SnCl2-mediated carbonyl allylation in fully aqueous media

Systematic studies were performed on SnCl₂-mediated carbonyl allylation reaction between aldehydes and allyl halides in fully aqueous media. Totally three valuable reaction systems were discovered, which were SnCl₂/CuCl₂, SnCl₂/TiCl₃, and SnCl₂/PdCl₂. They all provided good to excellent yields in the allylation of aliphatic and aromatic aldehydes under very mild and convenient conditions. SnCl₂, by itself, was also found to be effective for the allylation reaction when allyl bromide was employed. However, the SnCl₂-only reaction could only tolerate very small amount of water as the solvent. The SnCl₂/CuCl₂, SnCl₂/TiCl₃, and SnCl₂/PdCl₂-mediated reactions exhibited good regioselectivity favoring the γ-adduct when cinnamyl halides were employed as the allylation reagent. The same reactions with cinnamyl halides also showed good diastereoselectivity favoring the anti-product. Mechanistic studies using proton NMR techniques suggested that the additive (i.e., CuCl₂, TiCl₃, PdCl₂) could accelerate the formation of allyltin intermediate, but this step was shown not to be the most important for the allylation. Thus we proposed that the Lewis acid catalysis effect exerted by the additive was the main reason for the observed reactivity enhancement.     

Kinetic parameters of the In(III)/In(I) electrode reaction in bromide medium

The electrode kinetic parameters of the In(III)/In(I) couple in acidic 4M bromide solution have been determined by means of the rotating disc electrode technique.

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Die elektrochemisch-kinetischen Parameter des In(III)/In(I)-Redoxsystems in Bromidlösung (Kurze Mitteilung)

Zusammenfassung Die elektrochemisch-kinetischen Parameter am In(III)/In(I)-Redoxsystem wurden in saurer 4-M-Bromidlösung mittels der rotierenden Scheibenelektrode bestimmt.

     

Direct spectrophotometric method for the determination of cobalt with indane 1,2,3-trionetrioxime in aqueous medium

A simple, sensitive and selective Spectrophotometric method has been developed for the determination of cobalt using indane 1,2,3-trionetrioxime (ITT): The method is based on the colour reaction between ITT and cobalt(II) in sodium acetate-acetic acid buffer (pH 4.5–7.5) medium. The calibration graph for measurement at 320 nm is linear in the range 1.18–23.60g of cobalt per 25 ml, with molar absorptivity of 5.32×10⁴1mol^–1 cm^–1. The effect of interfering ions has been studied and the method was applied to the determination of cobalt in alloys, with good results.     

Monolayer adsorption isotherms and a disordered medium model

A model of disordered medium is proposed to describe the monolayer adsorption isotherm on heterogeneous surfaces. The model is based on the premise that adsorption medium consists of separate regions in each of which there is a permanent local equilibrium constant, the character of the changes of which is determined by the disorder parameter of the medium. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 189–193, May–June, 2006.     

Electrostatic interaction between ion-penetrable membranes in a salt-free medium

A set of coupled equations is given which determines the distributions of the electric potential and counterions in a system of two interacting identical ion-penetrable membranes of thickness d at separation h immersed in a salt-free medium containing only counterions. The solution to these coupled equations also gives the electrostatic repulsive force between the membranes. It is shown that the interaction force remains finite at h-->0, unlike the case of the interaction between two planar charged surfaces (d-->0), and that the interaction force becomes independent of the membrane fixed charge and membrane thickness d at very large h. Finally, an approximate single transcendental equation giving the solution to the coupled equations is derived.     

Optimized POCl3-assisted synthesis of 2-amino-1,3,4-thiadiazole/1,3,4-oxadiazole derivatives as anti-influenza agents

Although recent decades have witnessed the synthesis of 1,3,4-thiadiazoles via phosphorus POCl₃-promoted cyclization reaction, simultaneous access to 2-amino-1,3,4-thiadiazole and 2-amino-1,3,4-oxadiazole analogs remains unexpected and elusive. Herein, a detailed regiocontrolled synthesis of 2-amino-1,3,4-thiadiazoles in good to high yields with good regioselectivities from readily available thiosemicarbazides using POCl₃ was disclosed. Meantime, to establish a comprehensive structure–activity relationship, 2-amino-1,3,4-oxadiazole derivatives as single regioisomers were prepared via EDCI·HCl-triggered cyclization of the thiosemicarbazide intermediates. The in vitro anti-influenza assays proved that the selected compounds with the pyrazine/pyridine ring exhibited certain inhibitory activities against influenza A virus strains A/HK/68 (H3N2) and A/PR/8/34 (H1N1) in MDCK cells. Among them, N-(adamantan-1-yl)-5-(5-(azepan-1-yl)pyrazin-2-yl)-1,3,4-thiadiazol-2-amine (4j) was the most active compound, and exhibited favorable activity with EC₅₀ values of 3.5 μM and 7.5 μM, respectively. In addition, the molecular docking results explained the reason why compound 4j had dual inhibitory activity and revealed the reasonable binding mode of this compound with the M2-S31N and M2-WT ion channels. This compound had the potential to be further developed as an anti-influenza drug.     

Drift of Spiral Waves in Complex Ginzburg-Landau Equation

The spontaneous drift of the spiral wave in a finite domain in the complex Ginzburg-Landau equation is investigated numerically. By using the interactions between the spiral wave and its images, we propose a phenomenological theory to explain the observations.     

Kerr效应对非线性J-C模型辐射谱的影响

研究了Kerr介质腔中非线性J-C模型的辐射谱.导出了双模初始光场处于任意量子态时辐射谱的计算公式,给出了光场处于数态、相干态和压缩真空态时的数值结果,讨论了Kerr效应和初始场强对辐射谱的影响.发现在光子数态的情况下,Kerr效应使低频峰增强、高频峰减弱,并使各峰向右移动.在初始腔场为较强的相干态时,原子辐射谱明显地分成两个拱形的梳状峰群,Kerr效应的增强使左侧峰群增高,右侧的边峰受到抑制.在压缩真空态情况下,边带峰只出现在中心频率双峰的左侧,随Kerr效应和初始场的增强,边峰个数也随之增多.无论哪种情况都破坏谱结构的对称性,在强场条件下Kerr效应的影响更加显著.     

双层散射介质的单次后向散射光谱分析

从上皮组织的结构特点出发,基于米氏(Mie)散射理论,建立了双层散射介质的单次后向散射光谱的理论模型,该模型通过偏振门屏蔽来自下层的噪声背景,只保留来自上层的单次散射光。计算分析了粒子的形态学参量如平均尺寸及其分布、相对折射率变化时,单次散射光谱的特征。并用傅里叶波形分析法研究了这些参量对单次后向散射光谱曲线形状及其谐波幅值的影响。结果表明,这些只经历了表层粒子单次散射的光谱信号对表层粒子的平均尺寸及其分布、相对折射率具有灵敏性。对光谱曲线波纹结构的幅值、频率,散射强度,光谱谐波的幅值有直接的影响。研究结果对早期癌症的散射光谱特征识别及其特征提取有重要的实用价值。     

短脉冲激光与介质相互作用的扩散模型

推导了扩散近似方程,通过半无限大均匀介质计算,用扩散理论分析解验证了数值方法的有效性.模拟了光在非均匀介质内的传输过程,给出了介质内光通量随时间变化的空间分布.结果表明,该基于扩散模型的数值方法能够模拟短脉冲光在强散射介质中的传播过程以及漫散射光的时间变化特性,并且借助于光通量空间分布能够准确模拟非均匀介质内内含物的位置.