SSZ-53 and SSZ-59: two novel extra-large pore zeolites

The syntheses, structure solutions, and physicochemical and catalytic characterizations of the novel zeolites SSZ-53 and SSZ-59 are described. SSZ-53 and SSZ-59 were synthesized under hydrothermal conditions with the [1-(4-fluorophenyl)cyclopentylmethyl]trimethyl ammonium cation and 1-[1-(4-chlorophenyl)cyclopentylmethyl]-1-methyl azocanium cation, respectively, as structure-directing agents. The framework topology of SSZ-53 was solved with the FOCUS method, and the structure of SSZ-59 was determined by model building. Rietveld refinement of synchrotron X-ray powder diffraction data confirms each proposed model. SSZ-53 and SSZ-59 each possess a one-dimensional channel system delimited by 14-membered rings. Results from transmission electron microscopy, electron diffraction, catalytic experiments (spaciousness index and constraint index tests), and argon and hydrocarbon adsorption experiments are consistent with the proposed structures.     

Activation of trisacryl gels with chloroformates and their use for affinity chromatography and protein immobilization

In this study we describe the activation with chloroformates of Trisacryl-GF-2000, a new synthetic gel support that is stable, hydrophilic, and contains large amounts of hydroxyl groups available for activation. Of all the reagents tested, the activation withN-hydroxysuccinimide-chloroformate andp-nitrophenylchloroformate in organic solvents provides the best activation yield and subsequent coupling. When Trisacryl was activated in acetone with the chloroformates in the presence of 4-dimethylaminopyridine as base and catalyst, up to 30% of the hydroxyl groups, (i.e., 1/repeating unit) could be activated. Amino-containing ligands and proteins could be coupled to these carriers at pH 8 or higher. For better results in affinitychromatographic applications, spacers of ε-amino caproic acid or diaminohexane were introduced. The efficacy of these columns was demonstrated by purification of enzymes, antibodies, and antigens. The performance of these new columns were compared with that of Sepharose columns activated in various ways. In every case, the properties of the Trisacryl support proved superior with particular reference to the purity of the product obtained.     

安眠镇静药物的串联质谱分析方法

气相色谱以及气相色谱／质谱联用经常被用来分析生物体液样品中的药物。用这些方法分析时，需要在色谱分析前，进行长时间的样品制备和衍生化过程。本文描述了用地识别１６安眠镇静药物的ＥＩ／ＭＳ／ＭＳ过程，并且对两例服毒自杀者的尿样进行了检测。     

信息型常见毒物质谱用户库的建立及其在毒物快速筛选上的应用研究

质谱定性是目前世界上最通用的定性分析方法之一,在法庭科学领域毒物分析实践中,质谱一直是对未知样品进行药毒物筛选检测的利器.     

Synthesis and Crystal Structure of p-tert-Butylthiacalix[8]arene: A New Member of Thiacalixarenes

Even though it was obtained in poor yield, p-tert-butylthiacalix[8]arene (TC8A) has been synthesized as a new member of thiacalix[n]arenes by the terephthalate-induced cyclization of a mixture of acyclic oligomers, which was obtained by the reaction between p-tert-butylphenol and sulfur with CaO in ethylene glycol/diphenyl ether system. Slow evaporation of the chloroform solution of TC8A afforded guest-free crystals consisting of TC8A itself. The close-packed crystal structure of TC8A resembles that of p-tert-butylcalix[8]arene (C8A) closely, containing a plated loop molecular structure.This revised version was published online in July 2005 with a corrected issue number.     

固定pH滴定法测定弱酸弱碱性药物

报道一种水溶液吕测定弱酸弱碱性药物的新型滴定分析方法－固定ｐＨ滴定法，其理论基础是弱酸弱碱在水溶液中各种存在形式的分布系数在ｐＨ值固定时为常数，对甲硝唑，盐酸美西律等离散常数在１０＾－８至１０＾－１１范围内的７种弱酸弱碱性药物进行测定。结果与药典法吻合，回收率在９９．４％～１００．６％，方法简便，快速，准确，制剂中的赋形剂及色物不影响测定。     

Polyelectrolyte microcapsules templated on poly(styrene sulfonate)-doped CaCO3 particles for loading and sustained release of daunorubicin and doxorubicin

A strategy to incorporate and release anti-cancer drugs of daunorubicin (DNR) and doxorubicin (DOX) in preformed microcapsules is introduced, which is based on charge interaction mechanism. Oppositely charged poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) were assembled onto PSS doped-CaCO₃ colloidal particles in a layer-by-layer manner to yield core-shell particles. After removal of the carbonate cores, hollow microcapsules with entrapped PSS were fabricated, which showed spontaneous loading ability of positively charged DNR and DOX. The drug loading was confirmed quantitatively by observations under confocal laser scanning microscopy, transmission electron microscopy and scanning force microscopy. Quantification of the drug loading was performed under different conditions, revealing that a larger amount of drugs could be incorporated at higher drug feeding concentrations and higher salt concentrations. However, putting additional polyelectrolyte layers on the microcapsules after core removal resulted in weaker drug loading efficiency. The drug release behaviors from the microcapsules with different layer numbers were studied too, revealing a diffusion controlled release mechanism at the initial stage (4 h).     

Synthetic receptors based on calix[4]arene functionalized at the lower rim in molecular recognition of dicarboxylic, α-hydroxycarboxylic,and α-amino acids

New calix[4]arenes, di- and tetrasubstituted at the lower rim, with different functional groups were synthesized. They were studied as carriers of a series of dicarboxylic and -hydroxycarboxylic acids through a liquid impregnated membrane. The calix[4]arenes under study are capable of molecular recognition of oxalic acid in the series of structurally similar dicarboxylic and -hydroxycarboxylic acids. The regularities found make it possible to change purposefully the receptor ability of 1,3-disubstituted calix[4]arenes by variation of the nature of substituents.     

Detection of potential membrane receptor proteins concerning circadian rhythmic leaf movement of legumes using novel photoaffinity probe compounds

Circadian rhythmic plant leaf movement, called nyctinasty, is controlled by a time-course change in the internal concentration of the leaf-movement factor in the plant body. We report that specific binding protein (210 and 180 kDa) for a leaf-movement factor, potassium lespedezate, is contained in the plasma membrane of the plant motor cell. These proteins would be potential receptors for leaf-movement factor to control the leaf movement.     

Human topoisomerase I poisoning: docking protoberberines into a structure-based binding site model

Summary Using the X-ray crystal structure of the human topoisomerase I (top1) – DNA cleavable complex and the Sybyl software package, we have developed a general model for the ternary cleavable complex formed with four protoberberine alkaloids differing in the substitution on the terminal phenyl rings and covering a broad range of the top1-poisoning activities. This model has the drug intercalated with its planar chromophore between the −1 and +1 base pairs flanking the cleavage site, with the nonplanar portion pointing into the minor groove. The ternary complexes were geometry-optimized and relative interaction energies, computed by using the Tripos force field, were found to rank in correct order the biological potency of the compounds; in addition, the model is also consistent with the top1-poisoning inactivity of berberine, a major prototype of the protoberberine alkaloids. The model might serve as a rational basis for elaboration of the most active compound as a lead structure, in order to develop more potent top1 poisons as next generation anti-cancer drugs.