Overloaded elution band profiles of ionizable compounds in reversed‐phase liquid chromatography: Influence of the competition between the neutral and the ionic species

The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pK_a are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C₁₈‐bonded packing materials, including the 5 μm Xterra‐C₁₈ (121 Å), 5 μm Gemini‐C₁₈ (110 Å), 5 μm Luna‐C₁₈(2) (93 Å), 3.5 μm Extend‐C₁₈ (80 Å), and 2.7 μm Halo‐C₁₈ (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant _W^WpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pK_a and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution.     

Feedback stabilization of snap-through buckling in a preloaded two-bar linkage with hysteresis

We study a linearly damped preloaded two-bar linkage that exhibits hysteresis due to the presence of multiple attracting equilibria. The dynamics at the unstable equilibrium, through which a snap-through buckle occurs, are not linearizable due to a solution-dependent singularity. We stabilize the unstable equilibrium using two distinct non-linear controllers. The feedback-linearization controller requires knowledge of the linkage parameters, whereas the robust version of the intrinsic non-linear proportional-derivative controller requires only an upper bound on the stiffness.     

Geometry and electronic structure of a heterometallic cluster Mo<Subscript>2</Subscript>Mg<Subscript>2</Subscript> in different oxidation states of Mo: a DFT study

Reduction of tetranuclear heterometallic complex Mo₂Mg₂ was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo^VIO₂Mg(MeOH)₂(OMe)₄]₂ and a partially reduced Mo^V complex are in good agreement with experimental data. The reduced Mo^III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.     

试析当前美国实力地位的变化

当前,美国深陷伊拉克战争泥潭,有人提出美实力地位正发生由盛转衰的变化.通过分析可知美国硬实力仍举世无双,软实力在世界各地仍具有重要影响,而美国创新机制和自我修复能力为美提供巨大的力量来源.在未来较长时间内美国仍将保持一超独霸地位.另一方面,世界各国对美国更加缺乏信任,伊拉克战争大大销蚀美实力等,都构成了美国实力的局限.鉴此,美国不得不加强国际合作,承担相应国际责任,外交政策最终向现实主义回归.     

生姜增产技术及病害的防治

研究了催芽大小,遮荫程度,常用肥料-氮、磷、钾肥、微肥-锌、硼、植物激素-乙烯利和绿植灵对生姜的增产作用及生姜常见病害--姜瘟病、班点病和炭疽病的症状,病原、传播途径、发病条件及防治方法.     

ON THE UNIFORM DISSIPATIVITY OF SOME FIFTH-ORDER NON-LINEAR DIFFERENTIAL EQUATIONS

This paper studies the problem of uniformly dissipative solutions of somefifth order non-linear differential equations by the use of frequency domaintechnique. We use the generalized theorem of Yacubovich on dissipativity toobtain some new sufficient conditions of the existence of solutions that aredissipative for (1.1) and (1.2).     

Reaction of silyl ketene acetals with epoxides: a new method for the synthesis of γ-butanolides

Titanium tetrachloride promoted reaction of silyl ketene acetals with epoxides, followed by acidic work-up, affords butanolides in moderate/good yields. With epihalohydrins the reaction is regioselective and occurs at the less substituted end of the epoxide; the γ-haloalkyl-γ-butanolides thus obtained can be further transformed into various products.     

New tri- and tetracyclic diterpenes from Euphorbia villosa

Three new tetracyclic diterpenes were isolated from the chloroform-soluble extract of Euphorbia villosa, together with one new and one known lathyrane diterpene. The structures were elucidated by means of various spectroscopic methods, including HREI-MS, HRFAB-MS, UV, and 1D and 2D NMR techniques. Spectral analyses revealed that two of the tetracyclic compounds contain the rare 5-6-6-4 fused ring system, while the third has a 5-6-7-3 fused diterpene core. Such diterpene skeletons have previously been found only in euphoractines A-E isolated from Euphorbia micractina. As a new structural feature, the diterpene framework described here has a C-2 epimer configuration. The new lathyrane diterpene is a diester of a hitherto unknown polyfunctional parent alcohol.     

Motion Control by ZV Shaper Synthesis Extended for Fractional Systems and Its Application to CRONE Control

Shaping command input or preshaping is used for reducing system oscillation in motion control. Desired systems inputs are altered so that the system finishes the requested move without residual oscillation. This technique, developed by N.C. Singer and W.P. Seering, is used for example in the aerospace field, in particular in flexible structure control. This paper presents the study of ZV shaper for explicit fractional derivative systems (generalized derivative systems). A robustness study of ZV shaper is then presented and applied to improve second generation CRONE control response time. Results from simulation and from a DC motor bench are also given.     

医疗和危险废物高温洁净热处理及环境力学

结合2003年中国的突发危害公众健康的事件，分析了医疗、化学战剂及危险废物的分类、特性，比较了各种高温热处理技术的基本要求，方法分类和设备特点，包括：各类焚烧炉、热解炉和等离子体裂解装置．还对前处理工艺要求，尾气处理工艺等进行了分析讨论，讨论了防止二次污染的技术手段，特别介绍了二噁英等高危险性产物的特性．还介绍了发达国家的医疗废物和危险废物的管理、处置和二次污染防治等情况．