三种手性MOFs的合成及其作为固定相在气相色谱的应用

发布时间：2018-05-25 02:19

本文选题：手性金属-有机骨架材料 + 气相色谱　；参考：《新疆师范大学》2017年硕士论文

【摘要】：金属-有机骨架材料(MOFs)因具有多功能性如孔隙率、催化和光学性质,以及手性而广泛应用于分离小分子气体,碳水化合物,无机阴离子,甚至巨大的有机离子。而MOFs好的选择性吸附和化学稳定性能也使得这类材料非常适用于气相色谱(GC)和液相色谱。最近,MOFs也已经作为色谱固定相被应用到气相色谱的分离应用中。为了克服MOFs填充柱差的分辨率(因为笨重的包装而产生相当大的扩散阻力),为了提高分离效率,MOFs涂层的毛细管柱也已被报道。虽然这种材料的分离应用非常有前景,但是迄今为止只有少数的例子被报道,特别是用作气相色谱固定相的分离应用。本研究拟从待分离物质的结构特征对我们MOFs结构特殊位点的对应性出发,可控制备出一系列具有手性永久性孔道结构的手性金属-有机骨架材料,作为气相色谱固定相,并且制备MOFs涂覆毛细管柱探索其应用于高分辨气相色谱分离。主要研究内容如下:(1)合成出一个具有永久性的手性开发孔道的MOF[Zn2(bdc)(L-Lac)(DMF)]·(DMF)(L-lac=L-lactate),并去溶剂成为不饱和配位的[Zn2(bdc)(L-Lac)]拥有接近10?的直径。把它作为一种新型的固定相制作出气相色谱毛细管柱进行分离。实验结果证明这个毛细管柱对含有不同官能团的单萜类化合物具有良好的选择性。除此之外,还对一系列含有不同官能团(R-OH,H-C(R)=O,C(RR')=O,HO-(R)C=O,R-O-(R')C=O,R-O-R')取代的直链烷烃、芳香碳水化合物以及环形碳水化合物有广泛的分离应用。高分辨率分离和检测这些单萜类化合物为分析分子结构与物理性质以及分子间的作用力之间的关系提供了一个机会,这也同样是食品、医药、香料和材料科学领域关注的重点。(2)利用一种具有平面Mn4O结构的手性金属-有机骨架材料Me2NH2)2[Mn4O(D-Cam)4]·(H2O)5然后去溶剂得到[Mn4O(D-Cam)4]2-作为新型手性固定相在气相色谱上进行分离,实验结果证明这个毛细管柱对含有不同官能团的单萜类化合物具有良好的选择性。除此之外,还对一系列含有不同官能团(R-OH,H-C(R)=O,C(RR')=O,HO-(R)C=O,R-O-(R')C=O,R-O-R')取代的直链烷烃、芳香碳水化合物以及环形碳水化合物有广泛的分离应用。(3)一个Mn基手性金属-有机骨架材料:具有手性层的[Mn3(HCOO)4(D-Cam)]n,用作新型气相色谱固定相制备了毛细管柱。实验结果表明MOFs涂覆的毛细管柱对六种含有不同官能团(R-OH,H-C(R)=O,C(RR')=O,HO-(R)C=O,R-O-(R')C=O,R-O-R')取代的直链烷烃、芳香碳水化合物以及环形碳水化合物具有良好的分离能力。
[Abstract]:The metal-organic framework material (MOF) is widely used in the separation of small molecular gases carbohydrates inorganic anions and even giant organic ions because of its multifunctional properties such as porosity catalytic and optical properties and chirality. The good selective adsorption and chemical stability of MOFs also make these materials very suitable for gas chromatography and liquid chromatography. Recently, MOFs have been used as stationary phase in gas chromatography. In order to overcome the difference resolution of MOFs packed columns (resulting in considerable diffusion resistance due to heavy packing), it has also been reported that capillary columns coated with MOFs have been reported to improve the separation efficiency. Although the application of this material is very promising, only a few examples have been reported so far, especially for gas chromatographic stationary phase separation. In this study, a series of chiral metal-organic skeleton materials with chiral permanent pore structure were prepared from the correspondence of the structural characteristics of the substances to be separated to our MOFs structural special sites, which were used as gas chromatographic stationary phases. MOFs coated capillary column was prepared to explore its application in high resolution gas chromatographic separation. The main contents of this study are as follows: (1) Synthesis of a chiral MOF with permanent chiral development pore [Zn _ 2N _ 2 BDC ~ (2 +) ~ L ~ (-) [Zn _ (2) B ~ (2 +) BDC ~ (2 +)] [Zn _ (2) BDC ~ (2 +)] [Zn _ (2) BDC ~ (2 +)] (L-Laci) has nearly 10 ~ (th)? The diameter of It was used as a new stationary phase to produce gas chromatographic capillary column for separation. The experimental results show that the capillary column has good selectivity for monoterpenes containing different functional groups. In addition, a series of linear alkanes, aromatic carbohydrates and annular carbohydrates, which contain different functional groups, R-OHH ~ (H-C) ~ (-) ~ (~) ~ (?) The high resolution separation and detection of these monoterpenes provide an opportunity to analyze the relationship between molecular structures and physical properties and intermolecular forces, which are also food and medicine. In the field of spice and materials science, the chiral metal-organic skeleton material Me2NH2)2 [Mn4O(D-Cam)4] H _ 2O _ 5 with planar Mn4O structure was used to separate [Mn4O(D-Cam)4] _ 2- as a new chiral stationary phase by gas chromatography. The experimental results show that the capillary column has good selectivity for monoterpenes containing different functional groups. In addition, a series of straight chain alkanes containing different functional groups, R-OHHHHHHH-Con, RRO- OHO-OOOOOOO-OOOOR-O-RGN), have been substituted for a series of alkanes, which have been replaced by a series of alkanes with different functional groups (R-OHH, H-Con, OHO-R), and a series of alkanes, which are replaced by different functional groups. Aromatic carbohydrates and ring carbohydrates have been widely used in the separation of aromatic carbohydrates and ring carbohydrates. A Mn-base chiral metal-organic skeleton material: [Mn3HCOOO4D-Cam4D-Cam4] n has been used as a new gas chromatographic stationary phase to prepare capillary columns. The experimental results show that the capillary column coated with MOFs has good separation ability for six alkanes, aromatic carbohydrates and ring carbohydrates, which are replaced by six alkanes, aromatic carbohydrates and ring carbohydrates.
【学位授予单位】：新疆师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O652.6

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