One-pot synthesis of N-methylimidazolium-based porous polymer monolith for capillary electrochromatography via free radical copolymerization and quaterisation

One-pot synthesis of porous polymer monolith decorated with N-methylimidazolium in a capillary was described. The polymer matrix was synthesized by in situ copolymerization and quaterization of 3-chloro-2-hydroxylpropyl methacrylate (CHPMA), ethylene dimethacrylate (EDMA), and N-methylimidazole (N-MIz). The influencing factors including amount of cross-linkers, composition of porogenic solvents, and polymerization temperature on the formation of the monolithic column were investigated. The monolithic column exhibited high column efficiency for thiourea, up to 135 000 plates per meter, and phenylmethanol, up to 102 000 plates per meter. Different types of compounds including alkylbenzenes, phenols, and inorganic anions were successfully baseline separated by capillary electrochromatography (CEC). The separation of theses analytes on the column indicated typical reversed-phase and anion-exchange chromatographic retention mechanism.     

一种卡宾配合物的合成及其在Suzuki反应中的应用

合成了一种N-杂环卡宾的钯配合物,可用于高效地催化芳基溴化物和对甲苯磺酸芳酯对芳基硼酸的Suzuki偶联反应.该反应在二氧六环溶剂中以醋酸钾为助剂、空气氛下80℃即可进行,具有收率高、催化剂容易制备等优点.     

Electronic Coupling between Two Amine Redox Sites through the 5,5′‐Positions of Metal‐Chelating 2,2′‐Bipyridines

Electron delocalization of new mixed‐valent (MV) systems with the aid of lateral metal chelation is reported. 2,2′‐Bipyridine (bpy) derivatives with one or two appended di‐p‐anisylamino groups on the 5,5′‐positions and a coordinated [Ru(bpy)₂] (bpy=2,2′‐bipyridine), [Re(CO)₃Cl], or [Ir(ppy)₂] (ppy=2‐phenylpyridine) component were prepared. The single‐crystal molecular structure of the bis‐amine ligand without metal chelation is presented. The electronic properties of these complexes were studied and compared by electrochemical and spectroscopic techniques and DFT/TDDFT calculations. Compounds with two di‐p‐anisylamino groups were oxidized by a chemical or electrochemical method and monitored by near‐infrared (NIR) absorption spectral changes. Marcus–Hush analysis of the resulting intervalence charge‐transfer transitions indicated that electron coupling of these mixed‐valent systems is enhanced by metal chelation and that the iridium complex has the largest coupling. TDDFT calculations were employed to interpret the NIR transitions of these MV systems.     

Preparation and application of molecularly imprinted polymer solid‐phase microextraction fiber for the selective analysis of auxins in tobacco

As signal molecules, auxins play an important role in mediating plant growth. Due to serious interfering substances in plants, it is difficult to accurately detect auxins with traditional solid‐phase extraction methods. To improve the selectivity of sample pretreatment, a novel molecularly imprinted polymer ‐coated solid‐phase microextraction fiber, which could be coupled directly to high‐performance liquid chromatography, was prepared with indole acetic acid as template molecule for the selective extraction of auxins. The factors influencing the polymer formation, such as polymerization solvent, cross‐linker, and polymerization time, were investigated in detail to enhance the performance of indole acetic acid‐molecularly imprinted polymer coating. The morphological and chemical stability of this molecularly imprinted polymer‐coated fiber was characterized by scanning electron microscopy, infrared spectrometry, and thermal analysis. The extraction capacity of the molecularly imprinted polymer‐coated solid‐phase microextraction fiber was evaluated for the selective extraction of indole acetic acid and indole‐3‐pyruvic acid followed by high‐performance liquid chromatography analysis. The linear range for indole acetic acid and indole‐3‐pyruvic acid was 1–100 µg/L and their detection limit was 0.5 µg/L. The method was applied to the simultaneous determination of two auxins in two kinds of tobacco (Nicotiana tabacum L and Nicotiana rustica L) samples, with recoveries range from 82.1 to 120.6%.     

Dynamics of two elliptical particles sedimentation in a vertical channel: chaotic state

The LB-DF/FD method derived from the Lattice Boltzmann Method and direct forcing/fictitious domain method is used to numerically investigate the dynamics and interaction of two elliptical particles settling in an infinitely long channel. One particle (EP0) is initially kept horizontal (major axis perpendicular to sedimentation) for all simulations while the other's (EP1) orientation is varied. It is found that if EP1strays away from horizontality, the particles undergo transitions from a steady state to reach a chaotic state. Furthermore, there are two distinct chaotic states for the particle motion when EP1 orientation is varied, in which a turning point is observed to distinguish the two states.     

一类非线性矩阵方程对称解的双迭代算法

利用逆矩阵的Neumann级数形式,将在Schur插值问题中遇到的含未知矩阵二次项之逆的非线性矩阵方程转化为高次多项式矩阵方程,然后采用牛顿算法求高次多项式矩阵方程的对称解,并采用修正共轭梯度法求由牛顿算法每一步迭代计算导出的线性矩阵方程的对称解或者对称最小二乘解,建立求非线性矩阵方程的对称解的双迭代算法.双迭代算法仅要求非线性矩阵方程有对称解,不要求它的对称解唯一,也不对它的系数矩阵做附加限定.数值算例表明,双迭代算法是有效的.     

综合性、设计性实验教学的探讨

综合性、设计性实验是培养学生的创新意识、创新精神和创新能力的有效措施;本文就开设综合性、设计性实验的意义、内涵、与基础实验的关系以及如何设计项目内容进行了初步的探讨。     

Vortex-lattice melting in magnesium diboride in terms of the elastic theory

In the framework of elastic theory, we study the vortex-lattice melting transitions in magnesium diboride for magnetic fields both parallel and perpendicular to the anisotropy axis. Using the parameters from experiments, the vortex-lattice melting lines in the H-T diagram are located systematically by various groups of Lindemann numbers. It is observed that the theoretical result for the vortex melting with parallel and perpendicular fields agrees well with the experimental data. Therefore, it is suggested that the phenomenological elastic theory is universal to various type-II superconductors, including two- and multi-band superconductors.     

A novel azide-free asymmetric synthesis of oseltamivir phosphate (Tamiflu) starting from Roche’s epoxide

A novel azide-free asymmetric synthesis of oseltamivir phosphate 1 (Tamiflu®) starting from Roche’s epoxide is described. Roche epoxide 2 was converted into N-acetyl aminoalcohol 3 in 95% yield via a BF₃·OEt₂-catalyzed epoxide-opening with acetonitrile as a nucleophile. Compound 3 was then transformed into a methanesulfonate 4 in 98% yield. Compound 4 was converted into aziridine 5 in 91% yield. Aziridine 5 was subsequently converted into oseltamivir phosphate 1 via two paths (a and b). In the path a, compound 5 underwent aziridine-opening with diallylamine as a nucleophile to afford compound 7 in 93% yield; compound 7 could then be converted into oseltamivir phosphate 1 in 88% yield. In path b, compound 5 underwent aziridine-opening with isopropyl 2,2,2-trichloroacetimidate as a nucleophile to afford compound 8 in 94% yield, which was then converted into oseltamivir phosphate 1 in 82% yield.     

Synthesis of SnO_2 nanorods from aqueous solution:The effect of preparation conditions on the formed patterns

<正>SnO_2 nanorods were deposited on the Si substrates in an aqueous solution containing both SnCl_4 and CO(NH_2)_2.It is found that different self-assembled patterns of SnO_2 nanorods can be obtained by changing the deposition conditions such as the molar ratio of CO(NH_2)_2 to SnCl_4 and the pretreatment of the substrate.Scattered SnO_2 nanorods,for example,can be changed into flower-like patterns when the molar ratio of CO(NH_2)_2 to SnCl_4 is raised,and well-aligned nanorod arrays can be formed when the pretreatment of the substrate is changed.In addition,some interesting patterns,e.g.tree-like patterns,can also be observed.