Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

烟气中Hg的氧化机理的研究

本文对Ｈｇ与Ｃｌ２在烟气中的氧化反应进行了热力平衡计算和动力学计算。平衡计算的结果表明有ＣＩ元索存在时Ｈｇ的氧化率为１００％，而在相同的条件下动力学计算纺果为Ｈｇ的氧化率在２０％～８０％之间变化，与实验结果吻合。实际的氧化反应是一种超平衡状态，不能达到理想的平衡状态。因此应采用动力学与热力平衡分析相结合的方法研究Ｈｇ在烟气中的反应机理。同时，计算结果显示Ｃｌ含量对Ｈｇ的氧化率的影响很大．     

Global fit analysis including the ν9 + ν4 − ν4 hot band of ethane: Evidence of an interaction with the ν12 fundamental

The ν₉ fundamental band of ethane occurs in the 12 μm region. It is the strongest band of ethane in a terrestrial window and is commonly used for the identification of ethane in the Jovian planets. The ν₉ + ν₄ − ν₄ band occurs in the same region; neither can be analysed as an isolated band, since both are embedded in the torsional bath of the ground vibrational state. We report here two global fit models including data from both of these bands as well as the ν₃ fundamental and the ν₄, 2ν₄ − ν₄, and 3ν₄ torsional transitions. The first is restricted to −5 ? KΔK ? 15 in the hot band and gives an excellent fit to the included data. Three resonant interactions are identified in this fit—a Coriolis interaction with two resonant cases between the ν₉ torsional stack and that of the ground vibrational state (gs) and a resonant Fermi interaction between the ν₃ fundamental and the gs. Hot band lines with KΔK < −5 are influenced by a fourth perturbation, with a crossing at −11 < KΔK < −10, which has been attributed to an interaction with the ν₁₂ fundamental. A second fit, demonstrating a promising treatment of this interaction, is also presented.     

长白山土壤腹足类物种多样性初步研究

自1993年5月至10月对吉林长白山森林生态系统定位站的土壤腹足类进行了多样性调查，据初步调查的结果显示，长白山地区土壤腹足类种类少而单调，采样区仅发现15种，隶属于腹足纲9科13属，采样区土壤腹足类物种多样性指数和丰富度指数都是5月份最低，8月份达最大值，之后逐渐减小；均匀度指数5月份最高，7月份最低；单纯度指数也是5月份最高，最低值出现在10月份，土壤表层的陆生贝类物种多样性指数高于上层。     

Crystallographic report: Diiodo[tris(2‐pyridyl)amine]mercury(II), [(C5H4N)3N]HgI2

In mononuclear HgI₂[(C₅H₄N)₃N], mercury is tetrahedrally coordinated by two nitrogen atoms of a tris(2‐pyridyl)amine ligand and two iodides. The coordination moieties are connected by weak intermolecular Hg(II)···I interactions to give a one‐dimensional structure. Copyright © 2003 John Wiley & Sons, Ltd.     

EQCM Study of the Couple Thallium(I)/Thallium Amalgam at a Thin Film Mercury Electrode

EQCM and voltammetric data show that thallium(I) ions, which are adsorbed in the region of the positive surface charge, most probably, in the form of the ionic pairs, are not reduced. In this potential region, thallium(I) ions are reduced directly from the solution. At more negative potentials, the previously adsorbed stable ionic pairs slowly undergo transition into the less stable form. From this form, thallium(I) ions can be reduced or desorbed into the solution. The process is best described by a model of one electron, i.e., full charge transfer.     

A MICROFOUNDATION OF PREDATOR‐PREY DYNAMICS

ABSTRACT. Predator‐prey relationships account for an important part of all interactions betweenspecies. In this paper we provide a microfoundation for such predator‐prey relations in afood chain. Basic entities of our analysis are representative organisms of species modeled similar to economic households. With prices as indicators of scarcity, organisms are assumed to behave as if they maximize their net biomass subject to constraints which express the organisms' risk of being preyed upon during predation. Like consumers, organisms face a ‘budget constraint’ requiring their expenditure on prey biomass not to exceed their revenue from supplying own biomass. Short‐run ecosystem equilibria are defined and derived. The net biomass acquired by the representative organism in the short term determines the positive or negative population growth. Moving short‐run equilibria constitute the dynamics of the predator‐prey relations that are characterized in numerical analysis. The population dynamics derived here turn out to differ significantly from those assumed in the standard Lotka‐Volterra model.     

Characterization of NOx species in dehydrated and hydrated Na- and Ba-Y, FAU zeolites formed in NO2 adsorption

Adsorbed ionic NO_x species formed upon the interaction of NO₂ with dehydrated or hydrated Na- and Ba-Y, FAU zeolites were characterized using FT-IR/TPD, solid state NMR, and XANES techniques. NO₂ disproportionates on both dehydrated catalyst materials forming NO⁺ and NO₃⁻ species. These ionic species are stabilized by their interactions with the negatively charged zeolite framework and the charge compensating cations (Na⁺ and Ba²⁺), respectively. Although the nature of the adsorbed NO_x species formed on the two catalysts is similar, their thermal stabilities are strongly dependent on the charge compensating cations. In the presence of water in the channels of these zeolite materials new paths open for reactions between NO⁺ and H₂O, and NO₂ and H₂O, resulting in significant changes in the adsorbed ionic species observed. These combined spectroscopic investigations afforded the understanding of the interactions between water and NO₂ on these zeolite catalysts.     

几种常见光源特性的研究

本通过大学物理实验中常用光源特性的分析，说明了实验中光源使用的合理性。     

苯并噻唑重氮氨基偶氮苯与汞（Ⅱ）的显色反应及其应用

报道了新试剂苯并噻唑重氮氨基偶氮苯的合成及其与汞（Ⅱ）的显色反应，在ＴｒｉｔｏｎＸ－１００存在下弱碱性介质中，试剂与汞形成２：１的橙红色络合物，最大吸收波长位于５２０ｎｍ处，表观摩尔吸光系数为１．５１×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。汞量在０～１．２ｍｇ／Ｌ范围内遵守比尔定律，直接应用于废水中微量汞的测定，结果满意。