Determination of traces of fluorine or sulfur by x-ray analysis

New X-ray methods have been developed for the determination of as little as 1 μg of fluorine or as little as 0.1 μg of sulfur. Fluorine as fluoride is precipitated as lanthanum fluoride in 75% ethanol-water mixture and determined by measuring the amount of lanthanum present in the precipitate. Sulfur as sulfate is precipitated as barium sulfate from a barium sulfate saturated 50% ethanol-buffer mixture, using selenate as a coprecipitant, and determined by measuring the amount of sulfur present. Sulfur as sulfide is precipitated as cadmium sulfide and determined by measuring the amount of sulfur or cadmium in the precipitate.     

Catalytic enantioselective Strecker reaction of ketoimines using catalytic amount of TMSCN and stoichiometric amount of HCN

Catalyst loading as low as 0.1 mol % was achieved in the enantioselective Strecker reaction of ketoimines. Excellent enantioselectivity was obtained with a combined use of a catalytic amount of TMSCN and a stoichiometric amount of HCN as a reagent, and a chiral gadolinium complex as a catalyst.     

GC-MS Determination of an Unknown Pesticide. II. An Experiment Investigating Quality of Analysis Using Random Sampling and Estimation of Variance

Newly devised components are described which significantly enhance both the scientific and pedagogical components of a previously published, qualitatively oriented experiment for students in an undergraduate instrumental analysis course. To provide a laboratory exercise containing as much real-world experience as possible, the earlier experiment was modified in such a way as to allow its use as a quantitative experiment illustrating such principles as sampling, experimental design, analysis of variance, and the use of internal standards.     

Synthesis of a bicyclic analogue of AZT restricted in an unusual O4'-endo conformation.

The [3.2.0]bicyclic beta-nucleoside analogue 5 has been designed as a conformationally restricted analogue of the anti-HIV drug AZT. The synthesis of 5 as well as its alpha-anomer 29 is hereby described. The synthesis was accomplished from D-arabinose via a modified Corey-Link procedure stereoselectively incorporating the azide moiety as well as a methyl ester function. When the tert-butyldiphenylsilyl group was used as a permanent protecting group, a selective formation of an oxetane ring failed. When using the p-methoxyphenyl group as a permanent protecting group, 5 and 29 were efficiently obtained via a selective reduction of the ester, a nucleobase coupling followed by separation of the anomers and ring-closing procedures. The nucleoside 5 is conformationally restricted in an unusual O4'-endo (East) conformation, which is an intermediate between the North- and South-type conformations. Nevertheless, neither 5 nor 29 displayed any anti-HIV activity.     

核-壳型赤藓红分子印迹聚合物的制备及吸附性能的评价

以氨基化修饰的SiO_2为内核,人工合成色素赤藓红为模板,甲醇/水为溶剂,4-乙烯基吡啶为功能单体,二甲基丙烯酸乙二醇酯为交联剂,偶氮二异丁腈为引发剂,采用表面印迹技术,制备核-壳型赤藓红分子印迹聚合物。通过红外光谱对其结构进行表征,并通过动力学吸附、等温饱和吸附和实际样品加标实验对其吸附性能进行评价。结果表明,核-壳型赤藓红分子印迹聚合物具有较快的吸附能力,在15min左右达到吸附平衡,有较好的吸附容量,能够从复杂的食品样品中选择性吸附模板,且回收可达85%。     

Effect of butterfly-shaped sulfur-bridged ligand and counter anions on the catalytic activity and diastereoselectivity of organobismuth complexes

In the direct Mannich reaction and synthesis of α,β-unsaturated ketones, the use of organobismuth complexes as catalysts leads to high diastereoselectivity and products of single trans conformation. In this paper, we illustrate the relationship between structure and catalytic activity as well as diastereoselectivity of organobismuth complexes having a 5,6,7,12-tetrahydrodibenz [c,f][1,5]thiobismocine framework as well as bearing a butterfly-shaped sulfur-bridged ligand and tunable anions. With the exposed bismuth center acting as a Lewis acid site and the uncoordinated lone pair electrons of sulfur as a Lewis base site, the cationic organobismuth complexes work as bifunctional Lewis acid/base catalysts. Due to the steric influence of the butterfly-shaped structure and synergistic effect of Lewis acid and Lewis base centers, the complexes can direct substrate attack in organic synthesis. By adjusting the electron-withdrawing ability of the counter anions, the S-Bi bond strength can be regulated, leading to a significant change in Lewis acidity and Lewis basicity as well as catalytic activity. Through synergistic modulation of the above effects, one can control the diastereoselectivity of the organobismuth complexes for the generation of a single diastereoisomer.     

Effects of macromolecules on the crystallization of CaCO3 the Formation of Organic/Inorganic Composites

The effects of macromolecules as soluble additives and solid matrices have been examined for the crystallization of CaCO₃. A vaterite form grows on a glass substrate in the presence of poly(glutamic acid) (PGA) containing a carboxylic acid group as a soluble additive. In contrast, no crystal growth has been observed when poly(acrylic acid) (PAA) exists as an additive though it has the same functional group. The conformation or the backbone structure of the polymers may have an influence on the crystal polymorph of CaCO₃. Thin film states of CaCO₃ crystals have been obtained as organic/inorganic composites with chitosan that acts as a solid matrix in the presence of PAA or PGA as a soluble additive.     

用双锂引发剂制备热塑弹性体S(IB)S

苯乙烯-二烯烃热塑弹性体(SDS)是橡胶代用品和热熔压敏胶的主体材料。其粘接强度低、耐老化性差常需配以增粘剂、防老剂。苯乙烯．异戊二烯嵌段共聚物(SIS)性能比SBS和EvA优越,我国异戊二烯原料不足、价格较高。以正丁基锂为引发剂的热塑弹性体S(IA)S性能与SIS相近。本文以有机双锂为引发剂、苯乙烯、丁二烯和异戊二烯为共聚单体,采用两步加料法合成热塑弹性体S(IB)S,对其结构、性能进行了表征。     

醋酸和丙三醇对制备SrTiO3的影响

醋酸和丙三醇对制备ＳｒＴｉＯ_３的影响颜秀茹，霍明亮，王建萍，王菲，曾淑兰（天津大学化学系天津３０００７２）关键词　冰醋酸，溶胶－凝胶过程，丙三醇，ＳｒＴｉＯ_３ＳｒＴｉＯ３是电子材料中使用最广的材料之一，有关它的制备已有不少报道。一般可以通过ＳｒＣＯ...     

Synthesis of All Stereoisomers of RK460 and Evaluation of Their Activity and Selectivity as Abscisic Acid Receptor Antagonists

The PYR/PYL/RCAR protein families have recently emerged as receptors of the phytohormone abscisic acid (ABA, 1 ), which regulates plant responses to environmental stress. These families have multiple members with different physiological actions, and so selective agonists or antagonists are needed both as tools to elucidate functional differences and as lead compounds for agrochemicals. We previously identified RK460 (rac- 3 a ) as a PYR1-selective antagonist, and showed that it possesses five stereocenters on a 6,5-cis-bicyclo skeleton. Here, we synthesized all the stereoisomers of RK460 and evaluated their activity towards a panel of receptors. Relative stereochemistry as well as absolute stereochemistry was important for selective action.     

Influence of architecture on the kinetic stability of molecular assemblies

The strength of a multimolecular system depends on the number of interactions that hold it together. Using dynamic force spectroscopy, we show how the kinetic stability of a system decreases as the number of molecular bonds is increased, as predicted by theory. The data raise important considerations for experimental tests of bond strength and, as a paradigm, suggest both routes to and pitfalls in methods for computational simulation of molecular transitions, such as ligand binding and protein folding.     

Direct Visualization of Electromagnetic Microfields by Superposition of Two Kinds of Electron Holograms

A new electron holographic method is presented to directly visualize pure phase objects such as electromagnetic microfields, which is achieved by superposition of two kinds of electron holograms. The method is very simple and is twice as sensitive as the conventional double-exposure electron holography and the four-electron-wave interference. Using this technique, an electric field around a charged latex sphere and a magnetic field around a barium ferrite particle have been directly observed.     

Design of Nanoscopic Vehicles for Drug Targeting Based on Micellization of Amphiphiuc Block Copolymers

Block copolymers in a selective solvent (a good solvent for one block but a nonsolvent for the other) form micellar structures through the association of the insoluble segments. Micelles formed through the association of amphiphilic block copolymers have several advantageous features as drug carrier systems due to their considerable thermodynamic stability as well as to the formation of a hydrophobic core separated from the outer aqueous milieu by the palisade of hydrophilic segments. The core acts as the microcontainer of hydrophobic drugs. This paper presents a concept and strategy for using a block copolymer micelle as a nanoscopic virus-mimicking carrier of anticancer drugs to treat solid tumors.     

Aspects of Electrochemical Behavior of Aldehydes and Ketones in Protic Media

Reduction of carbonyl group in aldehydes and ketones, as well as oxidation of numerous aldehydes is discussed, as well as those reductions of organic compounds where the C?O group activates cleavage of an adjacent C? X bond where X is a good leaving group like halogen, OH, NH₂ or SR or activates hydrogenation of an adjacent C?C group. Survey involves aliphatic and aromatic aldehydes, aryl alkyl and diaryl ketones, as well as α‐ketoacids, 1,2‐diketones and compounds where the carbonyl group is a part of a ring. The role of acid–base, hydration–dehydration and in some cases keto–enol equilibria on electrochemical behavior is pointed out, as well as the role of buffer kind and concentration and the nature of the cation of supporting electrolyte. Better understanding of these factors promises finding of best conditions for electroanalytical procedures.     

Electrochemical polymerization of acetylene on a surface of platinum

Polyacetylene (PA) deposited on a platinum surface is synthesized by electrochemical polymerization of acetylene in a cell with platinum strip as cathode, nickel strip as anode, and nickel bromide in acetonitrile as electrolyte. The electrolytic solution is presaturated with acetylene. The PA so produced has a granular morphology and high surface area (79 m²/g), and is insoluble. Polymerization at lower temperature gives higher content in cis units. It has the same chemical structure as that produced using the Shirakawa method as examined by elemental analysis, infrared spectroscopy, x-ray diffraction, and differential scanning calorimetry.     

Solid-phase synthesis of lipidated peptides

Characteristic partial structures of lipidated proteins embodying different lipid groups as well as additional fluorescent tags or a maleimide for coupling to proteins can be synthesized readily by means of a new solid-phase technique employing the oxidative cleavage of the hydrazide linker as well as on-resin farnesylation and palmitoylation after appropriate deprotection of cysteine thiol groups as the key steps.     

Criteria of efficiency of cellulose acetate plasticization

Using cellulose acetate plastics as an example, it was shown that the search for the optimal concentrations of plasticizers should take into account the compatibility of components, as well as the thermophysical and mechanical properties of plasticized polymers. It was suggested that the temperature range of durability of a plastic, i.e., the difference between its glass-transition and brittle temperatures, be used as a plasticization efficiency criterion. Plasticizers that are well compatible with a polymer at processing temperatures but show a limited compatibility at its service temperatures make it possible to manufacture goods with an extended durable temperature range.     

Effects of nanoconfinement on the morphology and reactivity of organic materials

When organic materials are placed in environments which physically confine the materials at the nanometre scale, interfacial effects and confinement-induced loss of entropy can significantly alter materials' properties such as the glass transition temperature as well as the nanoscale morphology as compared to a "free" system. In block copolymers, nanoconfinement leads to a range of unusual self-organized nanoscale morphologies. In this article, attempts to induce nanoconfinement effects in new polymer systems as well as at interfaces will be highlighted and some possible future implications for organic synthesis and biology will be discussed.