Conductance studies in amide-water mixtures. II. Sodium salts inN,N-dimethylformamide-water mixtures at 35°C

Conductance data for sodium nitrite, chloride, and acetate in water andN,N-dimethylformamide (DMF)-water mixtures (74.82D42.48) for the concentration range 0.001–0.04N, as well as the densities, viscosities, and dielectric constants of the solvent mixtures at 35°C, are reported. The data have been analyzed by the Fuoss (1975) equation. The existence of a maximum in the viscosity at a 13 mole ratio of DMF and water is indicated. The Walden products for all the three salts pass through a maximum while the equivalent conductances show a minimum with increasing DMF content. The maxima in the Walden product are attributed to the dehydration of ions by the cosolvent (DMF).Part I:Indian J. Chem. 14A, 1015 (1976).Deceased.     

Bioanalytical methods applied to endocrine disrupting polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. A review

The usual methods for determining polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) are generally expensive and time consuming. This fact has favored the development of faster and cheaper techniques, based on immunoassays and bioassays. This paper reviews these bioanalytical methods and their analytical importance at the present moment.     

盾构隧道围岩与衬砌协同作用纵向位移计算法

盾构机掘进过程中,千斤顶顶进力的不均匀引起的纵向位移是管片间初始错台的主要原因之一;基于Timoshenko梁理论的隧道纵向位移计算方法,未能考虑隧道开挖后围岩卸载破坏的变形特征及围岩与衬砌结构的协同作用效应,预测误差较大。建立了考虑围岩卸载扩容效应的等效地基抗力系数计算方法,提出了能考虑螺栓个数的等效抗剪刚度计算公式,建立一种基于Timoshenko梁理论的改进管片拼装式隧道纵向位移理论计算方法。实际工程案例分析表明：考虑围岩开挖卸载过程中围岩的非线性体积相关塑性变形（即扩容效应）更合理;考虑壁后注浆液固化过程的时效性,采用改进的滑移边界条件计算的纵向位移最大值是传统的固定端边界的计算值的2.3倍,边界条件对计算结果影响较大,本文计算方法更符合实际情况,也更安全。     

试验与服役数据融合的飞机结构安全寿命分析

针对飞机结构安全寿命分析中样本容量偏少的问题,综合考虑结构分散性和载荷分散性的飞机结构疲劳寿命是否服从对数正态分布或威布尔分布的情况,根据等损伤原理,将服役飞机实际飞行小时数等效转化为在同一试验载荷谱下的当量飞行小时数,以实现飞机结构试验疲劳寿命与服役使用数据的融合,采用随机右截尾情形下的极大似然估计方法估算疲劳寿命分布函数的参数,进行飞机结构安全寿命分析;最后以飞机结构疲劳寿命服从对数正态分布为例进行了算例分析,分析结果表明:在相同的可靠度和置信水平下,利用试验数据与服役使用数据融合方法可以显著增大样本容量,从而充分挖掘飞机结构可靠性的储备。     

等效连续裂隙岩体渗流与应力全耦合分析

推导了等效连续裂隙岩体渗透性与应力变形的关系,根据应变等效原则推导了等效连续裂隙岩体的弹性矩阵,首次采用四自由度全耦合法,建立了等效连续裂隙岩体渗流与应力的全耦合有限元方程组,进行了等效连续裂隙岩体渗流与应力的全耦合分析。     

PWM开关变换器符号分析的统一算法

用等效小参量法对开环ＰＷＭ型ＤＣＤＣ开关变换器进行了分析,得到了一种适合于这类电路的统一算法．通过设立一个表明非线性函数性质的标志,进行简单的矩阵运算,求得变换器的输出直流值和纹波解析解．仿真结果证实了这种算法的正确性和通用性．     

等效剂在合成中的应用研究：Ⅵ.合成二氢茉莉酮的新途径

茉莉酮和二氢茉莉酮是一类名贵的香料,此类化合物的合成一直是人们所关注的问题。已有许多报道,其中包括庚醛、1-硝基庚烷与甲基乙烯基酮进行Michael加成和以硝代甘缩酮与庚醛进行硝-醛缩合制得1,4-二酮,再进行分子内缩合为二氢茉莉酮。这些合成方法,有的对反应条件要求较苛刻,不易操作,有的则反应步骤较多,收率低。最近,白俊才等以甲基乙烯基酮和1-己烯为原料,合成了二氢茉莉酮,此法虽然新颖,但氧硼杂环己烷中间体     

Ab initio studies on reaction H2C=C(OH)Li+CH3 + (CH3 -)

The possible structures and isomerizations of H₂C=C(OH)Li are studied theoretically by the gradient analytical method at RHF/6-31+G level. According to these results, reactions of H₂C=C(OH)Li with CH₃ ⁺ and CH ₃ ^- are investigated thoroughly. When H₂C=C(OH)Li reacts with CH ₃ ⁺ , H_zC=C(OH)Li firstly changes from structure1 to structure4, and then combines with CH₃ ⁺. In this reaction, the configuration of central carbon is retained. When H₂C=C(OH)Li reacts with CH ₃ ^- , structure1 firstly breaks its C-O bond to give contact ion-pair. Then through transition state16 which is similar to structure2, the attack of CH ₃ ^- from the opposite side of^-OH replaces^-OH group and inverts the configuration of carbenoid carbon atom. All the results show that the ambident reactivity of carbenoid has close relationship with the stability of special structures. Project supported by the National Natural Science Foundation of China (Grant No. 29773025).     

Formal total synthesis of hemibrevetoxin B by a convergent strategy

Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1.     

Cathodic electrochemiluminescence at double barrier Al/Al2O3/Al/Al2O3 tunnel emission electrodes

Double insulating barrier tunnel emission electrodes were fabricated by adding a new pure aluminum layer upon oxidized aluminum electrodes by vacuum evaporation and thermally oxidizing the new aluminum layer in air at room temperature. Resulting Al/Al₂O₃/Al/Al₂O₃ electrodes allow the use of various aluminum alloys in the electrode body necessary for hardness or shaping ability of the electrode while obtaining the luminescence properties of pure aluminum oxide. During electrical excitation of luminescent labels by cathodic hot electron injection into aqueous electrolyte solution, the background noise is mainly based on high-field-induced solid-state electroluminescence and F-center luminescence of the outer aluminum oxide film. The more defect states and/or impurity centers the outer oxide film contains, the higher is the background emission intensity. The present electrode fabrication method provides a considerable improvement in signal-to-noise ratio for time-resolved electrochemiluminescence (TR-ECL) measurements when the original native oxide film of the electrode body contains luminescence centers displaying long-lived luminescence. The excellent performance of the present electrodes is demonstrated by extremely low-level detection of Tb(III) chelates, luminol, Pt(II) coproporphyrin and Tb(III) labels in an immunometric immunoassay by time-resolved electrochemiluminescence.