新型氨基酸（醇）类手性离子液体的合成及其应用研究

发布时间：2018-06-05 00:03

本文选题：功能性离子液体 + 手性离子液体　；参考：《浙江大学》2017年博士论文

【摘要】：功能性离子液体是指在离子液体的阳离子、阴离子或者阴阳离子中引入目标官能团,使其具有特殊的性能,满足实际应用的需要。常见的功能性离子液体有手性离子液体、酸性离子液体和含金属离子液体等。本文着重关注手性离子液体及其应用研究。自1997年Howarth等首次报道手性离子液体以来,其已作为手性催化剂应用于不对称合成,以及作为手性拆分剂应用于光谱和色谱等领域。然而,无论是手性离子液体的种类,还是应用范围都还有很大的发展空间。鉴于此,我们以氨基酸或氨基醇类单构型分子为起始原料,经多步衍生合成出一系列含有脲基或酰胺的手性离子液体,并将其应用于手性拆分或手性识别。具体内容包括以下四个部分:1、基于手性选择性配位络合对四种对映体的快速分析和分离研究:以(S)-苯丙氨酸为起始原料,经三步反应合成了两种新型的手性离子液体。研究发现,该离子液体可以作为手性拆分剂分离和识别色氨酸、色氨醇、苯丙氨酸以及苯丙氨醇四种对映体。在不同溶剂中,其具有不同的表现形式。如:以水(或者甲醇)作为溶剂和手性离子液体与铜离子作为手性配体,(S)-色氨酸能够与(S)-CIL络合成键并产生沉淀;以二甲亚砜作为溶剂和手性离子液体与铜离子作为手性配体,(S)-色氨酸与(S)-CIL混合后为蓝色,(R)-色氨酸与(S)-CIL混合后为绿色。此外,我们也利用1HNMR和理论计算猜测了其可能的络合成键方式。2、基于席夫碱反应的多组分自组装实现手性化合物的高效拆分:以(S)-苯丙氨醇为起始原料,经两步反应合成出目标手性离子液体并作为手性拆分剂。利用胺类及氨醇类化合物与3-吲哚甲醛(3-羟基苯甲醛)反应生成的席夫碱,在手性配体的配位成键作用下,成功对10种对映体进行手性拆分,e.e.值最高可以达到95%,产率最高为94%。同时,我们也以(S)-CIL-1+CoC12为手性识别剂,实现了基于1屯NMR对5种胺类对映体的手性识别。3、基于手性离子液体双水相体系对氨基酸对映体的手性拆分研究:以(R)-2-氨基-1-丁醇为原料,经多步反应合成出目标功能性离子液体,并研究了基于该手性离子液体的双水相体系对氨基酸的手性拆分效果。首先,通过浊点法测定,确定了离子液体、硫酸钠和水三元体系的组成。其次,以拆分苯丙氨酸为例,对可能影响萃取结果的因素进行了筛选优化,如:温度、时间和以及离子液体与水的体积比。并利用该方法对其他19种氨基酸进行了对映体拆分。结果表明,该双水相体系对六种氨基酸有一定的手性拆分能力。若经多步萃取,手性拆分效率明显提高,e.e.值最高可以达到92%。4、基于功能性离子液体修饰的金纳米粒子对氨基酸快速定性、定量分析研究:以胱氨酸为起始原料,经多步反应设计合成出目标功能性离子液体,并将其作为修饰剂和稳定剂键合到金纳米粒子表面。通过FTIR,UV-vis和TEM的表征,证实离子液体已经成功修饰金纳米粒子。在铜离子的络合作用下,该材料能够对5种氨基酸进行快速定性(颜色变化)检测,并具有很好的定量关系。此外,我们也利用该方法检测人体尿液中组氨酸的含量。
[Abstract]:Functional ionic liquids refer to the introduction of target functional groups in ionic liquids, anions or yin and yang ions, so that they have special properties and meet the needs of practical applications. The common functional ionic liquids include chiral ionic liquids, acidic ionic liquids and metallic ionic liquids. This paper focuses on chiral ionic liquids. Since the first report on chiral ionic liquids, such as Howarth in 1997, it has been used as a chiral catalyst for asymmetric synthesis and as a chiral separation agent in the fields of spectroscopy and chromatography. However, there is still a lot of space for the types and applications of chiral ionic liquids. A series of chiral ionic liquids containing ureas or amides are synthesized by multistep derivatization with amino acid or amino alcohols as starting materials, and are applied to chiral separation or chiral recognition. The specific content includes four parts: 1, rapid analysis and separation of four enantiomers based on chiral selective complexing. Study: using (S) - phenylalanine as the starting material, two new chiral ionic liquids have been synthesized by three steps. It is found that the ionic liquid can be used as a chiral separation agent to separate and identify four enantiomers of tryptophan, tryptophan, phenylalanine and phenylalanine. In different solvents, it has different forms. As a solvent and chiral ionic liquid and copper ion as chiral ligand, (S) - tryptophan can synthesize bonds with (S) -CIL collaterals and produce precipitation; with two methyl sulfoxide as solvent and chiral ionic liquid and copper ions as chiral ligands, (S) - tryptophan and (S) -CIL mixed blue, (R) - tryptophan and (S) -CIL mixed green. In addition, we also used 1HNMR and theoretical calculations to guess the possible complex bond mode.2. The high efficiency separation of chiral compounds based on the multi component self-assembly of Schiff base reaction: using (S) - phenylpropanol as the starting material, the target chiral ionic liquid was synthesized by two steps and used as a chiral resolution agent. The Schiff base, which is produced with 3- indolaformaldehyde (3- hydroxybenzaldehyde), successfully chiral separation of 10 enantiomers under the coordination of chiral ligands. The highest E.E. value can reach 95% and the highest yield is 94%.. We also use (S) -CIL-1+CoC12 as a chiral recognition agent to realize the hand of 5 amine enantiomers based on 1 Tuen NMR. .3, based on the chiral separation of amino acid enantiomers based on chiral ionic liquid biaqueous system: using (R) -2- amino -1- butanol as raw material, the target functional ionic liquid was synthesized by multistep reaction, and the chiral separation effect of amidic acid based on the chiral ionic liquid was studied. First, the determination of the amino acid by the cloud point method. The composition of the ionic liquid, sodium sulfate and water three element system is determined. Secondly, the factors that may affect the extraction results are screened and optimized for the separation of phenylalanine, such as temperature, time, and the volume ratio of the ionic liquid to the water. And the other 19 amino acids are separated by the method. The results show that the double water is the double water. The phase system has a certain chiral separation ability for six kinds of amino acids. If multistep extraction, the efficiency of chiral separation is obviously improved and the highest E.E. value can reach 92%.4. Based on the functional ionic liquid modified gold nanoparticles, the amino acids are qualitative and quantitative analysis. The target is designed and synthesized with cystine as the starting material by multistep reaction. A functional ionic liquid, which is bonded to the surface of gold nanoparticles as a modifier and a stabilizer. Through the characterization of FTIR, UV-vis and TEM, it is proved that the ionic liquid has successfully modified the gold nanoparticles. Under the complexation of copper ions, the material can detect fast qualitative (color change) of 5 kinds of amino acids and have good quantitative determination. In addition, we also used this method to detect histidine in human urine.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O645.1

【参考文献】