5种取代四苯基氧代钼卟啉化合物的合成

以乙酸和丙酸为混合溶剂,硝基苯为氧化剂,合成了5种取代四苯基卟啉配体。再以十氢萘为溶剂,五氯化钼为金属盐反应合成了氧代钼卟啉化合物。经紫外-可见光谱和红外光谱对目标产物进行了结构表征。进一步考察了反应温度、五氯化钼金属盐用量和卟啉配体浓度对金属化产物的收率影响。金属化收率达到了86%～96%,采用两步法合成氧代钼卟啉的总收率达17.7%～44.4%。     

A Novel Rhodium‐Catalyzed Cascade Cyclization: Direct Synthesis of 3‐Substituted Phthalides from Aldehydes and Aromatic Acids

A novel rhodium(III)‐catalyzed direct functionalization of ortho C H bonds of benzoic acid derivatives and an intramolecular cyclization sequence generates 3‐substituted phthalides in moderate to good yields. This cascade cyclization involves a Grignard‐type arylation of an aldehyde and subsequent intramolecular nucleophilic substitution. No theoretical waste except for water is generated in the reaction.     

2-甲基-5-取代苯硫基-1,3,4-噻二唑的合成研究

以取代碘苯和2-巯基-5-甲基-1,3,4-噻二唑为原料,合成了一系列2-甲基-5-取代苯硫基-1,3,4-噻二唑类化合物,确定最佳合成条件为:以碘化亚铜作催化剂、2-吡啶甲酸作配体,于70～80℃在二甲基亚砜中反应24～36h。目标化合物结构经核磁共振氢谱、核磁共振碳谱、红外光谱、质谱分析确证。     

新型羟基苯基苯并咪唑类衍生物的合成及其光谱性质研究

合成了8个具有不同结构的羟基苯基苯并咪唑类荧光化合物,通过1 H NMR,IR对其进行了结构表征,并研究了它们在甲醇溶液中的光谱性质及取代基对光谱性质的影响。该类化合物的荧光量子产率在0.006～0.75之间,Stokes位移大(>117nm)。实验结果表明,化合物上所连取代基的性质对其光谱有显著影响,具有推电子基团的羟基苯基苯并咪唑类化合物在光激发下出现荧光双发射峰,而具有吸电子基团的化合物在光激发下仅出现激发态质子转移荧光发射峰,表现出Stokes位移大和荧光量子产率高的优点。     

DFT方法研究取代芳烃结构与急性毒性的定量关系

对取代芳烃进行DFT-B3LYP/6-311G**水平全优化得到其优势构象,结合分子图形学技术获得相应电子结构参数和几何结构参数,并将这些参数与取代芳烃对发光菌、大型蚤和呆鲦鱼的急性毒性关联,得到了良好的相关性,相关系数依次为0.9524、0.9742和0.9700,所建QSARs模型具有良好的稳定性和预测能力,估算结果优于文献,结果表明:(1)分子疏水性参数logP较大时,化合物的毒性较大;(2)DELH越小,化合物毒性越大;(3)取代基的吸电子能力越强,化合物的毒性越大。     

山梨酸酯类C60衍生物的合成及非线性光学性质

为了更深入地探讨C60衍生物的非线性光学性质,用5-(2-硫甲基-4-甲基)-嘧啶基-戊二炔-1-醇山梨酸酯与富勒烯C60进行加成反应,获得了一种新型的山梨酸酯类C60衍生物,用MALDI-TOF-MS,IR,UV-vis,1H NMR,DEPT和13CNMR进行了结构表征。利用Q倍频ns/ps Nd:YAG激光脉冲以及z扫描技术和光限辐实验研究了该化合物的非线性折射和光限辐特性,并获得了3阶非线性光学系数和非线性吸收系数。结果表明,C60衍生物有很强的非线性吸收和非线性折射,并具有较低的光限幅箝位值,是一种非常有前途的非线性光学材料。     

Theoretical investigation of electroluminescent alkoxy substituted 4,4′-bis(2-phenylethenyl)biphenyls as guest in blue OLEDs

A quantum-chemical investigation on the structural and opto-electronic properties of several alkoxy substituted 4,4′-bis(2-phenylethenyl)biphenyls (PEBP) as building blocks for π-conjugate polymer is performed in order to display the effect of changing the position of alkoxy substituents on the peripheral phenyl rings on their opto-electronic and physico-chemical properties. Added to the good agreement between theoretical and experimental observations, it has been observed that the substitution effect depends on the position of the methoxy group: in ortho- or para-positions it acts as a mesomeric electrons donor, while as an inductive electrons acceptor in meta-positions. Substitution in ortho-positions causes significant structural deformations of PEBP backbone due to the steric interaction between the substituents and the hydrogens of the vinylene functions. Bridging of ortho, para-PEBP (24PEBP) by CC(CN)₂ decreases significantly its band gap. This model can have very interesting opto-electronic ownerships.     

MEDV用于取代苯酚定量构效关系研究

基于定量结构-活性关系(QSAR)研究取代苯酚化合物的性质具有重要意义.分子电性距离矢量(MEDV)是1种描述分子二维结构的拓扑描述子,由4种类型原子间的相互作用得到的10个矢量组成.采用MEDV表征取代苯酚化合物的分子结构,运用多元线性回归技术,同时采用逐步回归结合统计检测对模型变量进行筛选,建立了取代苯酚诱发浮萍萎黄活性、取代苯酚臭氧氧化表观速率常数与MEDV的QSAR模型,继用留一法和外部样本检验模型稳定性能.其复相关系数(R)、留一法(LOO)交互校验复相关系数(Rcv)和外部样本校验复相关系数(Qext)分别为0.9850、0.9621、0.8218;0.8579、0.7621、0.7966.结果表明,MEDV计算简单,对于取代苯酚的结构表征能力较强,所建OSAR模型具有良好的稳定性和预测能力.     

微波合成掺锶羟基磷灰石

以SrCl2、Ca(NO3)2和(NH4)2HPO4为原料,采用微波法合成了掺锶羟基磷灰石。对制备的SrHAP进行元素含量分析,采用XRD对其结构进行了表征,并测定粉体产物的粒度。研究结果表明:采用微波法可以制备出元素组成接近原料计算化学计量比的掺锶羟基磷灰石;采用微波法可以快速得到结晶性好的SrHAP;掺锶量对微波合成的SrHAP的结构有显著影响;微波法比常规方法制备出的SrHAP粉体的粒度小。     

Synthesis of Ti-containing SBA-15 materials and studies on their photocatalytic decomposition of orange II

Titanium substituted SBA-15 mesoporous materials have been successfully prepared by conventional hydrothermal method and they were also used as support on TiO₂ loaded SBA-15 photocatalysts. The synthesized materials were characterized by XRD, UV–vis DRS, FT-IR, BET and TEM. We also examined the activity of these materials as photocatalysts for the decomposition of orange II. The incorporation of titanium into framework of SBA-15 makes the pore diameter and pore volume to decrease and slightly decreases the surface area compared to SBA-15. In addition, the pore size distribution becomes broaden with an increase of titanium amount in the SBA-15 framework. For Ti-SBA-15 and TiO₂ loaded Ti-SBA-15 photocatalysts, the IR absorption at 960 cm⁻¹ commonly accepted the characteristic vibration of Ti–O–Si bond. From the TEM images, the regular silica morphology is maintained in the case of Ti-SBA-15(Si/Ti = 50) but the Ti-SBA-15 sample having Si/Ti ratio = 10 partially destroys the hexagonal highly ordered structure and the mesopore structure is disappeared by the clogging of mesopore channels by the titanium dioxides particles for the 50 wt.% TiO₂/Ti-SBA-15 samples. The photocatalytic activity increases with an increase of Ti content (decrease of Si/Ti ratio) and with an increase of TiO₂ loading content.