CH_3自由基和O（~3P）反应机理的量子化学研究

用分子轨道从头计算MP2（full）方法和密度泛函理论（DFT）中的B3LYP方法 研究了CH_3自由基和三线态O原子反应的微观机理，优化得到了反应途径上的反应 物、过渡态、中间体和产物的几何构型，通过振动分析对过渡态和中间体构型进行 了确认，在G3不平上计算了能量，同时用经典过渡态理论对该反应的绝对速率常数 进行了理论计算。研究结果表明：CH_3自由基与O（~3P）反应有四条不同的放热反 应通道，主反应通道为IM1→TS1→CH_2O + H，同时反应可彻底裂解生成CO, H_2 及H。     

Anticancer Drugs ( Ⅳ )——New Derivatives of Podophyllotoxin

Four new derivatives of podophyllotoxin, N'-podophyllic acid-N-[3-(2, 2, 5, 5-te-tramethyl-pyrrolinenyloxy)] semicarbazide(GP-11, 6), podophyllic acid [3-(2,2,5,5-te-tramethyl-pyrrolinenyloxy)]hydrazone (GP-12, 7), podophyllic acid-[4-(2, 2, 6, 6-tetramethyl-1-hydroxy piperidine)]hydrazone(GP-1-OH, 8) and podophyllic acid[4-(2,2, 6, 6-tetramethyl piperidine)]hydrazone(GP-1-H, 9) were synthesized. The inhibition effect of the four new compounds on L-1210 cells were determined. The antitumor activity and toxicity of GP-1(2), GP-1-OH(8), GP-1-H(9) and VP-16-213(1) were discussed.     

Synthesis,Crystal Structure,and Biological Activity of 4-Chlorobenzaldehyde (2-trifluoromethylTrifluoromethyl-5,6,7,8-tetrahydrobenzo[4 ,5]-thieno[2,3-d]pyrimidin-4-yl)hydrazone Monohydrate

The novel title compound 4-chlorobenzaldehyde (2-trifluoromethyl-5,6,7,8- tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-yl)hydrazone monohydrate (C18H14ClF3N4SH2O, Mr = 428.86) has been synthesized by a condensation reaction of 4-chlorobenzaldehyde with (2-trifluoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-yl)hydrazine, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 7.4252(7), b = 26.344(2), c = 10.3095(9) , = 109.407(2)°, V = 1902.0(3) 3 , Z = 4, Dc = 1.498 g/cm3 , μ = 0.356 mm-1 , F(000) = 880, the final R = 0.0564 and wR = 0.1681 for 2343 observed reflections with I > 2 (I). X-ray diffraction analysis reveals that the title hydrazone molecule is nearly planar except for the cyclohexene and trifluoromethyl moieties. In the crystal packing, the molecules form stacks by a three-dimensional framework, which results from intermolecular N(3)-H(3)···O(1), O(1)-H(1B)···N(2), O(1)- H(1B)···N(4) and O(1)-H(1A)···F(1) hydrogen bonds via water molecules together with π-π stacking interactions. Molecular geometry of the title compound in the ground state optimized by B3LYP functional with 6-311G** basis sets indicates that the calculations are in agreement with the experimental data. The preliminary bioassay suggested that the title compound exhibits relatively good fungicidal activity against Fusarium oxysporium f.sp.vasinfectum and Dothiorella gregaria.     

“手持技术”与化学教学整合的文献统计分析

以《化学教育》《化学教学》《中学化学教学参考》3种期刊为研究对象,通过CNKI搜索和查阅原始文献,从论文作者所在区域、作者单位、论文年代分布、作者合作情况、论文内容等几个方面对2004-2014年有关手持技术与化学教学整合的研究论文进行情报统计分析和评价,从另一侧面探讨了我国手持技术与化学教学整合的历程、现状、存在的问题和发展趋势。     

Preliminary communication - The synthesis and thermotropic liquid crystalline behaviour of novel main chain poly(aryl ether ketone)s containing a lateral phenyl group

Novel main chain poly(aryl ether ketone)s containing a lateral phenyl group were synthesized by nucleophilic substitution reactions of 4,4-biphenol and phenylhydroquinone with either 4,4-difluorobenzophenone or 1,4-bis(4-fluorobenzoyl)benzene and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. Thermotropic liquid crystalline behaviour was observed in the copolymers containing 50 and 70 mol% biphenol. Melting (Tm) and isotropization (Ti) transitions both appeared on the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline nematic state. As expected, each of the copolymers had a relatively lower melting transition than the biphenol-based homopoly(aryl ether ketone)s because of the copolymerization effect of the crystal-disrupting monomer phenylhydroquinone.     

松花粉中16种常量和微量元素的TXRF对比分析

采用微波消解前处理,全反射X射线荧光分析法(TXRF)同时测定松花粉中16种元素,并对马尾松、云南松、油松、黑松、赤松等五种松花粉中16种元素含量进行了测定与比较。结果表明:五种松花粉中都含有这16种元素;Ca,Ti,Mn,Zn和Rb等五种元素平均含量在不同树种间均存在极显著性差异(p≤0.01);K,V,Fe,Co,Cu和Sr等六种元素平均含量在不同树种间均存在显著性差异(p≤0.05);Cr,Ni,As,Pb和Se等五种元素平均含量在不同树种间不存在显著性差异(p>0.05);研究还表明松花粉具有温性或偏寒凉性药的元素谱征。研究结果可以初步断定,松花粉中这16种元素的含量和树种有关,和生长环境、地域等密切相关。     

光子四维量子态隐形传输

多维量子纠缠态比二维纠缠态可加载更多的信息,多维量子系统是量子信息处理中一个很重要的资源,本文采用已实现的光子四维纠缠态,给出了光子四维量子态的张量表达式,并描述了四维量子态隐形传输的一般表示方法；通过讨论光子四维量子态系统的量子通道参数矩阵和测量矩阵的特性,得到实现完全传输和非零概率传输的充要备件,最后,本文给出在多种量子通道下的四维态的量子隐形传态方案,这一过程在张量分析表示下十分清晰明了.     

基于供应方生产能力的应急物资生产模型

利用期权契约所建立的政企合作储备应急物资模式能够有效解决政府单独储备模式所造成的物资储备量过少或过多而引起的困境。然而由于应急物资的需求特性,若应急物资供应企业采用按单生产方式安排生产储备计划,势必会造成库存水平升高,引发资金周转困难等问题,对政企之间的长期合作造成不利影响。基于此,本文设计了基于供应方生产能力的应急物资生产模型。该模型在政府利用批发价格契约与期权契约采购应急物资的基础上,研究了供应方根据自身生产能力进行柔性生产时的生产与储备问题。通过推导政企双方最优决策后,重点分析了期权权利金,执行价格,加急生产成本等参数对供应方生产决策的影响,并证明与按单生产模式相比,柔性生产模式可有效降低供应方的库存量与生产成本,提高其利润,继而提高整体供应链的利润水平,有助于促进政企之间长期稳定的合作。     

时间敏感选项依赖下的基础设施恢复决策研究

突发事件发生后,基础设施之间的恢复依赖为恢复过程带来了严重挑战。为了能够在突发事件后高效而有序的实现基础设施恢复运行,根据相互之间的恢复依赖关系制定合理的恢复决策非常关键。本文基于网络流理论,以累积恢复效能最大化为目标,建立了时间敏感选项依赖下的恢复设计与调度决策混合整数规划模型。然后,讨论了模型在完全中心化、完全分散和信息共享决策环境下的应用方法。最后,通过真实基础设施数据集测试了模型,结果表明:(1)该模型在突发事件后的基础设施恢复决策中具有应用可行性;(2)决策环境显著影响存在恢复依赖的基础设施网络整体累积恢复效能;(3)与完全分散决策环境相比,在信息共享决策环境下独立决策的整体累积恢复效能可以得到大幅提升。     

用于液体激光介质的Nd~(3+)离子掺杂氟化镧纳米颗粒的制备与性能表征

设计并合成了掺杂不同Nd3+离子浓度的氟化镧纳米颗粒,并用油酸进行了表面修饰,使得这类纳米颗粒可分散于常见的有机溶剂中形成透明、均一、稳定的溶液。对纳米颗粒的结构、晶相以及发光性能进行了表征。固体和溶液材料在1 060 nm都有强的发射峰,说明纳米晶格可有效地保护Nd3+离子免受外界环境对发光的猝灭影响。纳米颗粒有机溶液的吸收损耗和散射损耗测试结果表明,其总损耗系数能够满足激光介质材料的损耗要求,为该材料的实用化打下了基础。