乙酸/氧气法高效合成取代卟啉

卟啉在结构上可视为是由4个吡咯类亚甲基的α-碳原子通过次甲基桥互联而形成的大分子杂环化合物,具有高度共轭结构。 随着卟啉与金属的配合物即金属卟啉的催化特性受到广泛关注,取代卟啉的高效合成日益显示出重要的学术和应用价值。 但是现有的丙酸法和乙酸/硝基苯法存在卟啉收率低、环境污染严重等问题,导致取代卟啉的成本居高不下,限制了其广泛应用。 本文利用乙酸/氧气法,在120 ℃下控制反应物浓度为0.24 mol/L,并在反应第一阶段(前30 min)通入氧气,得到四(4-溴苯基)卟啉(化合物d),产率高达53.8%。 该方法是高效合成取代卟啉的新方法,卟啉骨架形成和氧化两个反应同时进行,方法简单、绿色且收率高,有望大幅度降低取代卟啉的合成成本。     

Oxygen permeation and phase structure properties of partially A-site substituted BaCo_(0.7)Fe_(0.225)Ta_(0.075)O_(3-δ) perovskites

Ba0.9R0.1Co0.7Fe0.225Ta0.075O3-δ(BRCFT, R = Ca, La or Sr) membranes were synthesized by a solid-state reaction. Metal cation Ca2+,La3+or Sr2+doping on A-site partially substituted Ba2+in BaCo0.7Fe0.225Ta0.075O3-δoxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, H2-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2+, La3+or Sr2+, whose ionic radii are smaller than that of Ba2+, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experiments showed that BRCFT with A-site fully occupied by Ba2+exhibited good oxygen permeation flux under He flow, reaching about 2.3mL min-1 cm-2at 900 ℃ with 1 mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation(Ba2+La3+Sr2+Ca2+).     

尾式甘氨酸四苯基卟啉锌与吡啶类化合物轴配反应光谱和热力学

取代四苯基卟啉锌配合物与咪唑类和吡啶类等含氮化合物轴向配位反应的研究在模拟生物体中锌酶的作用机理方面具有重要意义。在现有的文献中 ,人们的研究主要集中在四苯基卟啉的苯环上连有如卤素、甲氧基、甲基等较小取代基的卟啉锌上[1～3] ,对于结构不对称且苯环上连有氨基酸的四苯基卟啉锌与含氮化合物轴向配位反应的研究尚不多见。有关尾式氨基酸四苯基卟啉锌配合物的合成和性质我们进行过较系统的研究[4～6] 。本文以 5 ( 4 甘氨酸丁氧苯基 ) 1 0 ,1 5 ,2 0 三苯基卟啉锌 (ＺｎＰ)为锌酶的模型化合物 ,用热力学方法研究了它与吡啶 (…     

Polarity and steric effect of the lateral substituent on the mesophase behaviour of some newly prepared liquid crystals

Eight homologous series of 2- (or 3-) substituted phenyl 4?-(4?-alkoxy phenylazo) benzoates (In_a–h) were prepared in which, within each homologous series, the length of the terminal alkoxy group varies between 6, 8, 10 and 12 carbons, while the other substituent, X, is a laterally attached polar group that alternatively changed from CH₃, H, F, Br and CN. Compounds prepared were characterised by infrared and ¹H-NMR spectroscopy, and their mesophase behaviour investigated by differential scanning calorimetry and identified by polarised light microscopy. The results were discussed in terms of polarity and steric effects. The stability of the mesophase was correlated once with the dipolar anisotropy of the whole molecule and another with the dipolar anisotropy of the substituent, X. A comparative study was made between the investigated compounds and their previously prepared linear 4-substituted isomers, namely 4-substituted phenyl 4?-(4?-alkoxy phenylazo) benzoates (In_i–k).     

双(取代水杨醛)间苯二甲酰腙有机锡配合物的一锅溶剂热法合成、结构和荧光性质

以间苯二甲酰肼、取代水杨醛和有机锡前体化合物进行一锅溶剂热法反应,合成了5个双（取代水杨醛）间苯二甲酰腙有机锡配合物m-Ph （CONH-N=CH （o-O） PhR¹）（SnR²）₂：R¹=Naphth,R²=Cy （1）; R¹=3-t-Bu,R²=n-Bu （2）; R¹=5-F,R²=Ph （3）; R¹=4-Cl,R²=Ph （4）; R¹=3-t-Bu,R²=Ph （5）。经元素分析、红外光谱、（¹H、¹³C和¹¹⁹Sn）核磁共振谱表征,并用X射线衍射方法确证了配合物1~5的晶体分子结构。配合物1~4为三斜晶系P1空间群,配合物5为单斜晶系P2₁空间群。中心锡与配位原子组成五配位畸形三角双锥构型。将水杨醛酰腙链与有机锡配位形成远离中心苯环的构型称为"反式",将与中心苯环取向相同的构型称为"顺式"。通过C1-C2或C4-C8单键旋转,中心苯环上的2个配位链发生构型翻转。配合物1形成"反-反"式构型,配合物2形成"顺-顺"式构型,配合物3、4和5形成"顺-反"式构型。荧光研究表明,配合物具有发光性能,特别是配合物1和4的有机溶液具有很强的荧光性能。     

取代1-氯蒽醌中分子内卤键的电子密度拓扑分析

运用量子化学密度泛函B3LYP方法,在6-311＋＋G（d,p）基组水平上对邻位和间位取代1-氯葸醌的分子内卤键进行了研究．用电子定域函数和“分子中的原子,,理论对分子内卤键的性质进行了电子密度拓扑分析．通过对计算得到的密度矩阵进行σ-π兀分离,得到了π-键的键径和分子图,并讨论了。电荷密度和兀电荷密度对卤键的影响．结果表明,键鞍点和环鞍点处的电子密度拓扑性质均可作为衡量分子内卤键强度的量度．键鞍点和环鞍点处的电荷密度P越大,键鞍点与环鞍点的距离越大,卤键强度越大．除σ电荷密度外,π电荷密度对分子内卤键的性质也有明显影响．     

不同类型卟啉自组装膜的制备及表征

制备了不同类型的巯基卟啉自组装膜,借助多种表征技术（紫外可见光谱、电化学和X射线光电子能谱）研究了不同类型卟啉自组装膜的结构特点;研究结果表明,卟啉分子中巯基取代基数目的不同（-[SH]n-,n=1,4）,导致了卟啉环在自组装膜表面的构型不同,从而表现出不同巯基卟啉自组装膜性能的差异。 在此基础上,提出了不同巯基卟啉自组装膜的结构模型。     

取代苯酚的定量结构－活性／性质相关性研究

在分子拓扑理论基础上,提出了一个新的价连接性指数~nG=∑(E_i·E_j· E_k...),其中~0G=∑(E_i),~1G=∑(E_i·E_j),并用~0G,~1G研究了取代苯酚（ 含Cl,Br,INH_2,NO_2,COOH,烷基、环烷基、苯基等）的溶解度,辛醇／水分 配系数及对黑曲霉、浮萍、细胞色素P－450、酵母菌等的生物活性,给出了相关方 程。结果表明,新方法计算简单,使用方便,预测值与相应的实验值较好吻合。     

THE CRYSTALLIZATION BEHAVIOR OF URETHANE SUBSTITUTED POLYDIACETYLENE

The crystalline behavior of urethane substitute polydiacetylene was studied by using pohrized light and electron microscopy. The lamellar morphological structure was observed in the crystallized films. The thickness of lamellae is about 300A, being independent of the crystalline temperature. But the size and density of lamellae were dependent on the crystallization temperature. If the molten film was sheared during the crystallzation process the oriented lamellae grew with their long axes perpendicular to the direction of shear and the chain direction was normal to the lamellar surface.     

2-羟基-4-(1′-甲庚氧基)苯烷酮肟的合成

具有邻位羟基的酮肟化合物(1)作为过渡金属螯合剂已在铜的萃取-电积工艺中得到广泛应用,如:LIX 64N(1a),LIX84(1b)及LIX 860(1c)。从萃取动力学行为来衡