取代水杨醛席夫碱金属配合物结构对硫化物催化氧化性能的影响

将取代水杨醛席夫碱分别与Co(NO₃)₂、Ni(NO₃)₂反应合成了7种席夫碱金属配合物(C1～C7),并考察了其载氧性能,对模型硫化物1-己硫醇、二丁基硫醚、2-甲基噻吩的催化氧化性能及其影响因素。结果表明:配合物的载氧性能主要受其中心离子种类、配体取代基电子效应和空间效应及共轭程度的影响;中心离子与O₂的配位能力越强、配体取代基推电子能力越大且空间位阻越小、共轭链越长越有利于配合物载氧,其中每摩尔C7配合物的载氧量为0.523 mol;配合物的催化氧化性能由其载氧性能和在正辛烷中的溶解度共同决定,载氧量越高、溶解度越大,则对硫化物的催化氧化性能越好;配合物C6的催化氧化性能最佳,且对1-己硫醇和二丁基硫醚的催化氧化性能优于对2-甲基噻吩。     

Boron substitution effect on adsorption of H2 molecules on organometallic complexes

Hydrogen adsorption properties of Be/Sc doped pentalene complexes are investigated using second ordered Møller-Plesset method (MP2). In order to study the boron substitution effect, pentalene is further modified by substituting two and four boron atoms for carbon atoms at different positions and named as TBP1 and TBP2 for two boron atom substituted structures and FBP1 and FBP2 for four boron atom substituted structures. Two H₂ molecules get adsorbed on each Be doped complex and having 3.25, 3.31, 3.31, 3.38 and 3.38 wt% H₂ uptake capacity for C₈H₆Be₂, TBP1Be₂, TBP2Be₂, FBP1Be₂ and FBP2Be₂ complexes respectively. All Sc doped pentalene and boron substituted pentalene complexes can interact with nine H₂ molecules except TBP2Sc₂ complex. The TBP2Sc₂ complex can adsorb eight H₂ molecules. The H₂ uptake capacity is found to be 8.63, 8.73, 7.84, 8.83 and 8.83 wt% for C₈H₆Sc₂, TBP1Sc₂, TBP2Sc₂, FBP1Sc₂ and FBP2Sc₂ complexes respectively. Gibbs free energy corrected adsorption energy plots show that the H₂ adsorption on all Be doped complexes is possible at all temperatures and pressures considered here. The TBP1Sc₂ complex seems to be more promising hydrogen storage material among all Sc doped complexes over a wide range of temperature and pressure. The H₂ desorption temperatures obtained for the Be doped complexes are higher than the Sc doped complexes. Stability of the complexes is predicted with the help of the gap between the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals.     

Effect of Chlorine or Ester Incorporation on Diketopyrrolopyrrole -Based Polymeric Semiconductors

Organic photovoltaic materials incorporating either chlorine atoms or ester groups have been studied as replacement strategy for fluorinated compounds. However, the characteristics of such materials when used in organic field-effect transistors (OFETs) remain unclear. The present work synthesized three polymers via the copolymerization of diketopyrrolopyrrole (DPP) with monothiophene units having no substituents or incorporating either chlorine atoms or ester groups. All three materials were found to have similar photophysical and electrochemical properties even though their repeating units had different substituents. The maximum hole mobility values for the polymer specimens were determined to be 0.37 cm² V⁻¹ s⁻¹. The introduction of chlorine into the DPP-based polymer generated an amorphous semiconductor material that makes it a very promising candidate for commercial OFETs since its properties are independent of fabrication conditions. The new polymeric semiconductors demonstrated herein suggest the viability of such materials with regard to incorporation in organic field-effect transistors.     

多面体碳烷的结构规则研究

在 CNDO/2计算的基础上,提出了多面体碳烷和取代多面体碳烷的结构规则,即 BMO=n+l+BO.     

取代酚类化合物LC_(50)的QSAR模型建立与分析

基于定量结构.活性(QSAR)研究取代酚类化合物的急毒性具有重要意义。采用DFT-B3LYP方法,在较高基组6-311G~(**)水平下,全优化计算21种取代酚。从中获得分子最高占用和最低空轨道能(E_(HOMO)和E_(LUMO))、分子次最高占用和次最低空轨道能(E_(NHOMO)和E_(NLUMO))、分子总能量(E_T)、氢原子所带的最高正电荷(q_H~+)、最负非氢原子的静电荷(q~-)、分子偶极矩(μ)和分子体积(V)等描述符。结合文献中标题化合物对梨形四膜虫的毒性值(-lg LC_(50))和疏水性系数(10g Kow),由多元线性回归方法建成QSAR模型,采用内外双重验证的办法,深入分析和检验模型的稳健性。最佳模型的复相关系数(R~2),去一法(LOO)交替检验复相关系数(R_(cv)~2),外部预测样本复相关系数(R_(ext)~2)分别为0.924,0.922和0.830,故所建QSAR模型的稳定性和预测能力良好。由此推断,标题物对梨形四膜虫的毒性作用分为两步,首先穿过细胞壁在细胞内富集,以log Kow描述;其次与亲核试剂发生亲电反应,以点E_(NLUMO)表示。     

氰乙基化可溶性蛋白质锚定钯催化合成查耳酮的研究

制备了以超细二氧化硅为载体的氰乙基化可溶性蛋白质-钯催化剂，研究了它在三丁基芳基锡和取代肉桂酰氯的偶联反应中的催化行为。结果表明，该催化剂对偶联反应具有较高的催化活性和化学选择性，分离容易，可以重复使用。XPS分析说明催化剂中的活性中心质点是金属态的钯。     

水溶液中取代乙酸的量化计算模型

应用量子化学理论、超分子方法和ＣＮＤＯ／２计算方法，结合回归分析，对所选的７种模型进行量化计算，从中得出能模拟水溶液中羧酸的最佳量化计算模型。     

两种N-硝基取代苯胺的合成研究

以邻硝基苯胺、对硝基苯胺为原料,以乙酰硝酸酯做硝化剂,代替直接以发烟硝酸做硝化剂合成N-硝基取代苯胺类化合物。从一定程度上减少因苯胺氧化等反应的副产物,从而提高收率。对实验优化条件进行一定的研究探索,温度对收率影响较大。产物化学结构经IR、1HNMR、质谱,元素分析表征。     

未来农药的发展趋势

本文综述了农药的重要性以及农药的广泛使用所引起的日益严重的环境污染问题，指出了未来农药的发展趋势应该是绿色农药。绿色农药包括手性农药、光敏化农药、转基因农药、生物农药及绿色农药制剂等。     

无溶剂微波法合成meso-苯基四苯井卟啉锌

采用无溶剂微波固相法，合成了meso-苯基四苯并卟啉锌（Zn-PnTBP，n=1，2，3，4），通过紫外一可见光谱表征了其结构。结果表明原料配比、研磨时间、微波辐射时间等对反应的主要产物和产率都有很大影响，最终确定了形成Zn-P。TBP的最佳条件：n（邻苯二甲酰亚铵）：n（苯乙酸）：n（乙酸锌）=1．0：1．4：0．8、研磨时间为5min，在中等微波辐射下反应13min，产率达到28％。