Synthesis of 2,3,8,9-tetramethoxy-11-phenyl-5,6-dihydrodibenz[2,3;7,8]indolizine

2,3,8,9-Tetramethoxy-11-phenyldibenz[2,3;7,8]indolizine was obtainedinhighyieldfrom (6,7-dimethoxyisoquinolin-1-yl)-(3,4-dimethylphenyl)phenylcarbinol by cyclization in the presence of formic acid. The behavior of (6,7-dimethoxyisoquinolin-1-yl)-(3,4-dimethoxyphenyl)methylcarbinol and (6,7-dimethoxyisoquinolin-1-yl-(3,4-dimethoxyphenyl)carbinol was studied under these same conditions. 2,3,7,8-Tetramethoxy-11-phenyl-5,6-dihydrodibenz[2,3;7,8]indolizine was obtained by hydrogenation on rhenium heptasulfide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1233–1238, September, 1993.     

On the origin of changes in topicity observed in Diels–Alder reactions catalyzed by Ti–TADDOLates

New C₂ symmetric TADDOLs containing different groups at the 2-position of the dioxolane ring have been prepared. The Ti catalysts derived from these have been studied in the Diels–Alder reaction of cyclopentadiene and (E)-2-butenoyl-1,3-oxazolidin-2-one. Substituents at the C-2 position of the dioxolane ring can play an important role in determining the selectivity as well as the nature of the major isomer. This effect is more important for TADDOLs containing bulky aromatic groups such as 3,5-dimethylphenyl- or 1-naphthyl at the -positions. Experimental evidence supports the hypothesis that π–π interactions between aromatic groups at the C-2 and the ones at the -positions are critical in this respect.     

Preconcentration and Voltammetric Determination of the Antihypertensive Doxazosin on a C8 Modified Carbon Paste Electrode

 An electrochemical study of the doxazosin oxidative process at carbon paste electrodes using different voltammetric techniques has been carried out. The process is irreversible and controlled by adsorption, giving rise to an oxidation wave around 1.0 V in citric acid-citrate buffer (pH 3.0). A mechanism based on the oxidation of the amine group is postulated. Two methods based on adsorptive stripping (AdS) of doxazosin at the C₈-modified carbon paste electrode (C₈-MCPE), before its voltammetric determination, are studied, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. By means of AdS-DPV and C₈-MCPE, doxazosin can be determined over the 1.0 × 10⁻⁹ to 3.0 × 10⁻⁸ mol L⁻¹ range with a variation coefficient of 2.2% (2.0 × 10⁻⁸ mol L⁻¹) and a limit of detection of 7.4 ×10⁻¹⁰ mol L⁻¹. If AdS-SWV is used, a linear range from 1.0 × 10⁻⁹ to 4.0 × 10⁻⁸ mol L⁻¹ is obtained, the variation coefficient being 2.8% (2.0 × 10⁻⁸ mol L⁻¹, and the limit of detection reached 7.7 × 10⁻¹⁰ mol L⁻¹. The AdS-DPV procedure was applied to the determination of doxazosin in urine and formulations. Received March 13, 1999. Revision December 23, 1999.     

麻疹病毒抗体的酶免疫电化学分析法研究

建立了测定麻疹病毒抗体的酶免疫电化学分析法。其原理是在异相酶联免疫之后用极谱法检测酶促产物。本法采用小型三电极系统“ＤＭＥ－Ｐｔ－Ａｇ／ＡｇＣｌ”直接与商品酶联板配套使用，简化了操作步骤。对测定麻疹抗体的合适条件以及灵敏度，特异性等作了考察。结果表明，本法特异性强，灵敏度高，检测范围宽，不受样品颜色、浊度、杂散光及酶联板自身光吸收不均一的影响；应用于测定三批共１１８份血清样品，阳性率分别为１５％（６／４０），６２．５％（２５／４０）和３１．５８％（１２／３８），用４６份样品对本法和ＥＬＩＳＡ作相关性检验，其相关性良好（γ＝０．７７．ｔ＿ｒ＝１０．８４，Ｐ＜０．００１，相关显著）。     

Improvement of the properties of polyarylate reinforced with liquid crystalline polymers

Blends of polyarylate of bisphenol A, PAr, with two commercial main chain liquid crystalline polymers, Vectra A950 and Vectra B950, are studied. From dynamic viscoelastic measurements it is deduced that both systems (PAr/Vectra A950 and PAr/Vectra B950) are immiscible and scanning electron microscopy (SEM) micrographs show the presence of spherical domains of the liquid crystalline polymer when PAr constitutes the matrix. Extrusion capillary measurements reveal that, under conditions of temperature and shear rate similar to those of processing, the viscosity is reduced to approximately 10% of its value when the content of liquid crystalline polymer is only 20%. This great improvement of the rheological properties is observed in both PAr/Vectra A950 and PAr/Vectra B950 blends. The effect of draw ratio on Young's modulus for different compositions is also analyzed, pointing out the reinforcing action of both liquid crystalline polymers on polyarylate: for instance, 20% of Vectra B950 in the blend gives rise to a 700% increase of the modulus of fibres prepared at a draw ratio of 50. SEM of the extrudates reveals that the spherical domains are elongated at the entrance of the capillary giving rise to a microfibrillar morphology which is related to the excellent rheological and mechanical properties of the blends.     

CRYSTAL AND MOLECULAR STRUCTURE OF THE COMPLEX OF METHOXYCARBONYLETHYLTIN TRICHLORIDE WITH SALICYLIDENE－M－TOLUIDINE

ＣＲＹＳＴＡＬＡＮＤＭＯＬＥＣＵＬＡＲＳＴＲＵＣＴＵＲＥＯＦＴＨＥＣＯＭＰＬＥＸＯＦＭＥＴＨＯＸＹＣＡＲＢＯＮＹＬＥＴＨＹＬＴＩＮＴＲＩＣＨＬＯＲＩＤＥＷＩＴＨＳＡＬＩＣＹＬＩＤＥＮＥ－Ｍ－ＴＯＬＵＩＤＩＮＥＦａｎｇＸｉｎＦＵ；ＸｉｕＪｕａｎＬＩ；Ｈ...     

Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.     

On Transition Structures for Hydride Transfer Step in Enzyme Catalysis. A Comparative Study on Models of Glutathione Reductase Derived from Semiempirical, HF, and DFT Methods

As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling.     

Decomposition of pseudo-radioactive chemical products with a mathematical approach

The aim of this paper is to study the decomposition of pseudo–radioactive products that follow a dynamics determined by a trigonometric factor. In particular for maps of the form $e^{\cos (\pi t)}$ is proved that an asymptotic sampling recomposition property, generalizing the classical Shannon–Whittaker–Kotel’nikov Theorem, works.