Accelerated Hydrolysis of p-Nitrophenyl Picolinate Catalyzed by Metallomicelle Made from a Novel Macrocyclic Polyamine Copper（Ⅱ） Complex

A copper（Ⅱ） complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,11-bis（hydroxylethyl）-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane （L） has been synthesized and characterized. Rate enhancement for hydrolysis of p-nitrophenyl picolinate （PNPP） catalyzed by 1 was studied kinetically under Brij35 micellar condition. For comparision, the catalytic activity of corresponding copper（Ⅱ） complex 2 of non-substituted macrocyclic polyamine ligand, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane （L＇） toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic polyamine copper（Ⅱ） complex 1 effectively catalyzed the hydrolysis of PNPP, and the pendant ligand hydroxyl group or deprotonated pendant ligand hydroxyl group can act as catalytically active species in the reaction. A ternary Complex kinetic model involving metal ion, ligand and substrate has been proposed, and the results confirmed the reasonability of such kinetic model.     

含吡咯烷酮基丙烯酸酯类单体的合成及聚合

轻度交联的聚甲基丙烯酸2-羟乙酯(HEMA)是众所周知的医用水凝胶,即所谓的“Hvdron”。但其吸水率一般在59%(EWC为37%),并不尽人意。近年来,为了提高这类水凝胶的亲水性及生物相容性,常用一些亲水性的烯类单体进行表面改性或通过共聚以达到此目的,N-乙烯基吡咯烷酮是较为常用的这类单体之一。本文合成了含吡咯烷酮基丙烯酸酯类的单体,即丙烯酸2-N-吡咯烷酮基乙酯(PyEA),甲基丙烯酸2-N-吡咯烷酮基乙醋(PyEMA),并研究了这两种单体在甲基丙烯酸二甲氨乙酯(DMAEMA)与过硫酸钾(KPS)所组成的氧化还原引发体系下的聚合。     

有机金属络合物用于高分子富氧膜的研究进展

本文介绍了能够可逆吸附分子氧的有机金属络合物用于高分子富氧膜的研究进展，以及以双重吸附理论进行的膜的促进输送机理。     

N-(4-苯甲酰苯基)衣康酰亚胺与甲基丙烯酸-N,N-二甲氨基乙酯组成的可聚合光氧化还原体系引发的丙烯腈光聚合

Ｎ （４ 苯甲酰苯基）衣康酰亚胺与甲基丙烯酸 Ｎ，Ｎ 二甲氨基乙酯组成的可聚合光氧化还原体系引发的丙烯腈光聚合高青雨杨更须崔元臣张福莲张举贤（河南大学化学化工学院开封４７５００１）李福绵（北京大学化学系北京１００８７１）关键词Ｎ （４ 苯甲酰苯基）...     

MODIFICATION OF TRANSITION METAL CATIONS TO POLYMER-STABILIZED PLATINUM COLLOIDAL CLUSTERS IN ENANTIOSELECTIVE HYDROGENATION OF METHYL PYRUVATE

Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate. Compared to the enantiomeric excess (e.e.) value (71.4%) obtained without the presence of metal cations, obvious e.e. enhancement (up to 82.5%) was resulted from the addition of Zn^2 but with a certain decrease in activity. The reaction parameters in the presence of Zn^2 were also studied. It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.     

A Novel Cu-Mo／ZSM-5 Catalyst for NOx Catalytic Reduction with Ammonia

The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wet impregnation method, and their catalytic performance for selective catalytic reduction of NOx was studied. The results showed that Cu-Mo/ZSM-5 is a very effective catalyst for NOx catalytic reduction with ammonia, especially when Cu/Mo molar ratio is about 1.5. It not only exhibited the extremely high catalytic activity, but also showed good stability for 02. The bulk phase structure of Cu-Mo/ZSM-5 catalysts was determined by XRD technique, and the results indicated that there is a maximum dispersion for Cu species when Cu/Mo molar ratio is 1.5, and an interaction between Cu and Mo along with HZSM-5 may be present in Cu-Mo/ZSM-5, which may possibly result in a special structure favorable for the catalytic reduction of NOx over Cu-Mo/ZSM-5 catalyst.     

水热法合成Ce0.67Zr0.33O0.2固溶体研究

采用两种不同前驱体通过水热法合成了Ce0.67Zr0.33O0.2固溶体,并通过XRD,BET,TPR等手段考察了样品的相结构,比表面及还原特性.结果表明,在180℃,12 h的水热条件下,以共沉淀产物为前驱体所制得的Ce0.67Zr0.33O0.2固溶体比表面积较高,但存在一定程度的相分离;以凝胶产物为前驱体制得的Ce0.67Zr0.33O0.2固溶体结构更完整,具有良好的还原特性及热稳定性.     

金属有机框架化合物为前驱体制备MgO微粒

在溶剂热条件下,以氯化镁与3-(吡啶-3-甲氧基)邻苯二甲酸为原料,成功合成了一个镁和甲酸根构筑的三维金属有机框架化合物,X射线单晶衍射确定了其晶体结构.通过对所合成的配合物高温煅烧,得到了氧化镁微粒,应用红外光谱、粉末衍射和扫描电子显微镜等对其结构和形貌进行了表征,结果表明,合成的氧化镁纯度高,晶型完整,颗粒分布较为均匀,粒径约为50μm.     

离子液体中用Heck反应合成2-取代萘烯丙醇化合物

利用Heck反应, 在离子液体、金属钯或镍、碱和膦配体反应体系中, 由卤代萘与烯丙醇反应, 制得了高收率和高选择性的2-取代萘烯丙醇化合物. 该方法原料便宜易得、操作简单、反应体系可循环使用. 并讨论了醋酸镍替代醋酸钯、不同膦配体、溶剂及碱对反应转化率的影响. 通过核磁共振、红外光谱、质谱和元素分析对产物的结构进行了表征.     

单硼五元杂环配体(C~4BH~5)过渡金属夹心高聚物的理论研究

用一维自洽场晶体轨道法探讨了过渡金属夹心高聚物[(C~4BH~5)M]~n(M=Cr,Mn,Fe,Co,Ni)的一维链结构和电子结构.计算表明,堆积单元(C~4BH~5)M中价电子数为奇数的高聚物结构会发生Peierls畸变,而价电子数为偶数的将取规则结构,由能带结构得到, [(C~4BH~5)Mn]~n的前线能带出现交叉,可能会发生进一步的结构畸变,但也有可能保持非满状态,成为异体.[(C~4BH~5)Ni]~n可能是不稳定的.其余三个高聚物为半导体或绝缘体,这系列高聚物电荷载流子通路主要依赖于金属d轨道重叠.