溶胶-凝胶法制备丙二酰胺型二氧大环多胺用作开管柱电色谱固定相的研究

This paper covers the preparation of a sol gel derived macrocyclic dioxopolyamine(1,4,7,10 tetraazaclotridecane 11,13 dione) stationary phase for open tubular capillary electrochromatography(OTCEC). The sol gel derived macrocyclic dioxopolyamine capillary columns have shown improved separations of neurotransmitters, isomeric nitrophenols, isomeric dihydroxybenzenes, isomeric aminophenols, isomeric diaminobenzenes and three ortho halogen anilines, in comparison with those of untreated capillaries. The characteristics of the sol gel derived macrocyclic dioxopolyamine capillary columns are compared with the capillary column modified with the macrocyclic dioxopolyamine by chemically bonded method after etching. The sol gel method provided a porous silica material with stationary phase in place within the same experimental procedure. This provided speedy fabrications of high efficiency columns with high surface area and improved phase ratio. We achieved high efficiencies of 60 000-340 000 plates/m for the various isomeric compounds. The reproducibility migration time and the plate number were pretty good.

手性二氧大环多胺对苦杏仁酸的手性识别研究

以自合成的手性二氧大环多胺作为手性溶解剂,采用NMR技术对苦杏仁酸进行手性识别研究。当主客体混合后,主客体的质子峰在1HNMR图谱中均发生不同程度的化学位移,且苦杏仁酸的α-次甲基氢的化学位移变化值在主客体摩尔比为1∶1时达到最大,从而表明主客体之间可能形成了较为稳定的摩尔比为1∶1的超分子复合物。这一研究结果表明手性二氧大环多胺与苦杏仁酸具有较强的超分子作用,可用于苦杏仁酸的手性识别及对映体拆分。

L-脯氨酸衍生的手性二氧大环多胺的晶体结构(英文)

以L-脯氨酸为原料合成了刚性手性二氧大环多胺(12S)-1,4,7,10-四氮杂二环[10.3.0]十五烷-3,11-二酮,通过元素分析、红外光谱、1HNMR、13CNMR和质谱进行了结构表征,并用X-射线单晶衍射测定了其晶体结构。该化合物为正交晶系,空间群为P2(1)2(1)2(1),晶体结构数据为:Mr=258.33,a=0.51019(8)nm,b=1.26981(18)nm,c=2.0130(3)nm,V=1.3041(3)nm3,D=1.316g/cm3,μ=0.097mm-1,F(000)=560,Z=4,R1=0.0712,ωR2=0.1302。化合物通过分子间氢键(N—H…O)形成了一系列沿a轴的微孔手性通道。

两种二茂铁甲基二氧大环多胺的电化学性质

利用循环伏安法对我们新设计合成的两种二茂铁甲基二氧大环多胺化合物——１－二茂铁甲基－１，４，８，１１－四氮杂环十三烷－５，７－二酮（简称ＦｃＣＨ２Ｌ１）和１－二茂铁甲基－１，４，７，１１，１４－五氮杂环十六烷－３，１５－二酮（简称ＦｃＣＨ２Ｌ２）——的电化学性质进行了研究，包括酸碱度的影响以及它们对Ｚｎ２＋，Ｃａ２＋，Ｃｄ２＋，Ｃｕ２＋，Ｎｉ２＋，Ｃｏ２＋等金属离子的电化学响应情况．在乙醇和水的混合溶剂体系中化合物ＦｃＣＨ２Ｌ１对Ｎｉ２＋具有选择性络合。

丙二酰胺型大环多胺键合固定相在毛细管开管电色谱中的应用

The macrocyclic dioxopolyamine compounds, 1,4,7,10-tetraazacyclotridecane-11,13-diones were used as stationary phases with the aid of 3-(2-cyclooxypropoxyl)propyl-trimethoxy silane as a bridge in open-tubular capillary electrochromatography(OTCEC). The capillaries were etched by aqueous sodium before being coated. These modified capillaries had shown improved separations of neurotransmitters, isomeric dihydrobenzenes, isomeric nitrophenols and isomeric aminophenols in comparison with untreated capillaries.