A Large Conformational Change of a Bridged β-Cyclodextrin Dimer in Aqueous Solution

A novel bridged β-CD dimer in which two β-cyclodextrins were linked by a naphthalene at positions 2 and 7 has been synthesized. 1H and 13CNMR measurements showed that a large change in the conformation of the dimer occurred in aqueous solution. The dimer interacted with methyl and ethyl orange to form stable inclusion complexes via "induced fit" mechanism.     

含氮宾或卡宾的金属羰基簇合物的结构化学研究——Ⅰ.H_2Fe_3(N-C_6H_5)(CO)_9和Fe_3(N-C_6H_5)(μ_3-CO)(CO)_9的合成和结构

含氮宾的两个三核羰基铁簇合物是由[Et_3NH][HFe_3(CO)_(11)]与C_6H_5NCO在苯中反应获得。应用四园衍射仪测定了H_2Fe_3(N-C_6H_5)(CO)_9(Ⅰ)和Fe_3(N-C_6H_5)(μ_3-CO)(CO)_9(Ⅱ)的晶体结构。晶体数据为:C_(15)H_7NO_9Fe_3(Ⅰ),空间群P2_1/a,a=18.343(2),b=9.072(1),c=11.451(1)(?),β=102.03(1)°,V=1863.7(?)~3,Z=4,D_c=2.143g/cm~3;C_(16)H_5NO_(10)Fe_3(Ⅱ),空间群P2_1/c,a=8.634(1),b=13.026(1),c=17.642(2)(?),β=97.68(1)°,V=1966.3(?)~3,Z=4,D_c=1.820g/cm结构系用直接法解出,最后R_(Ⅰ)因子为0.033,R_(Ⅱ)因子为0.027。测定结果表明,(Ⅰ)和(Ⅱ)分子均具有C_s对称性,且三个Fe原子共面,呈近似等边三角形结构。(Ⅰ)中面桥N原子以不对称方式与三个Fe原子成键;(Ⅱ)中面桥羰基以不对称方式与三个Fe原子键连。Fe-N和Fe-C键长分别在1.896-1.938(?)和2.006-2.110(?)之间。     

Application of diaza-18-crown-6-capped beta-cyclodextrin bonded silica particles as chiral stationary phases for ultrahigh pressure capillary liquid chromatography

Two bonded chiral stationary phases (CSPs), 8-aminoquinoline-2-ylmethyl- and 8-aminoquinoline-7-ylmethyl-diaza-18-crown-6-capped [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl silica particles (non-porous, 1.5 microm), have been prepared and evaluated using capillary liquid chromatography at high pressures (> or = 8000 p.s.i.). High column efficiency (up to 400 000 plates m(-1)) was achieved for chiral separations. These CSPs with two recognition sites, i.e. substituted-diaza-18-crown-6 and beta-cyclodextrin combined with high chromatographic efficiency provide good resolution of a variety of enantiomers and positional isomers in relatively short times under reversed-phase conditions. After inclusion of a Ni (II) ion from the mobile phase, the positively charged crown ether-capped beta-cyclodextrin facilitates specific static, dipolar, and host-guest complexation interactions with solutes.     

铽(Ⅲ)-1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4]体系荧光性质的研究及应用

本文研究了Tb(Ⅲ)-1,4-双(′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](BPMPBD)-溴化十六烷基三甲胺(CTMAB)体系的荧光性质,探讨了响影体系荧光性质的诸因素,确定了最佳实验条件。该体系中Tb(Ⅲ)浓度以2.0×10~(-5)～1.0×10~(-10)mol/L范围内与其荧光强度呈线性关系,检测限可达到5.0×10~(-11)mol/L。应用于合成样品中微量Tb(Ⅲ)的分析,结果令人满意。     

Aerobic oxidation assisted by ligand-free palladium catalysts

Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view.     

The Study of Anti-tumor Activity of Trichosanthin by Cyclic Voltammogram

IthasbeenreportedthatTrichosanthi11(TCS),isolatedfromrkiI-ilolt)ii,hasanti-tumorI-4andanti-vira1activities5-'.Someanti-tun1orremedies,whicharedesignedfromTCS,arebeingtestedanddeveloped'-.'.StudyingthebioIogicalphenomenonbyelectrochemicalmethodsisanewhotresearchspotemerginginrecentyears".Manyresultsshowedthatnotonlytheenzymesystemsuchassuccinatedehydrogenasedisplayedthediode-likebehaviorduringtheelectrontransferprocess",butalsothehigh1yorganizedorganeIle,forexample,mitochondria,andevenintac…     

Investigation of radical cation in electrophilic fluorination by ESI-MS

Reaction solutions of selectfluor (1) with triphenylethylene (4a) and tetraphenylethylene (4b) were monitored by ESI-MS and ESI-MS/MS. Detection and characterization of the key radical cationic intermediates 5a.+ and 5b.+) fully supports the SET mechanism in electrophilic fluorination as depicted above. [reaction: see text]     

有机锗化合物中碳氢的快速测定

报道了用Co3O4 作覆盖氧化剂分析有机锗化合物中碳氢元素的方法。通过对 9个样品的十几次分析 ,碳、氢的相对误差分别小于± 1.30 % ,4 .4 0 %。方法简便 ,结果稳定可靠 ,可用于含锗有机化合物的碳氢分析。     

超临界二氧化碳介质中钯催化炔烃羰基化反应

研究了以超临界二氧化碳为反应介质实现改善钯催化炔烃羰基化反应绿色性的方法 .研究结果表明 :醇的用量、二氧化碳压力和反应温度等因素均对钯催化炔烃羰基化反应的化学选择性均有影响 ,即存在炔烃的羰基化反应与氧化偶合反应的竞争