对比法在有机反应机理教学中的运用

对比是在分析和综合的基础上将各种事物加以比较 ,并确定它们之间异同的一种思维方法 ,是认识客观事物的科学方法之一。在教学中如果善于运用 ,就能更好地提高教学质量。　　在有机化学教学过程中 ,可以进行对比的概念和反应很多 ,如基本概念的对比 ,反应类型的对比 ,反应条件的对比 ,中间体的对比 ,反应活性的对比等。本文仅就对比法在有机反应机理教学中的运用作一探讨。　　在基础有机化学教学中 ,所涉及到的有机反应机理从反应类型上来分主要有自由基反应(包括自由基取代和自由基加成 ) ,离子型反应 (包括亲电取代、亲电加成、亲核取代…     

Synthesis,structure and biological activity of diorganotin derivatives with pyridyl functionalized bis(pyrazol‐1‐yl)methanes

Three pyridyl functionalized bis(pyrazol‐1‐yl)methanes, namely 2‐[(4‐pyridyl)methoxyphenyl] bis(pyrazol‐1‐yl)methane (L¹), 2‐[(4‐pyridyl)methoxyphenyl]bis(3,5‐dimethylpyrazol‐1‐yl)methane (L²) and 2‐[(3‐pyridyl)methoxyphenyl]bis(pyrazol‐1‐yl)methane (L³) have been synthesized by the reactions of (2‐hydroxyphenyl)bis(pyrazol‐1‐yl)methanes with chloromethylpyridine. Treatment of these three ligands with R₂SnCl₂ (R = Et, n‐Bu or Ph) yields a series of symmetric 2:1 adducts of (L)₂SnR₂Cl₂ (L = L¹, L² or L³), which have been confirmed by elemental analysis and NMR spectroscopy. The crystal structures of (L²)₂Sn(n‐Bu)₂Cl₂·0.5C₆H₁₄ and (L³)₂SnEt₂Cl₂ determined by X‐ray crystallography show that the functionalized bis(pyrazol‐1‐yl)methane acts as a monodentate ligand through the pyridyl nitrogen atom, and the pyrazolyl nitrogen atoms do not coordinate to the tin atom. The cytotoxic activity of these complexes for Hela cells in vitro was tested. Copyright © 2010 John Wiley & Sons, Ltd.     

A rapid assay for angiotensin‐converting enzyme activity using ultra‐performance liquid chromatography–mass spectrometry

Angiotensin‐converting enzyme (ACE) plays an important role in the renin–angiotensin system and ACE activity is usually assayed in vitro by monitoring the transformation from a substrate to the product catalyzed by ACE. A rapid and sensitive analysis method or ACE activity by quantifying simultaneously the substrate hippuryl–histidyl–leucine and its product hippuric acid using an ultra‐performance liquid chromatography coupled with electrospray ionization‐mass spectrometry (UPLC‐MS) was first developed and applied to assay the inhibitory activities against ACE of several natural phenolic compounds. The established UPLC‐MS method showed obvious advantages over the conventional HPLC analysis in shortened running time (3.5 min), lower limit of detection (5 pg) and limit of quantification (18 pg), and high selectivity aided by MS detection in selected ion monitoring (SIM) mode. Among the six natural products screened, five compounds, caffeic acid, caffeoyl acetate, ferulic acid, chlorogenic acid and resveratrol indicated potent in vitro ACE inhibitory activity with IC₅₀ values of 2.527 ± 0.032, 3.129 ± 0.016, 10.898 ± 0.430, 15.076 ± 1.211 and 6.359 ± 0.086 mm , respectively. A structure–activity relationship estimation suggested that the number and the situation of the hydroxyls on the benzene rings and the acrylic acid groups may play the most predominant role in their ACE inhibitory activity. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrochemical performance of a nonaqueous rechargeable lithium-air battery

Nonaqueous rechargeable lithium-air battery has so high specific capacity and specific energy that it is being widely researched by academia, corporation, and different research institutes. When used in dried air and absorbing oxygen form the air, this battery is called lithium-air battery, and its specific capacity based on cathode active material (oxygen) is infinite. However, its cycle performance is very limited as reported by the state-of-the-art researches. This cycle problem is mainly caused by instability of electrolyte. Based on electroanalysis of materials’ electrochemical property, a stable electrolyte solvent (sulfolane) and a lithium salt LiBF₄ are selected as electrolytes in this work. Coupled with other eligible battery materials and careful assembly, the lithium-air battery exhibits favorable cycle performance. Above all, this lithium-air system is evaluated objectively in this paper.     

Preparation and performance of sulfur–carbon composite based on hollow carbon nanofiber for lithium-sulfur batteries

A unique structured hollow carbon nanofiber–sulfur composite material (HCF–S) was fabricated and characterized in lithium-sulfur batteries. It is found that a part of spherical sulfur particles are located in the voids formed by the intertwined fibers and the others are confined in hollow channel of the HCF. The high conductive and porous HCF favors the construction of stable three-dimensional conducting network and convenient infiltration of the electrolytes into the cathode. The HCF–S cathode exhibits excellent electrochemical performance in the electrolyte with LiNO₃. By contrast, the ionic liquid electrolyte provides insufficient shuttle suppression and weakens ion transport, which leads to poor cycle and rate capability.     

Kinetic Study of the Degradation of PAC-1 and Identification of a Degradation Product in Alkaline Condition

A selective and validated stability-indicating LC method was developed for the kinetic study of the degradation of PAC-1, which was carried out in aqueous solutions at 37, 60, 80 and 100 °C with pH 1.5–9.0. Separation was performed on a Kromasil C₁₈ column with acetonitrile–water–fomic acid (30:70:0.1, v/v/v) as mobile phase with a flow rate of 1.0 mL min⁻¹ at 281 nm. The degradation rate obtained indicated a first-order reaction law and the activation energy (E _a) was calculated. The results showed that temperature and pH values were significant factors affecting the degradation of PAC-1. An unknown degradation product in alkaline condition was isolated using a reverse-phase semi-preparative LC system. The structure of the degradation product is identified as 2-hydroxy-3-(2-propenyl)-[[2-hydroxy-3-(2-propenyl)phenyl]methylene]hydrazone utilizing the ¹H NMR, ¹³C NMR, IR and Q-TOF-MS techniques.

     

Copper oxide nanoarray based on the substrate of Cu applied for the chemical sensor of hydrazine detection

This communication reports on a novel amperometric hydrazine sensor of CuO nanoarray based on a Cu substrate. Copper oxide nanoarray was directly grown on Cu substrates using a one-step facile hydrothermal method and was characterized using scanning electron microscopy and X-ray powder diffraction. The electrochemical study has shown that the CuO nanoarray exhibits higher catalytic effect on the hydrazine than the normal CuO nanoparticles. This may be attributed to the special structure of the nanomaterials esp. the substrate of the electric Cu. And the amperometric response showed that the CuO nanoarray modified glassy carbon electrode has a low detection and a high sensitivity for hydrazine.