含吡唑甲酰胺基E-β-法尼烯类似物的设计、合成及生物活性

为发现防治蚜虫的新型活性化合物,以蚜虫报警信息素E-β法尼烯(EBF)为先导,设计合成了20个未见文献报道的含吡唑环甲酰胺基EBF类似物,所有化合物结构均通过1H NMR,IR及HRMS确证.初步生物活性研究表明,部分目标化合物对五日龄豆蚜(Aphis craccivora Koch)在600mg/L时表现出较好的杀虫活性,其中5a及5k对豆蚜活性与商品化药剂氟虫腈及先导化合物EBF相当,甚至优于EBF.对影响目标化合物的活性因素进行了初步探讨.     

The synthesis of P-stereogenic MOP analogues and their use in rhodium catalysed asymmetric addition

The synthesis is reported of novel P-stereogenic binaphthyl substituted monophosphines via a short five-step synthesis using a nickel coupling reaction with separation of the borane-protected diastereomeric products. Extensive coordination studies of these ligands with a number of well-known metal precursors were performed to more effectively understand their behaviour during catalysis.These ligands and some previously reported P-stereogenic ligands were tested in the rhodium catalysed asymmetric addition of phenyl boronic acid to napthaldehyde. These studies in asymmetric catalysis were used to compare the chiral induction of ligands that combine both axial and central chirality with ligands lacking P-stereogenicity.     

Synthesis of mesoporous zeolite single crystals with cheap porogens

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), temperature-programmed desorption of ammonia (NH₃-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystal pores are randomly distributed in the whole crystal. ²⁷Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites.     

H-MCM-22沸石分子筛中Brnsted/Lewis酸协同效应的~1H 和~(27)Al双量子魔角旋转固体核磁共振研究

采用各种固体核磁共振 (NMR) 技术详细研究了 H-MCM-22 分子筛中 Brnsted/Lewis 酸的协同效应. 二维 1H 双量子魔角旋转 (DQ-MAS) NMR 结果表明, 在脱铝 H-MCM-22 分子筛中 Brnsted 酸位 (骨架桥式羟基) 和 Lewis 酸位 (非骨架铝羟基) 之间是空间邻近的, 暗示着可能存在 B/L 酸协同效应. 二维 27Al DQ-MAS NMR 结果揭示了各种铝物种之间的空间邻近性, 表明 B/L 酸协同效应优先发生在 H-MCM-22 分子筛超笼中的骨架 T6 位铝和非骨架铝物种之间. 2-13C-丙酮探针分子实验发现, 因 B/L 酸协同效应而导致脱铝 H-MCM-22 分子筛酸性明显增强, 氘代吡啶探针分子实验也证实在 H-MCM-22 分子筛的超笼中发生了 B/L 酸协同效应. 上述结果将有助于我们理解在脱铝 H-MCM-22 分子筛上发生的多相催化机理.     

Tannic acid-coated zeolite Y nanoparticles as novel drug nanocarrier with controlled release behavior and anti-protozoan activity against Trichomonas gallinae

In this study, a pH-sensitive drug release system was prepared by zeolite Y nanoparticles and tannic acid. Zeolite Y nanoparticles were synthesized via hydrothermal synthesis of colloidal suspensions and after that, were coated with tannic acid. In order to evaluate its performance, metronidazole as an anti-protozoan drug was loaded into nanocarriers via immersing method to study the in-vitro drug delivery behavior. This nanocomposite carriers represented pH-sensitive behavior and had more and faster release in acidic medium. In-vitro effects of metronidazole-loaded nanoparticles was measured against Trichomonas gallinae trophozoites in Trypticase Yeast extract Maltose medium. The results suggested that metronidazole-loaded and tannic acid-modified zeolite Y nanoparticles could be a potential anti-trichomonal agent.     

Adsorption of Benzene and Propylene in Zeolite ZSM-5： Grand Canonical Monte Carlo Simulations

The adsorption behavior of benzene and propylene in zeolite ZSM-5 was studied by Grand Canonical Monte Carlo(GCMC) simulations. It could be found that benzene and propylene molecules showed different adsorption behavior in the zeolite cavities. The loadings of propylene were significantly larger than those of benzene at 100 kPa. From the figures of potential energy distribution,the potential energy of benzene/zeolite was more negative than that of propylene/zeolite,so benzene could be adsorbed more stably t...     

H-ZSM-5分子筛上环己烯芳构化反应历程的理论研究

基于76T簇模型,采用量子力学和分子力学联合的ONIOM2(B3LYP/6-31G(d,p):UFF)方法研究了H-ZSM-5分子筛上环己烯芳构化反应历程.结果表明,环己烯首先吸附在分子筛酸性位上,与酸性质子共同脱除一个H2分子后,在分子筛骨架氧上生成烷氧配合物中间体;然后再脱质子得到环己二烯,同时酸性位复原;再经历脱氢和脱质子历程,最后得到产物苯,并吸附在复原的分子筛酸性位上.计算得到脱氢的活化能依次为279.64和260.21kJ/mol,脱质子的活化能依次为74.64和59.14kJ/mol.所有脱氢反应都是吸热过程,生成表面烷氧活性中间体,随后的脱质子反应能垒较低,而且是放热过程.此外,比较了环己烯在分子筛酸性位上的三个竞争反应,即脱氢、质子化和氢交换反应的活化能垒,证明环己烯优先发生脱氢反应.     

CuY型分子筛制备及吸附脱硫影响因素研究

通过液相离子交换法制备CuY型分子筛,并利用正交实验得到了制备过程中交换时间、交换温度、铜离子浓度的最佳条件。系统研究了CuY分子筛的焙烧温度、吸附时间、吸附温度对其吸附脱除模拟油中二苯并噻吩(DBT)的影响。采用XRD、ICP及BET比表面积分别对不同CuY分子筛的骨架结构及阳离子负载量进行了研究。结果表明,二次交换后,分子筛已达到交换平衡,最佳焙烧温度为450℃,温度过高会破坏分子筛的骨架结构;分子筛上的吸附水对其吸附脱除二苯并噻吩的能力有较大的影响。     

白藜芦醇类似物与人血清白蛋白的相互作用

采用荧光光谱、三维荧光光谱、紫外吸收光谱研究白藜芦醇类似物(Z)-2-(3,4-二甲氧苯基)-3-(4-二甲氨基苯基)丙烯腈(HCQ)与人血清白蛋白(HSA)的相互作用,探讨其作为抗肿瘤药物的可能。结果发现HCQ与HSA形成了基态配合物,HCQ主要结合于HSA的位点Ⅰ,与位点Ⅱ也有微量的结合,反应为自发的放热反应,其ΔH、ΔS、ΔG均小于零,二者之间的结合力为氢键或者范德华力,结合常数为104～105数量级。HCQ与HSA的结合使HSA构象发生变化,Trp-214所处的环境疏水性增加,使得其内源性荧光显著降低。说明合成的白藜芦醇类似物能够与人血清白蛋白结合。     

TS分子筛的催化氧化性能研究Ⅴ.环己酮氨肟化反应

研究了自制的钛硅分子筛(TS-1)催化H_2O_2参与的环己酮氨肟化反应.结果表明,降低反应溶液中H_2O_2的浓度、增加NH_3用量有利于H_2O_2利用率、环己酮肟收率和选择性的提高,适宜的n(H_2O_2):n(酮)<1.0,n(NH_3):n(酮)>2.0.反应时间应控制在3.5h左右.对溶剂的研究显示,叔丁醇在溶剂中所占的体积对反应有较大的影响,在叔丁醇体积分数为0.2到0.8之间,实验获得了较好的结果.当n(NH_3):n(H_2O_2):n(酮)=2.0:1.0:1.0,叔丁醇体积分数为0.5,反应时间2.5h,反应温度353K时,H_2O_2利用率、环己酮肟收率和选择性分别达95%,94%和97%以上.并对空白实验结果和TS-1的重复性试验进行了讨论.