RbCl由H2O至混合溶剂(H2O-DMF)标准迁移熵的测定

电解质迁移热力学性质的测定,对于离子溶剂化的研究具有重要意义.迁移自由能主要反映离子与溶剂分子间的相互作用,迁移熵则主要反映不同溶剂分子间的相互作用,迁移熵随温度及溶剂组成的改变可为溶剂的原有结构推测及溶液秩序改变提供信息.我们曾运用离子选择性电极测定了部分碱金属卤化物在水及含水混合溶剂中的热力学性质[1-3].本文用离子选择性电极方法,通过测定不同温度下电池的标准电动势,根据溶液热力学原理,求得ＲｂＣｌ由Ｈ2Ｏ至混合溶剂(Ｈ2ＯＤＭＦ)的标准迁移自由能ΔＧｔ及其温度系数,计算ＲｂＣｌ的标准迁移熵ΔＳｔ.结果尚未见…     

Ti-Al系金属间化合物的价电子结构分析

1　引言ＴｉＡｌ系金属间化合物因具有良好的高温性能与很低的密度在未来航空航天及兵工等方面有着美好的应用前景,但由于极低的室温脆性使其真正投入商用仍很困难.脆性一直是材料科学所关注的问题,这些年来虽在这方面做了大量工作,但大多研究仍停留在实验规律上[1].为深入理解脆性,从物理机理特别是化学键本质上探讨已势在必行.近年来已有人[2]从电子结构或电荷密度分布来解释ＴｉＡｌ的脆性本质,也有人[3]从价电子结构来分析Ｔｉ3Ａｌ的强韧性,但就整个ＴｉＡｌ系金属间化合物的全面分析而言,这些工作还缺乏系统性.固体与分子经验电子理论…     

金沙江龙蟠断陷谷地与河床覆盖层的成因初探

通过河床钻孔并结合野外踏勘,确定了隐伏的龙蟠断裂在宽谷的切错位置,指出古龙蟠谷地是在上新世末早更新世初由龙蟠断裂发生逆断走滑和白汉场断裂的正断左旋并伴随断块的垂直升降活动而形成。河床覆盖层由现代金沙江冲积层和下伏的一套古湖相堆积物组成,其中古湖相堆积具有明显的分层性,由底往上可划分为冰缘冻融泥流堆积物、含泥质的灰绿色细砂和黄褐色粉土层、崩坡积和冲洪积加积物、灰绿色淤泥质碎石土层,结合区域性地质环境演化背景,认为它们是受中更新世时期本区间歇性山体抬升和冰川活动等新构造运动影响的不同沉积环境下的产物,从而清晰地揭示了河床深厚覆盖层的成因,为认识金沙江宽谷河段发育史提供了极其重要的信息。     

不同磺化度下的磺化聚醚醚酮对全钒储能液流电池性质影响的研究

本文报道了采用浓硫酸作为磺化剂,成功合成了不同磺化度下的聚醚醚酮(PEEK)膜,并深入研究了磺化条件包括磺化时间和磺化剂的用量对所获薄膜性能的影响,获得了在不同磺化度（DS）下SPPEK膜的离子交换容,含水率,机械性能,质子电导率等参数,特别测定了在全钒液流电池工作条件下钒离子(Ⅳ)渗透率,首次为该类液流储能电池使用价廉质优的质子交换膜提供了基础实验数据。室温条件下的实验结果如下：1）磺化12小时后,膜的磺化度46%,含水量为28%,钒离子(Ⅳ)选择性最佳（钒离子渗透率为1.2×10-7 cm2/min-1,是Nafion117 (2.9×10-6 cm2/min-1)的1/24）,其质子电导率只有0.02 S/cm;2）磺化96小时其磺化度达79%的膜,质子电导率达0.16 S/cm,是Nafion117 (0.10S/cm) 的1.6倍, 但其机械性能最差;3）与Nafion117膜相比,磺化在36到48小时的SPPEK膜其机械力学性能好,薄膜的钒离子渗透率、离子交换容IEC、质子导电率和含水率高,且对钒离子的选择性佳,尤其价格仅为Nafion膜的1/13,是理想的Nafion膜的代替物,可望直接应用于全钒氧化还原液流（VRB）电池中。本文还讨论了磺化时间和不同磺化剂量对膜的性质的影响。     

地震纵横波时差耦合作用的斜坡崩滑效应研究

在燃烧室入口来流为Ma=2.64、T0=1483K、P0＝1.65MPa、T=724K、P=76.3kPa条件下,采用高速摄影和连续激光高速纹影对等截面型开窗燃烧室内氢气射流自燃过程、火花塞点燃氢气过程和引导氢气火焰点燃煤油过程进行了观测,获得了燃烧室内着火过程中火焰和流场波系结构的动态演化过程;观察到了初始火焰区首先起始于燃烧室下游,并逆流传播实现发动机着火的过程;分析表明燃料能否着火、以及着火位置与燃料着火时间、燃烧室流速和火焰稳定器安装情况相关,多火焰稳定区延长了燃料驻留时间,使燃料更容易着火。 关键词 超燃冲压发动机,点火过程,火焰传播,火焰稳定器     

First-principles study of ferromagnetism in Zn- and Cd-doped SnO2

The electronic structures and magnetic properties of Zn- and Cd-doped SnO₂ are investigated using first-principles calculations within the generalized gradient approximation (GGA) and GGA+U scheme. The substitutional Zn and Cd atoms introduce holes in the 2p orbitals of the O atoms and the introduced holes are mostly confined to the minority-spin states. The magnetic moment induced by doping mainly comes from the 2p orbitals of the O atoms, among which the moment of the first neighboring O atoms around the dopant are the biggest. The U correction for the anion-2p states obviously increases the moment of the first neighboring O atoms and transforms the ground states of the doped SnO₂ from half-metallic to insulating. The magnetic coupling between the moments induced by two dopants is ferromagnetic and the origin of ferromagnetic coupling can be attributed to the p–d hybridization interaction involving holes.     

Synthesis and Mesophase Behavior of Phenylthiophene Based Amphiphilic Molecules

Novel amphiphilic molecules consisting of a rigid 2‐phenylthiophene core, with a polar flexible tri(oxylethylene) moiety attached to the phenyl ring and one or two alkyl chains attached to the thiophene ring at the other side have been synthesized by using Ni(II) and Pd(0) catalyzed coupling reaction as key steps. The tri(oxylethylene) moieties were terminated with hydroxyl group, sodium carboxylate group and lithium carboxylate group respectively. The thermotropic and solvent induced liquid crystalline behavior of these substances was investigated by polarized optical microscopy, differential scanning calorimetry and X‐ray diffraction. Thereby the influence of the terminal groups attached to the tri(oxylethylene) moities as well as the influence of the length and the number of the alkyl chains on the mesophase behavior were investigated. The single alkyl chain Na‐carboxylate termianted derivatives show smectic A phases, double alkyl chain Na‐carboxylate terminated derivatives show a thermo tropic hexagonal columnar mesophase, while columnar mesophases are found in both single and double alkyl chain Li‐carbonate terminated derivatives. The model for molecular organization in the hexagonal columnar mesophase is established.     

FerriIridium: A Lysosome-Targeting Iron(III)-Activated Iridium(III) Prodrug for Chemotherapy in Gastric Cancer Cells

Reported is the Fe^III-activated lysosome-targeting prodrug FerriIridium for gastric cancer theranostics. It contains a meta-imino catechol group that can selectively bond to, and be oxidized by, free Fe^III inside the cell. Subsequent oxidative rearrangement releases Fe^II and hydrolyses the amine bond under acidic conditions, forming an aminobipyridyl Ir complex and 2-hydroxybenzoquinone. Thus, Fe^II catalyzes the Fenton reaction, transforming hydrogen peroxide into hydroxyl radicals, the benzoquinone compounds interfere with the respiratory chain, and conversion of the prodrug into the Ir complex leads to an increase in phosphorescence and toxicity. These properties, combined with the high Fe^III content and acidity of cancer cells, make FerriIridium a selective and efficient theranostic agent (IC₅₀=9.22 μm for AGS cells vs. >200 μm for LO2 cells). FerriIridium is the first metal-based compound that has been developed for chemotherapy using Fe^III to enhance both selectivity and potency.     

FerriIridium: A Lysosome‐Targeting Iron(III)‐Activated Iridium(III) Prodrug for Chemotherapy in Gastric Cancer Cells

Reported is the Fe^III‐activated lysosome‐targeting prodrug FerriIridium for gastric cancer theranostics. It contains a meta‐imino catechol group that can selectively bond to, and be oxidized by, free Fe^III inside the cell. Subsequent oxidative rearrangement releases Fe^II and hydrolyses the amine bond under acidic conditions, forming an aminobipyridyl Ir complex and 2‐hydroxybenzoquinone. Thus, Fe^II catalyzes the Fenton reaction, transforming hydrogen peroxide into hydroxyl radicals, the benzoquinone compounds interfere with the respiratory chain, and conversion of the prodrug into the Ir complex leads to an increase in phosphorescence and toxicity. These properties, combined with the high Fe^III content and acidity of cancer cells, make FerriIridium a selective and efficient theranostic agent (IC₅₀=9.22 μm for AGS cells vs. >200 μm for LO2 cells). FerriIridium is the first metal‐based compound that has been developed for chemotherapy using Fe^III to enhance both selectivity and potency.