Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

Effect of ionic additives on the elution of sodium aryl sulfonates in supercritical fluid chromatography

Addition of a small amount of polar solvent (i.e., modifier) to CO2 in packed column supercritical fluid chromatography (SFC) has shown major improvements in both polar analyte solubility and interaction of the polar analyte with the stationary phase. Recently, the addition of an ionic component (i.e., additive) to the primary modifier by one of us has been shown to extend even further the application of SFC to polar analytes. In this work, the effect of various ionic additives on the elution of ionic compounds, such as sodium 4-dodecylbenzene sulfonate and sodium 4-octylbenene sulfonate, has been studied. The additives were lithium acetate, ammonium acetate, tetramethylammonium acetate, tetrabutylammonium acetate, and ammonium chloride dissolved in methanol. Three stationary phases with different degrees of deactivation were considered: conventional cyanopropyl, deltabond cyanopropyl, and bare silica. The effect of additive concentration and additive functionality on analyte retention was investigated. Sodium 4-dodecylbenzene sulfonate was successfully eluted using all the additives with good peak shape under isocratic/isobaric/isothermal conditions. Different additives, however, yielded different retention times and in some cases different peak shapes.     

FFC-1离子交换纤维对酸碱有害气体吸附性能的研究

系统考察了不同直径及反离子形式的FFC-1聚羧酸离子交换纤维对酸碱有害气体的穿透吸附,各种温、湿度条件下的吸水率,以及作为有害气体吸附滤除材料的重复使用与再生性能。研究表明:FFC-1纤维直径的减小有利于提高对有害气体的动态吸附容量。在体系温度、相对湿度分别为15℃、50%时,以3D腈纶为起始原料的钠型FFC-1离子交换纤维的吸水率≥350mg/g.纤维;对SO2的穿透吸附容量可达200mg/g.纤维。FFC-1离子交换纤维具有良好的重复使用与再生能力,经20次再生循环使用后,纤维交换容量未见明显变化。     

Structural and bonding characteristics in transition metal-silane complexes

Transition metal-silane complexes containing metal-eta 2-H-Si coordination display different structural and bonding characteristics in comparison to other sigma-complexes, such as dihydrogen and alkane (agostic) complexes. The different characteristics can be related to the strong sigma*-accepting properties of the eta 2-silane ligand(s) because of the weaker H-Si sigma bond. Various examples of metal-silane complexes have been reviewed and their structural stabilities have been systematically discussed. Silyl-hydride complexes having substantial silyl-hydrido interactions have also been emphasized.     

Electronic-to-vibrational energy transfer reactions.X* + CO (X = O,I and Br)

The vibrational distribution of CO produced from the following two electronic-to-vibrational energy transfer reactions:

have been determined by means of infrared resonance absorption measurements employing a cw CO laser. The CO molecules formed in both reactions were found to be vibrationally excited up to the limits of available electronic energies carried by the excited atoms. A similar result was also observed in the Br(4²P_{$\text{1}\text{2}$}) + CO reaction, in which absorption occurred only in the 1 → 2 band. For the O^* + CO reaction the efficiency of E → V energy transfer was determined to be 16%. Our present results were found to be inconsistent with the impulsive (half-collision) model.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

Fluorescent sensors for the enantioselective recognition of mandelic acid: signal amplification by dendritic branching

Novel chiral bisbinaphthyl compounds have been synthesized for the enantioselective fluorescent recognition of mandelic acid. By introducing dendritic branches to the chiral receptor unit, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Study of the three generation sensors demonstrates that the generation zero sensor is the best choice for the recognition of mandelic acid because of its greatly increased fluorescence signal over the core and its high enantioselectivity. This sensor is potentially useful for the high throughput screening of chiral catalysts for the asymmetric synthesis of alpha-hydroxycarboxylic acids.     

人工神经网络X射线荧光光谱法测定钢中酸溶铝

建立了一种人工神经网络-X射线荧光光谱法测定钢中酸溶铝的方法，用X射线荧光光谱法测定低合金钢中总铝值，应用所建立的ANN-BP网络模型，输入总铝含量直接预测出酸溶铝含量。同时使用改进的BP算法，避免了神经网络学习中可能产生的麻痹现象。该方法用于钢中酸溶铝的测定，结果满意。     

Kinetics of the reaction of C6H5 with HBr

The rate constant for the reaction of phenyl radical with hydrogen bromide has been measured with the cavity-ring-down method at six temperatures between 297 and 523 K. The Arrhenius expression for the H abstraction reaction can be effectively given by: . The values of these parameters are similar to those for the H + HBr reaction, but are in sharp contrast to those for alkyl radical reactions. The gross difference between the alkyl radical reactions and the phenyl and H-atom reactions could be rationalized in terms of the inductive effects of these radicals as measured by Taft's σ* (polar) constants. © 1993 John Wiley & Sons, Inc.