三種手性MOFs的合成及其作為固定相在氣相色譜的應(yīng)用
發(fā)布時(shí)間:2018-05-25 02:19
本文選題:手性金屬-有機(jī)骨架材料 + 氣相色譜; 參考:《新疆師范大學(xué)》2017年碩士論文
【摘要】:金屬-有機(jī)骨架材料(MOFs)因具有多功能性如孔隙率、催化和光學(xué)性質(zhì),以及手性而廣泛應(yīng)用于分離小分子氣體,碳水化合物,無(wú)機(jī)陰離子,甚至巨大的有機(jī)離子。而MOFs好的選擇性吸附和化學(xué)穩(wěn)定性能也使得這類(lèi)材料非常適用于氣相色譜(GC)和液相色譜。最近,MOFs也已經(jīng)作為色譜固定相被應(yīng)用到氣相色譜的分離應(yīng)用中。為了克服MOFs填充柱差的分辨率(因?yàn)楸恐氐陌b而產(chǎn)生相當(dāng)大的擴(kuò)散阻力),為了提高分離效率,MOFs涂層的毛細(xì)管柱也已被報(bào)道。雖然這種材料的分離應(yīng)用非常有前景,但是迄今為止只有少數(shù)的例子被報(bào)道,特別是用作氣相色譜固定相的分離應(yīng)用。本研究擬從待分離物質(zhì)的結(jié)構(gòu)特征對(duì)我們MOFs結(jié)構(gòu)特殊位點(diǎn)的對(duì)應(yīng)性出發(fā),可控制備出一系列具有手性永久性孔道結(jié)構(gòu)的手性金屬-有機(jī)骨架材料,作為氣相色譜固定相,并且制備MOFs涂覆毛細(xì)管柱探索其應(yīng)用于高分辨氣相色譜分離。主要研究?jī)?nèi)容如下:(1)合成出一個(gè)具有永久性的手性開(kāi)發(fā)孔道的MOF[Zn2(bdc)(L-Lac)(DMF)]·(DMF)(L-lac=L-lactate),并去溶劑成為不飽和配位的[Zn2(bdc)(L-Lac)]擁有接近10?的直徑。把它作為一種新型的固定相制作出氣相色譜毛細(xì)管柱進(jìn)行分離。實(shí)驗(yàn)結(jié)果證明這個(gè)毛細(xì)管柱對(duì)含有不同官能團(tuán)的單萜類(lèi)化合物具有良好的選擇性。除此之外,還對(duì)一系列含有不同官能團(tuán)(R-OH,H-C(R)=O,C(RR')=O,HO-(R)C=O,R-O-(R')C=O,R-O-R')取代的直鏈烷烴、芳香碳水化合物以及環(huán)形碳水化合物有廣泛的分離應(yīng)用。高分辨率分離和檢測(cè)這些單萜類(lèi)化合物為分析分子結(jié)構(gòu)與物理性質(zhì)以及分子間的作用力之間的關(guān)系提供了一個(gè)機(jī)會(huì),這也同樣是食品、醫(yī)藥、香料和材料科學(xué)領(lǐng)域關(guān)注的重點(diǎn)。(2)利用一種具有平面Mn4O結(jié)構(gòu)的手性金屬-有機(jī)骨架材料Me2NH2)2[Mn4O(D-Cam)4]·(H2O)5然后去溶劑得到[Mn4O(D-Cam)4]2-作為新型手性固定相在氣相色譜上進(jìn)行分離,實(shí)驗(yàn)結(jié)果證明這個(gè)毛細(xì)管柱對(duì)含有不同官能團(tuán)的單萜類(lèi)化合物具有良好的選擇性。除此之外,還對(duì)一系列含有不同官能團(tuán)(R-OH,H-C(R)=O,C(RR')=O,HO-(R)C=O,R-O-(R')C=O,R-O-R')取代的直鏈烷烴、芳香碳水化合物以及環(huán)形碳水化合物有廣泛的分離應(yīng)用。(3)一個(gè)Mn基手性金屬-有機(jī)骨架材料:具有手性層的[Mn3(HCOO)4(D-Cam)]n,用作新型氣相色譜固定相制備了毛細(xì)管柱。實(shí)驗(yàn)結(jié)果表明MOFs涂覆的毛細(xì)管柱對(duì)六種含有不同官能團(tuán)(R-OH,H-C(R)=O,C(RR')=O,HO-(R)C=O,R-O-(R')C=O,R-O-R')取代的直鏈烷烴、芳香碳水化合物以及環(huán)形碳水化合物具有良好的分離能力。
[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.
【學(xué)位授予單位】:新疆師范大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2017
【分類(lèi)號(hào)】:O652.6
【參考文獻(xiàn)】
相關(guān)期刊論文 前4條
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2 謝生明;袁黎明;;金屬-有機(jī)骨架材料用于色譜固定相[J];化學(xué)進(jìn)展;2013年10期
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