A novel chiral ligand exchange capillary electrophoresis for diols and polyols using borate anion as a central ion of the chiral selector

使用硼酸根阴离子作为手性选择器的中心离子的新型二醇和多元醇手性配体交换毛细管电泳

• 批准号: 17550092
• 负责人: KODAMA Shuji
• 金额: $ 2.09万
• 依托单位: Toyama Institute of Health
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17550092/
• 关键词: borate; enantiomer; capillary electrophoresis; enantioseparation; borospirane; ligand exchange; diol; polyol; ホウ酸錯体; ジオール化合物; 単糖; ANTS; PMP

In chiral ligand exchange capillary electrophoresis(CLECE), copper(II) complexes with amino acids or their derivatives have been widely used as chiral selectors for the enantioseparation of amino acids, their derivatives, and α-hydroxy acids, where the ternary copper(II) complexes are formed by the ligand-exchange reaction of the chiral selector with the racemate. On the other hand, borate anion interacts with cis-1, 2- and cis-1, 3-diols to form monocyclic complex, and spirocyclic complex, which coexist in aqueous solution. Recently, we have found that native DL-pantothenic acid(DL-PTA) was enantioseparated by CLECE using borate as a central ion and(S)-3-amino-1, 2-propanediol(SAP) as a chiral selector. In this study, we studied (1) the mechanism of enantioseparation of DL-PTA in CLECE using a diol-borate system and (2) the application of CLECE for the enantioseparation of other diols and polyols. (3) In order to apply the proposed CLECE to real samples, we also studied covalent modif … More ication procedures to obtain capillary that gives reproducibile migration times for CE.(1) Using ^<13>C and^<11>B NMR, it was confirmed that the binary complexes and the ternary complexes coexist at equilibrium in the ternary system. Thermodynamic experiments by variable temperature ^<11>B NMR revealed that the ternary complex, [B(SAP)(D-PTA)]^-, was entropically more stable than [B(SAP)(L-PTA)]^-. Two geometrical isomers are possible for the respective ternary complexes, senuempmcal molecular orbital calculations indicated that(5) isomer is more probable for the respective ternary complexes with D^- and L-PTA. In the optimized structure of(S)-[B(SAP)(D-PTA)]^- in water, the SAP and D-PTA ligands were oppositely oriented to form a rather linear structure, while the diastereomer, (5)-[B(SAP)(L-PTA)]^-, have a folded structure. Because such a difference in the solvated structure of the ternary complexes can give different electrophoretic velocity in capillary electrophoresis, the enantioseparation of DL-PTA in CE is reasonably attributed to a difference in the observed electrophoretic mobility for the equilibrated ternary systems containing the respective ternary complexes.(2) We found that three compounds having 1, 2-diol structure(1-phenyl-1, 2-ethanediol, 3-phenoxy-1, 2-propanediol and 3-benzyloxy-1, 2-propanediol) were enantioseparated by ligand exchange micellar electrokinetic chromatography using(1S, 2S, 3R, 5S)-pinanediol as a chiral selector and borate anion as a central ion together with sodium dodecyl sulfate and that six reducing monosaccharides(mannose, galactose, fucose, glucose, xylose, and arabinose), which were derivatized with 8-aminonaphtalene-1, 3, 6-trisufonate, were simultaneously enantioseparated by CLECE using borate as a central ion and SAP as a chiral selector.(3) Sulfonated groups were chemically introduced to an inner wall of untreated fused silica capillary with 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane. The sulfona Less

在手性配体交换毛细管电泳（CLECE）中，铜（II）与氨基酸或其衍生物的配合物作为手性选择剂被广泛用于氨基酸及其衍生物和α-羟基酸的对映体分离，其中铜（II）三元配合物是通过手性选择剂与外消旋体的配体交换反应形成的。另一方面，硼酸根阴离子与顺式-1，2-和顺式-1，3-二醇相互作用形成单环配合物和螺环配合物，它们共存于水溶液中。最近，我们发现DL-泛酸（DL-PTA）在以硼酸根为中心离子，（S）-3-氨基-1，2-丙二醇（SAP）为手性选择剂的CLECE中得到了对映体分离。本论文主要研究了二醇-硼酸盐体系在CLECE中拆分DL-PTA的机理以及CLECE在其他二醇和多元醇拆分中的应用。(3)为了将CLECE应用于真实的样品，我们还研究了共价键的选择性 ...更多信息 毛细管电泳的迁移时间可重现。(1)用~ 1C<13>和~ 1H <11>B NMR证实了三元体系中二元配合物和三元配合物在平衡状态下共存。变温~ 1H B NMR热力学实验<11>表明，三元配合物[B（SAP）（D-PTA）]^-比[B（SAP）（L-PTA）]^-具有更高的熵稳定性。三元配合物可能存在两种几何异构体，半经验分子轨道计算表明，D^-和L-PTA三元配合物可能存在（5）种几何异构体。在优化的结构中，（S）-[B（SAP）（D-PTA）]^-的SAP和D-PTA配体的配位方向相反，形成了一个较好的线性结构，而（5）-[B（SAP）（L-PTA）]^-的非对映体则具有折叠结构。因为这样的三元复合物的溶剂化结构的差异，可以得到不同的电泳速度在毛细管电泳中，DL-PTA在CE中的对映体分离是合理地归因于所观察到的电泳迁移率的平衡的三元系统包含相应的三元复合物的差异。(2)我们发现三个具有1，2-二醇结构的化合物，... class ='class 1'&gt; 1-苯基-1，2-乙烷、3-苯氧基-1，2-丙二醇和3-苄氧基-1，2-丙二醇）对映体进行了分离.以（1 S，2S，3R，5S）-蒎烷二醇为手性选择剂，硼酸根离子为中心离子，十二烷基硫酸钠和六种还原性单糖（甘露糖、半乳糖、岩藻糖、葡萄糖、木糖和阿拉伯糖）的8-氨基萘-1，3，6-三磺酸酯衍生化后，以硼酸根为中心离子，SAP为手性选择剂，采用CLECE同时对映体进行分离。(3)用2-（4-氯磺酰基苯基）乙基三氯硅烷将磺化基团化学引入未处理的熔融石英毛细管的内壁。The sulfona收起

项目成果

Chiral ligand exchange capillary electrophoresis using borate anion as a central ion.

• DOI: 10.1039/b406875k
• 发表时间: 2004-11
• 期刊: The Analyst
• 作者: S. Kodama;A. Yamamoto;R. Iio;K. Sakamoto;A. Matsunaga;K. Hayakawa

還元性単糖誘導体のボロスピラン形成に基づくキラル分離

基于还原单糖衍生物的硼螺烷形成的手性分离

• 发表时间: 2006
• 作者: 小玉修嗣;他;小玉 修嗣;小玉 修嗣
• 通讯作者: 小玉 修嗣

Simultaneous enantioseparation of nicotine alkaloids in cigarettes by capillary Electrophoresis with aminated capillary and sulfated β-cyclodextrin as a chiral selector

以胺化毛细管和硫酸化β-环糊精为手性选择剂的毛细管电泳同时对映分离香烟中的尼古丁生物碱

• 发表时间: 2007
• 作者: Shuji Kodama;et al.;小玉 修嗣;小玉 修嗣;小玉 修嗣;Shuji Kodama;Shuji Kodama;Shuji Kodama
• 通讯作者: Shuji Kodama

ぶんせき 話題:キャピラリー電気泳動-より良い再現性を求めて-

主题：毛细管电泳 - 寻求更好的重现性 -

• 发表时间: 2008
• 作者: 小玉修嗣;他;小玉 修嗣;小玉 修嗣;Shuji Kodama;Shuji Kodama;小玉 修嗣;小玉 修嗣;Shuji Kodama;Shuji Kodama;小玉 修嗣;小玉 修嗣
• 通讯作者: 小玉 修嗣

Chiral ligand exchange micellar electro-kinetic chromatography using borate anion as a central ion

以硼酸根阴离子为中心离子的手性配体交换胶束电动色谱

• 发表时间: 2005
• 期刊: Electrophoresis 26
• 作者: S.Kodama;A.Yamamoto;R.Iio;S.Aizawa;K.Nakagomi;K.Hayakawa
• 通讯作者: K.Hayakawa