POLYMER-SUPPORTED CLUSTER II SYNTHESIS, CHARACTERIZATION AND CATALYTIC PROPERTIES OF POLYMERSUPPORTED HETEROPENTAMETALLIC CLUSTER FeCO3 (CO)12 (μ3-AuPph2CH2■-■)*

The polymer-supported cluster FeCo3 (CO)_(12) (μ3-AuPph_2 CH_2) (4) has been synthesized through reaction of CH_2 ph_2 PAuCl with the cluster anion FeCo_3 (CO)_(12)~-. They are characterized through IR spectra, electronic spectra and XPS, with homogenous analog FeCo_3 (CO)_(12) (μ3-AuPph_3) (3) as reference compound. The cluster (3) and the polymer-supported cluster (4) are good catalysts for hydroformylation of olefins. They have better activity and selectivity than the cluster (1) and (2).The supported cluster (4) is more stable and has catalytic activity at higher temperature than its homogeneous analog (3). From the metal core level binding energies in XPS and λ_(max) in electronic spectra, it is found that the metal-metal bonds in (4) are reinforced bypolymer supporter. The cluster (3) and (4) can be reused , and possibly do not fragment to one metal species in the course of catalytic reaction.     

二价铜离子和联咪唑催化的酚与碘代芳烃的乌尔曼反应研究

Ullmann-type diaryl ether synthesis can be performed at 100 ℃ in good to excellent yields by aryl iodides as the substrates under the assistance of copper（Ⅱ） and 2,2＇-biimidazolyl.     

ZIF-8@Fe_3O_4磁性固相萃取结合高效液相色谱法测定果汁中3种苯甲酰脲杀虫剂

发展了磁性沸石咪唑酯骨架材料(ZIF-8@Fe_3O_4)磁性固相萃取结合高效液相色谱-二极管阵列检测器,测定果汁中氟幼脲、四螨嗪和氟啶脲3种苯甲酰脲杀虫剂(BUs)的新方法。利用X射线衍射仪、傅立叶变换红外光谱仪、扫描电子显微镜和振动样品磁强计对合成的ZIF-8@Fe_3O_4吸附剂进行表征,考察了溶液pH值、吸附剂用量、吸附时间、洗脱溶剂种类和体积(单次洗脱体积×洗脱次数)对BUs萃取效率的影响。在最优实验条件下,氟幼脲和四螨嗪在2.0～200 ng/mL、氟啶脲在3.5～350 ng/mL范围内线性关系良好(相关系数r=0.999),检出限(S/N=3)和定量下限(S/N=10)分别为0.6～1.0 ng/mL和2.0～3.5 ng/mL。3个加标水平下的回收率为82.7%～98.6%,日内和日间(n=3)相对标准偏差(RSD)分别为1.2%～6.1%和1.3%～9.0%。当上样体积为10 mL时,ZIF-8@Fe_3O_4对果汁中3种BUs的富集倍数为43.4～48.1倍,吸附剂重复使用10次后,3种BUs回收率的RSD不大于8.8%。该方法灵敏、高效,可用于果汁样品中BUs的分析。     

Electrodeposition mechanism of Ni?Mo?P alloy in the solution of ammoniac citrate

The induced codeposition mechanism of Mo, P and Ni from the solution of ammoniac citrate was studied by means of steady-state polarization, AC impedance and X-ray Photoelectron Spectroscopy (XPS). The result of electrochemical measurements proved that [NiCit(NHs)₂]- is the electro-active species of nickel, though nickel ions exist mainly as [NiCit(NH₃)₃]^? in ammoniac citrate. XPS experiments proved the existence of tetravalent molybdenum corresponding to MoO₂ on the surface of mme deposits. The intermediate product, MoO₂, WM probably reduced to Mo in the alloy deposit by atomic hydrogen adsorbed on the induced metal nickel. The reduction of H₂PO^?₂ occurs through two distinctive steps with PH₃ an an intermediate, which subsequently reacts with atomic hydrogen to form P in the alloy deposit. The electrodeposition mechanism was proposed in this paper.     

[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O的水热合成与表征

首次合成了[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O,通过元素分析、红外光谱和X射线单晶衍射对合成产物进行了表征,并用TGA-DSC研究了化合物的热稳定性.晶体属单斜晶系,P21/m空间群,a=1.2596(3)nm,b=1.8715(4)nm,c=1.9816(4)nm,α=γ=90°,β=90.16(3)°,V=4.671(2)nm3,Z=2,Mr=4358.66,Dc=3.100g·cm-3,μ=19.978mm-1,F(000)=3792,R=0.0835,Rw=0.2026.结果表明,在晶体结构内形成了0.7364nm×0.8354nm的微孔.     

假橐吾中四对新的倍半萜结构研究

从假橐吾全草中分离得到四对新的(1/2,3/4,5/6,7/8)和一对已知的（9／10） 8，9－开环艾里莫芬内酯型倍半萜，每一对均为C－8位差向异构体。它们的结构通 过波谱方法阐明并通过酰化或酯化分离后得到证实。活性筛选实验表明，1／2和3 ／4具有细胞毒活性。     

K3[GdⅢ(nta)2(H2O)]·6H2O和(NH4)·[GdⅢ(Cydta)(H2O)2]·5H2O的合成及晶体结构

GdⅢ的配合物常被用作MRI造影剂[1,2]. GdⅢ的离子半径和电子结构分别为0.107 8 nm和高自旋f 7, 理论预测应与氨基多羧酸类配体形成稳定的九配位配合物[3～5]. 为证实理论预测并在此基础上寻找合适的可用于定向修饰的配体以及为提高GdⅢ配合物的脂溶性使其具有更好的细胞渗透性, 选择四齿配体nta和含有脂环烃的六齿配体Cydta分别合成了GdⅢ的配合物, 并测定了它们的分子结构. 结果显示, GdⅢ与nta形成九配位配合物, GdⅢ与Cydta形成八配位配合物.     

新磺酰脲类化合物的合成、结构及构效关系研究(I)——N-(2''''-嘧啶基)-2-甲酸乙酯-苯磺酰脲的晶体及分子结构

本文在合成标题化合物的基础上,测定了其晶体结构.晶体属单斜晶系,空间群为P2_1/a.晶胞参数a=0.7348(2)nm,b=2.1496(4)nm,c=0.9973(2)nm,β=90.19(2)°,V=1.576nm~3,Z=4.晶体结构由直接法解出,进行全矩阵最小二乘法修正,R=0.059.分子中的嘧啶磺酰脲、苯环及酯基三部分分别形成3个独立的平面共轭体系.S-N原子间形成d-pπ键并参加到第一个共轭体系中.分子中还存在着N与H原子间的分子内氢键.     

葡萄糖及半乳糖衍生的手性双膦-铑(Ⅰ)配合物催化苯乙烯不对称氢甲酰化反应

合成了四个从葡萄糖及半乳糖衍生的手性芳基双膦配体,制备了手性双膦-铑(Ⅰ)配合物催化剂,并将其用于苯乙烯不对称氢甲酰化反应中.结果表明,葡萄糖骨架手性中心与联萘基之间有协同作用,对映体过量值和转化率受配体C-4骨架立体中心的绝对构型影响,而产物的绝对构型则主要由联萘单元控制;配体4-双{[(S)-1,1′-联萘基-2,2′-双基]-磷}-苯基-3,6-脱水-β-D-葡萄糖的吡喃糖苷基和联萘基的匹配组合,给出41%的对映体选择性和74∶26(异构/正构)区域选择性.     

头孢克洛和δ-3-头孢克洛的毛细管区带电泳分离

建立了分离头孢克洛和δ-3-头孢克洛的毛细管区带电泳法(CZE)；在CZE中，以4-磺酸杯芳烃[6]作为异构体选择性试剂成功地分离了头孢克洛和δ-3-头孢克洛；当以4-磺酸杯芳烃[6]作为异构体选择性试剂时，背景缓冲液的pH值和4-磺酸杯芳烃[6]的浓度是影响头孢克洛和δ-3-头孢克洛分离的重要参数；同时还考察了有机溶剂和β-环糊精对分离的影响；并将该方法成功地用于测定口服头孢克洛干混悬剂中的有效成分——头孢克洛，结果令人满意。