades over time by formation of the carbide. We can maintain sharp peaks, high precision and good accuracy over more than 700 solid samples for both hydrogen and oxygen. The reactors last longer for water injections. The molybdenum in the columns does not contribute greatly to memory effects. The precision of analysis is dependent on other factors as well as the pyrolysis column, but for oxygen we typically achieve approximately <0.2 per thousand (sucrose), <0.25 per thousand (water) and <0.25 per thousand (leaf), sometimes using only a linear correction of drift, after dividing the run into 1 to 3 segments.     

The sixteen CB(11)H(n)Me(12-n)(-) anions with fivefold substitution symmetry: anodic oxidation and electronic structure

The 15 symmetrically methylated derivatives of the CB11H12(-) anion (1a) have been synthesized and found to vary greatly in ease of oxidation. Cyclic voltammetry in liquid SO2 yielded fully reversible oxidation potentials for five of those that have no adjacent unsubstituted vertices in positions 7-12; three others showed some indication of reversibility. The anions 1a-16a and the Jahn-Teller distorted neutral radicals 1r-16r have been characterized by ab initio and density functional theory calculations. In the state average CASSCF(13,12)/6-31+G* approximation, the ground state potential energy surface of 1r contains five symmetry-related pairs of minima. The computational results account for the reversible redox potentials very well when the solvent is included explicitly (RI-DFT(BP)/TZVP, COSMO). For display and for a semiquantitative understanding of methyl substituent effects in terms of perturbation theory, the molecular orbitals of 1a have been expressed in the symmetry-adapted cluster basis. The results serve as an underpinning for a set of additive empirical increments for redox potential prediction. Relative to the usual hydrogen standard, a single methyl group facilitates oxidation by approximately 50, 70, 70, and 10 mV in positions 1, 2, 7, and 12, respectively. This electron donor effect on the redox potential is due to a contribution, whereas those of (inductive and direct field) type are negligible.     

邻硝基乙酰苯胺衍生物的XPS振起伴峰及其价带谱的研究

研究了一组邻硝基乙酰苯胺衍生物的X射线光电子能谱(XPS).观察到硝基的N1s光电子谱有明显分裂,可认为是N1s振起伴峰的反映,而且苯环上的取代基对该振起伴峰强度有影响,按照Pignataro等关于振起伴峰与主峰的能量分离以及分子内电荷转移有关的观点,计算了振起伴峰与主峰的面积比.结果表明,峰间距与面积比的趋势一致.因此二者都可作为分子内电荷转移的粗略估计.     

Estimating rate constants in a convection-diffusion system with a boundary reaction

While performing biomolecular interaction analysis (BIA), scientistsoften use surface plasmon resonance (SPR) to measure rate constantsof the associated reactions. A mathematical model of a BIAcore^TM,a common SPR device, consists of a convection-diffusion equationin a channel with a reacting surface at the channel ceiling.Asymptotic and singular perturbation techniques are used toanalyse the concentration of the reacting species in two cases:when the reaction occurs much more slowly than diffusion, andwhen the reaction occurs on the same time-scale as diffusion.Linear and nonlinear integral equations result from the analysis;explicit and asymptotic solutions are constructed for physicallyrealizable cases. These expressions provide a direct way toestimate the rate constants from raw data.     

Dynamical mechanism for varying light velocity as a solution to cosmological problems

A dynamical model for varying light velocity in cosmology is developed, based on the idea that there are two metrics in spacetime. One metric g_μν describes the standard gravitational vacuum, and the other describes the geometry through which matter fields propagate. Matter propagating causally with respect to can provide acausal contributions to the matter stress-energy tensor in the field equations for g_μν, which, as we explicitly demonstrate with perfect fluid and scalar field matter models, provides a mechanism for the solution of the horizon, flatness and magnetic monopole problems in an FRW universe. The field equations also provide a ‘graceful exit' to the inflationary epoch since below an energy scale (related to the mass of ψ_μ) we recover exactly the standard FRW field equations.     

Growth,structure, and superconducting properties of Bi2Sr2Ca2Cu3O10 and (Bi,Pb)2Sr2Ca2Cu3O10‐y crystals

Large and high‐quality single crystals of both Pb‐free and Pb‐doped high temperature superconducting compounds (Bi_1‐xPb_x)₂Sr₂Ca₂Cu₃O_10‐y (x = 0 and 0.3) were grown by means of a newly developed “Vapour‐Assisted Travelling Floating Zone” technique (VA‐TSFZ). This modified zone‐melting technique was realised in an image furnace and allowed for the first time to grow Pb‐doped crystals by compensating for the Pb losses occurring at high temperature. Crystals up to 3×2×0.1 mm³ were successfully grown. Post‐annealing under high pressure of O₂ (up to 10 MPa at T = 500°C) was undertaken to enhance T_c and improve the homogeneity of the crystals. Structural characterisation was performed by single‐crystal X‐ray diffraction (XRD) and the structure of the 3‐layer Bi‐based superconducting compound was refined for the first time. Structure refinement showed an incommensurate superlattice in the Pb‐free crystals. The space group is orthorhombic, A2aa, with cell parameters a = 27.105(4) Å, b = 5.4133(6) Å and c = 37.009(7) Å. Superconducting studies were carried out by A.C. and D.C. magnetic measurements. Very sharp superconducting transitions were obtained in both kinds of crystals (ΔT_c ≤ 1 K). In optimally doped Pb‐free crystals, critical temperatures up to 111 K were measured. Magnetic critical current densities of 2�10⁵ A/cm² were measured at T = 30 K and μ₀H = 0 T. A weak second peak in the magnetisation loops was observed in the temperature range 40‐50 K above which the vortex lattice becomes entangled. We have measured a portion of the irreversibility line (0.1‐5 Tesla) and fitted the expression for the melting of a vortex glass in a 2D fluctuation regime to the experimental data. Measurements of the lower critical field allowed to obtain the dependence of the penetration depth on temperature: the linear dependence of λ(T) for T < 30 K is consistent with d‐wave superconductivity in Bi‐2223. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

一种新型四硫富瓦烯衍生物的合成与表征

以二硫化碳和金属钠为基础物质合成了四硫富瓦烯（TTF）锌的配合物（TTF）Zn（NBu4）2。利用该化合物与苯甲酰氯反应得到的稳定化合物C17H10O2S5在甲醇钠溶液中与2,3-二溴丙醇反应成功合成出目标化合物（一种新配体）,其化学组成为C6H6OS5。利用IR谱、^1HNMR谱及元素分析对此化合物进行了表征。     

强激光装置中玻璃疵病在线检测的光学系统设计

介绍了一种用于玻璃疵病在线检测的近摄工作距成像光学系统,其光组结构形式采用了光阑后置的准远心结构形式,主要光学参量为f′=14 mm;在物像距为250 mm约束条件下,物方视场达到90 mm（对角线）;F/number=3.56;光谱适应范围为400~800 nm,对应的空间分辨率为100 lp/mm时,调制传递函数大于0.29.     

新大线同沟敷设热力分析

针对新大线同沟敷设管道,采用非结构化有限容积法,分析了不同的物性条件下,常温输送原油对加热输送原油的热力影响.     

对-叔丁基杯[8]芳烃键合硅胶制备及其毛细管电色谱性能研究

以γ-(环氧丙氧)丙基键合硅胶为前体,于硅胶表面键合环氧基,在催化剂存在下以杯芳烃钠盐开环制备杯芳烃键合硅胶固定相.该方法反应条件温和,适用性强.将这个新方法首次用于制备对-叔丁基杯[8]芳烃电色谱键合固定相(C8BS),采用加压电色谱初步评价其电色谱性能.研究结果表明,C8BS电渗流(Electrosmoticflow,EOF)较小,但通过控制键合反应及使用压力辅助电色谱可部分弥补上述不足.该固定相的EOF受流动相pH影响小(pH=3-8),同时大环配体屏蔽效应能有效地克服硅羟基引起的碱性化合物拖尾现象,这对电色谱分离具有重要意义.通过分步封尾研究EOF的来源发现,杯芳烃酚羟基对EOF有弱的贡献,这与报道的杯芳烃涂层具有径向电渗流调控能力相一致.