Toward Metathesis Reactions on Vinylphosphaalkenes

Abstract

Attempts to utilize C-ethylenic phosphaalkenes in metathesis reactions are discussed. Unprecedented reactivity is observed where the vinylphosphaalkene undergoes the first step of the catalytic cycle and cross-metathesis with the phenylmethylene moiety of Grubbs 2nd generation catalyst. However, homo-metathesis reaction to form 1,6-diphosphahexa-1,3,5-triene is not observed, presumably due to steric constraints.     

氢键和π-π诱导的二维双层Zn(Ⅱ)配位聚合物的晶体结构和荧光性能

本文以间苯二吡啶(1,3-dpb)和4,4′-二苯醚二甲酸(H2oba)为配体,溶剂热合成了一个二维锌配位聚合物{[Zn(oba)(dpb)].H2O}n(1),对其进行了红外,热重,粉末单晶衍射等表征,配合物属于三斜晶系,空间群C2/c。相邻的Zn(Ⅱ)离子通过连接oba2-和dpb形成二维波浪形面,两个相邻的面相互互锁形成2D→2D的结构,并且面与面之间存在氢键。两组2D→2D的结构通过π-π作用进一步形成双层的二维超分子网络。此外,本文也研究了配合物的荧光性能。     

三氟乙酸修饰TiO_2纳米微粒的制备及磨擦学性能

采用化学法制备一种粒径约50nm的三氟乙酸修饰TiO2纳米微粒,并用高分辨透射电镜(HRTEM)、傅立叶红外(FTIR)和热分析(TG、DTA)、X射线粉末衍射(XRD)等手段对该纳米微粒进行了表征,用MRS 10A型四球磨擦试验机考察了该纳米微粒在液体石蜡中的磨擦学性能 结果表明:三氟乙酸修饰TiO2纳米微粒能分散于液体石蜡中且具有较好的抗磨性能,能极大地提高液体石腊的抗磨性和承载能力,降低了磨擦系数     

Pt/CexZr1-xO2 催化剂在含硫合成气中催化水煤气变换反应活性

 采用浸渍法制备了 Pt/Ce_xZr_1-xO₂ 催化剂, 通过 X 射线衍射和程序升温还原等方法对催化剂进行了表征, 并在固定床反应器中评价了催化剂在合成气和含硫合成气中的水煤气变换活性. 结果表明, 铈锆固溶体的氧化还原能力强于 CeO₂, Zr 的掺杂明显改善了 CeO₂ 的孔道结构, 其担载的 Pt 催化剂具有更高的金属分散度, 因而活性更高. 两种催化剂在含硫合成气中的催化活性较无硫合成气中的均有所降低, 且 H₂S 浓度越大, 催化剂活性下降越多, 但这种因吸附硫而引起的失活是可逆的, 即催化剂重新暴露在无 H₂S 重整气的还原性气氛下活性能基本恢复.     

O-羧甲基壳聚糖纳米微粒制备及对Ni~(2+)吸附研究

将壳聚糖与氯乙酸反应,通过控制反应条件制备了取代度为0.71的O-羧甲基壳聚糖,将改性后的O-羧甲基壳聚糖与多聚磷酸钠反应,制备了粒径分布在370-710nm的O-羧甲基壳聚糖纳米微粒,透射电镜观察表明该微粒呈球状,平均粒径为450nm.在此基础上研究了O-羧甲基壳聚糖纳米微粒对工业电镀镍废水Ni~(2+)吸附性能,考察了溶液pH、Ni~(2+)起始浓度、平衡吸附时间、粒径等因素的影响,结果表明:O-羧甲基壳聚糖微粒最佳吸附条件是Ni~(2+)溶液pH为8.0、Ni~(2+)溶液起始浓度为33.28mg/ml、平衡吸附时间为0.5h、粒径较小的O-羧甲基壳聚糖纳米微粒对Ni~(2+)的吸附量要大于粒径较大的吸附量.     

仪器定量分析中几个问题的探讨

详细介绍了分析方法的评价指标,包括检出限、测定限、灵敏度、精密度、准确度、动态范围和线性范围、抗干扰能力等,单因素优化方法与加标回收实验评定测定结果准确度的可靠性,并就分析工作中遇到的一些实际问题进行了讨论.     

Synthesis, photophysical and electrochemical properties and theoretical studies on three novel indolo[3,2-b]carbazole derivatives containing benzothiazole units

Three novel indolo[3,2-b]carbazoles derivatives were successfully synthesized by condensation reaction and structurally characterized by elemental analysis, mass spectrometry and proton nuclear magnetic resonance spectroscopy methods, which belong to donor-π-acceptor systems comprising an indolo[3,2-b]carbazole group as an electron donor and two benzothiazole rings as electron acceptors. The thermal, electrochemical and photophysical properties of the compounds were characterized by thermogravimetric analysis combined with electrochemistry, UV-vis absorption spectroscopy and fluorescence spectroscopy. On the other hand, the geometries, molecular orbitals, charge-injection and transport properties were determined by quantum chemical calculations. The results show that the compounds synthesized exhibit good thermal stability and high fluorescence quantum yields, indicating the potential application as optoelectronic materials.     

芳环超分子体系中的π-π作用

π-π作用是芳环超分子体系中广泛存在的一种重要的弱相互作用. 本文对π-π作用的特征、形式、有效参数和表征方法等作了比较全面的综述, 同时小结了影响π-π作用的一些重要因素, 最后还概述了近年来π-π作用在超分子组装、不对称催化、有机半导体材料等领域的研究进展.     

π-π Stacking and Magnetic Coupling Mechanism on a Mono-nuclear Mn(Ⅱ) Complex

A new mono-nuclear Mn(Ⅱ) complex [Mn(MPT)2(NCS)(HOCH3)]ClO4(MPT = 2-methoxyl-1,10-phenanthroline) has been synthesized with 2-methoxyl-1,10-phenanthroline and thiocyanate anion as ligands,and its crystal structure was determined by X-ray crystallography.The crystal data:monoclinic system,space group P21/c with a = 12.8849(17),b = 15.684(2),c = 14.2703(19) ,β = 92.126(2)°,V = 2881.9(7) 3,Z = 4,C28H24ClMnN5O7S,Mr = 664.97,Dc = 1.533 g/cm3,F(000) = 1364 and μ = 0.679 mm-1.In the crystal,MPT functions as a bidentate ligand and Mn(Ⅱ) ion assumes a distorted octahedral geometry.In the crystal there are two types of π-π stacking interactions among the adjacent complexes,which involves 1,10-phenanthroline rings.The theoretical calculations reveal that the two types of π-π stacking resulted in a weak anti-ferromagnetic coupling with 2J =-14.68 cm-1 and a weak ferromagnetic coupling with 2J = 0.70 cm-1,respectively.The theoretical calculations also reveal that there are both spin polarization and spin delocalization in the two π-π stacking systems,and the magnetic coupling signs are unable to explain with McConnell I spin-polarization mechanism.     

以PBL法进行药学实验基本技能教学的探索与实践*

根据西部少数民族地区院校的客观条件和教学特点,提出用以问题为导向的教学法(PBL)进行药学基本技能实验教学。实践证明,实验组(PBL法)的实践基本技能操作水平和发现、分析并解决问题的能力均显著高于对照组(传统教学法)。该法对提高西部少数民族地区药学本科生的创新能力具有较大意义,对其他地区药学本科生创新能力的培养也有一定的借鉴作用。