二正丁基锡二(邻氯苯甲酸)酯配合物{[n-Bu2Sn(O2CC6H4Cl)]2O}2的微波固相合成、结构及体外抗癌活性

二正丁基氧化锡和邻氯苯甲酸按物质的量比1∶2,通过微波固相合成法合成了二正丁基锡邻氯苯甲酸酯配合物{[n-Bu2Sn(O2CC6H4Cl)]2O}2。经X射线衍射方法测定了其晶体结构,配合物属三斜晶系,空间群为P 1,晶体学参数a=1.17653(4)nm,b=1.20672(4)nm,c=2.74090(9)nm,α=80.493(2)°,β=83.995(2)°,γ=64.260(2)°,V=3.4547(2)nm3,Z=2,Dc=1.525 g/cm3,μ(MoKα)=16.34 cm-1,F(000)=1592,R1=0.0414,wR2=0.1349。晶体中每一个结构单元包含了2个键参数完全不同的以Sn2O2构成的平面四元环为中心环的二聚体结构分子,锡原子均为五配位的畸变三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。     

模拟细胞色素P-450的仿生氧化反应的研究 I:氯合5,10,15,20-四苯基卟吩合铁(III)催化下不同亚碘酰芳烃及其衍生物的结构对环己烷充氧化反应的影响

在氯合5,10,15,20-四苯基卟吩合铁(III)[TPPFe(III)Cl]催化下, 带有不同取代基的亚碘酰苯和亚碘酰苯的衍生物作充氧化剂对环己烷进行了仿生单充氧化反应的研究.取代亚碘酰苯中对位取代基的电子效应和间位取代基的电子及立体效应对氧化产物环己醇的产率有良好线性相关性. 亚碘酰苯的衍生物苯亚碘酸二醋酐与苯亚碘酸单对甲苯磺酸酐对环己烷的充氧化能力和邻、间、对亚碘酰苯甲酸与邻亚碘酰苯甲酸酯相似, 环己醇产率接近零. 从而提出亚碘酰苯甲酸及邻亚碘酰苯甲酸酯存在分子内或分子间I(oh)oco成键结构的论点.     

模拟细胞色素P-450的仿生氧化反应的研究 T.氯合5,10,15,20-四苯基卟吩合铁(III)催化下不同亚碘酰芳烃及其衍生物的结构对环己烷充氧化反应的影响

在氯合5,10,15,20-四苯基卟吩合铁(Ⅲ)[TPPFe(Ⅲ)Cl]催化下,带有不同取代基的亚碘酰苯和亚碘酰苯的衍生物作充氧化剂对环己烷进行了仿生单充氧化反应的研究.取代亚碘酰苯中对位取代基的电子效应和间位取代基的电子及立体效应对氧化产物环己醇的产率有良好线性相关性.亚碘酰苯的衍生物苯亚碘酸二醋酐与苯亚碘酸单对甲苯磺酸酐对环己烷的充氧化能力和邻、间、对亚碘酰苯甲酸与邻亚碘酰苯甲酸酯相似,环己醇产率接近零.从而提出亚碘酰苯甲酸及邻亚碘酰苯甲酸酯存在分子内或分子间I(OH)OCO成键结构的论点.     

氯苯甲酸钠在DMF-水混合溶剂中的体积性质研究

DMF是分子间没有氢键形成的分子量最小的酰胺[1],在化学、化工领域应用广泛．本文对苯甲酸钠及o－,m－,p-氯苯甲酸钠在DMF-水混合溶剂中的体积性质进行研究,讨论了溶剂效应和取代基效应对溶质-溶剂相互作用的影响．1实验部分1．1试剂苯甲酸及NaOH为分析纯试剂;o－,m－,p-氯苯甲酸（分析纯）均经乙醇一水重结晶,干燥后备从DMF为分析纯;水为二次重蒸水．对应钠盐溶液按文献［2」方法配制,其它溶液由此溶液逐级稀释而成．DMF一水混合溶剂用称量法配制,DMF的质量分数为10％～80％．1．2仪器混合物密度用AntonPaarDMA55型精…     

邻乙氧基苯甲酸的氢键模式随温度的变化关系

晶体中邻甲氧基苯甲酸以分子间氢键形成的二聚体形式存在,但邻乙氧基苯甲酸却以分子内氢键形成的单体存在.本文用低温红外光谱,结合氘代和酰氯化实验揭示了邻乙氧基苯甲酸晶体中也存在二聚体,但室温时含量很少,随着温度降低,含量逐渐增加.     

碳纳米管/聚对甲基吡啶修饰电极测定硝基苯甲酸

采用滴涂法和循环伏安法在玻碳电极上电沉积一层稳定的单壁碳纳米管/聚对甲基吡啶纳米薄膜(SWNTs/POMP)。研究了邻、对硝基苯甲酸在此修饰电极上的电化学行为,建立了电化学同时测定邻、对硝基苯甲酸的新方法。实验结果表明:在0.1 mol/L HClO4溶液中,邻、对硝基苯甲酸在SWNTs/POMP电极上发生不可逆的还原反应,由于碳纳米管和聚合物薄膜的协同效应,SWNTs/POMP电极对邻、对硝基苯甲酸有很好的的电催化作用,并对其响应进行了定量分析。     

邻羧基苯甲酰二茂铁钠的合成、晶体结构及电化学性质

参照文献方法合成了邻羧基苯甲酰二茂铁钠,首次培养得到了它的单晶．发现在其固态结构中,邻羧基苯甲酰二茂铁阴离子与四水合钠阳离子通过分子内氢键相互作用;分子间的氢键又把多个二茂铁衍生物分子连接成二维的网状结构．研究了标题化合物在甲醇溶液中的电化学性质．     

2,5-二取代(口恶)唑的研究(Ⅱ)——HMO计算及光谱的取代基效应

本文对2-苯基上邻、间、对取代的三个系列2-苯基-5-联苯基噁唑的衍生物进行了HMO计算,并结合所得到的分子轨道能量和分子图,对取代基效应与光谱性质以及MO有关指数的影响做了量子化学说明;同时,考虑到基团的邻位效应对2-苯基邻位取代系列中的HMO参数进行了适当调整,所得计算结果与实验数据有较好的相关性。     

微波相转移催化氧化法合成氯代苯甲酸

在相转移催化剂存在下，用微波辐射快速合成氯代苯甲酸。考察了微波辐射功率、辐射时间、相转移催化剂对反应的影响。实验证明：在455W的微波辐射下，以季铵盐A-1为相转移催化剂，反应3min，对氯苯甲酸、邻氯苯甲酸的产率分别达72．5％和71．8％。     

有机亚碘酰化合物的研究(Ⅱ)——羧基及酯基取代亚碘酰芳烃的结构与性能的研究

本文对邻亚碘酰肉桂酸、邻亚碘酸苯乙酸、邻亚碘酰苯甲酸及其酯和间亚碘酰笨甲酸进行了波谱分析,认为它们都存在着分子内成环结构。     

Synthesis of Cyanobenzaldehydes （m—,o—,p—）by Molecular oxygen Oxidation Methods

Cyanobenzaldehydes (m-,o-,p-) were synthesized by oxidation of corresponding tolunitriles with molecular oxygen,catalyzed by cobalt acetate and sodium bromide.     

Effect of the methyl group on the isotope exchange rate for hydrogen in the o-, m-, and p-positions in tricarbonyltoluene chromium in alkaline media

Conclusions The hydrogen isotope exchange reaction of carbonyltoluene chromium in ethanol in the presence of a sodium alcoholate has been studied. The partial rate factors for the o-, m-, and p- positions in the aromatic ring in this system have been determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, no. 7, pp. 1622–1623, July, 1968.     

Letter: electron impact mass spectrometry study of a series of substituted 5- aminoalkylmethyl-cytosines and their 1-N-(o-, m- and p-)bromobenzyl-substituted derivatives

The electron-impact mass spectra of 5-aminoalkylmethyl-substituted cytosine and of their 1-N- o-(m- or p-)bromobenzyl-substituted derivatives are discussed. The influence of 5-aminoalkyl and 1-N-bromobenzyl substituents on the mode of mass fragmentation occurring upon electron impact ionization was demonstrated. The fragmentation pathways of all compounds and the characteristic ions in these spectra originating from the McLafferty rearrangement, RDA reactions and simple cleavages are presented.     

取代苯胺的化学氧化聚合

本文研究了甲苯胺(O-,m-,p-)在盐酸水溶中的聚合反应。结果表明,三种甲苯胺的聚合强烈依赖于氧化剂浓度和聚合介质的pH值。用IR、NMR和元素分析等手段表征了可溶聚合物。     

同时测定水中氯代芳烃、硝基芳烃及邻苯二甲酸酯的气相色谱法

分别用国产高聚物ＧＤＸ１０２、ＧＤＸ５０２小球及它们等质量比例混合的树脂对模拟水样中的痕量的有机物进行富集,带电子捕获检测器的毛细管气相色谱法同时分析水中邻、间、对二氯苯、硝基苯,对硝基甲苯,邻、间、对硝基氯苯,２,４－二硝基甲苯,邻苯二甲酸酯（二甲酯、二乙酯、二丁酯）共１２种有机物。上述有机物除二氯苯外,回收率达７０％以上,方法具有很高的灵敏度,适用于饮用水及水源水中痕量的有机物的分析。     

Piezoelectric detectors coated with liquid-crystal materials

The usefulness of liquid crystals as coating materials for quartz resonators in piezoelectric detectors of air-pollution has been tested. The concentration characteristics of the detector with respect to benzene, toluene, chlorobenzene, o- and m-dichlorobenzene, nitrobenzene, and o-, m- and p- diethylbenzene have been determined with the use of 4-pentyl-4'-cyanodiphenyl, 4-pentyl-4'-propylazo-benzene, 4-propyl-4'-methylazoxybenzene, and cholesteryl oleylcarbonate as coating materials. The effects of the quantity of coating material and of temperature on the sensitivity of the piezoelectric detector have been tested. The influence of the ordered structure of the liquid-crystal coating materials on the selectivity of the detector is discussed. Experiments have been performed to test the usefulness of the detector with liquid-crystal coating for detecting organophosphorus pesticides (DDVP and Phosdrin).     

乙二胺桥联环糊精二聚体的多重识别研究

本文合成了由两个乙二胺分子桥联的β-环糊精二聚体(1)。在碱性溶液中1与二价铜离子形成稳定的配合物(2), 根据客体分子被包合前后主、客体质子化学位移的变化研究了水溶液中三个主体分子: β-环糊精、1和2分别与对、间和邻氯苯酚及其钠盐的包合反应。通过比较主-客体包合物生成常数的大小可以推断2与有机阴离子客体之间存在多重识别作用。     

Azo-Derivatives of Gossypol and Its Imines

Azo-coupling of diazotized aromatic amines with gossypol and gossypolimines was studied. The physicochemical properties and interferon-inducing activity of the products were determined. It was found that the interferon-inducing activity depended on the reaction type, the position of functional groups (o-, m-, p-) in the added substituents, and the dose and contact time of the compounds with the cells.     

A Fully Non-fused Ring Acceptor with Planar Backbone and Near-IR Absorption for High Performance Polymer Solar Cells

Fused-ring electron acceptors have made significant progress in recent years, while the development of fully non-fused ring acceptors has been unsatisfactory. Here, two fully non-fused ring acceptors, o-4TBC-2F and m-4TBC-2F, were designed and synthesized. By regulating the location of the hexyloxy chains, o-4TBC-2F formed planar backbones, while m-4TBC-2F displayed a twisted backbone. Additionally, the o-4TBC-2F film showed a markedly red-shifted absorption after thermal annealing, which indicated the formation of J-aggregates. For fabrication of organic solar cells (OSCs), PBDB-T was used as a donor and blended with the two acceptors. The o-4TBC-2F-based blend films displayed higher charge mobilities, lower energy loss and a higher power conversion efficiency (PCE). The optimized devices based on o-4TBC-2F gave a PCE of 10.26 %, which was much higher than those based on m-4TBC-2F at 2.63 %, and it is one of the highest reported PCE values for fully non-fused ring electron acceptors.