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Chinese Journal of Chromatography
2016, Vol. 34, No. 1
Online: 08 January 2016

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Communications

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Synthesis of novel glucose-based polymers and their applications as chiral stationary phases for high performance liquid chromatography Tomoyuki IKAI, Takayuki YAMADA 2016, 34 (1):  4-9.  DOI: 10.3724/SP.J.1123.2015.10037 Abstract ( 448 )   [Full Text(HTML)] () PDF (667KB) ( 76 )   Two novel polymers containing glucose units as the main-chain that only differ in terms of their regioregularity were synthesized to evaluate their chiral recognition abilities as chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC). The regioregular polymer (poly-5) shows clear resolution ability for the racemate of cobalt (Ⅲ) acetylacetonate (Co(acac)3), whereas the corresponding regioirregular polymer (poly-3) does not show any chiral recognition for Co(acac)3. The regioregular polymer main-chain seems to play an important role not only in providing an efficient interaction with the racemate but also in expressing the chiral recognition ability as a CSP for HPLC.

Reviews

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Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers QI Xiaoyue, LI Xianjiang, BAI Yu, LIU Huwei 2016, 34 (1):  10-15.  DOI: 10.3724/SP.J.1123.2015.10005 Abstract ( 749 )   [Full Text(HTML)] () PDF (1740KB) ( 223 )   Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development, agricultural chemistry, pharmacology, environmental science, biology and many other fields. Chiral metal-organic frameworks (MOFs) are a new group of porous materials with special topology and designable pore structures, as well as their high specific surface area, porosity, excellent thermal stability, solvent resistance, etc. Thus, chiral MOFs are promising with various applications in the field of analytical chemistry. This review summarizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers, as well as related mechanism.

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Recent developments of chiral separation by capillary electrophoresis PAN Congjie, WANG Weifeng, CHEN Xingguo 2016, 34 (1):  16-20.  DOI: 10.3724/SP.J.1123.2015.09002 Abstract ( 688 )   [Full Text(HTML)] () PDF (792KB) ( 112 )   As the two enantiomers of chiral compounds have different chemical and physiologic properties, the enantioseparation of chiral compounds is of great significance in the fields such as medicine, biology, food and environment. Hence, the enantioseparation of different types of chiral compounds has become one of the hottest research topics in recent years. Capillary electrophoresis, owing to its unique advantages, has a wide application in the enantioseparation field recently. In this review, the latest research progresses in capillary electrophoresis enantioseparation are summarized from 2013 to 2015, and the future developments in this field is also prospected.

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Development of chiral ligand exchange capillary electrophoresis for enantioseparation of D,L-amino acids MU Xiaoyu, QI Li, SU Yuan, QIAO Juan, CHEN Yi 2016, 34 (1):  21-27.  DOI: 10.3724/SP.J.1123.2015.05038 Abstract ( 456 )   [Full Text(HTML)] () PDF (2263KB) ( 113 )   Enantioseparation of D,L-amino acids is of great significance in life science. As one of the most useful methods, chiral ligand exchange capillary electrophoresis possesses many advantages, including high efficiency, fast speed and tunable migration order, and it has attracted great research interest. This review summarizes the development of chiral ligand exchange capillary electrophoresis for enantioseparation of D,L-amino acids in recent years.

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A comment on chiral thin layer chromatography CHEN Xuexian, YUAN Liming 2016, 34 (1):  28-33.  DOI: 10.3724/SP.J.1123.2015.08014 Abstract ( 400 )   [Full Text(HTML)] () PDF (1621KB) ( 138 )   In recent eight years, authors' group has repeated a lot of experiments of chiral thin layer chromatography coming from literature. From the practical opinion, we summarized that there are nine characteristics for chiral thin layer chromatography. Some progresses of chiral thin layer chromatography are reviewed, and the enantioselectivity of a commercial chiral thin layer plate is introduced. The study of vancomycin as the chiral selector in thin layer chromatography is also reported.

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Advances in polymer materials as chiral stationary phase DAI Rongji, WANG Huiting, SUN Weiwei, DENG Yulin, LV Fang, LIU Xiujie 2016, 34 (1):  34-43.  DOI: 10.3724/SP.J.1123.2015.10023 Abstract ( 561 )   [Full Text(HTML)] () PDF (1067KB) ( 174 )   The applications of chiral drugs had a profound impact on human health. With the development of disciplines of chemistry, materials and life science, the research on the separation and analysis of chiral drugs became intensified. Chromatography and the selection of chiral stationary phase played important roles in resolving chiral drugs. The optimization of polymer materials and their derivatives as chiral stationary phase become the main issue in recent years. Recent studies as well as prospects in polymer materials used as chiral stationary phase are presented in this paper.

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Progress of chiral countercurrent chromatography YUAN Liming 2016, 34 (1):  44-49.  DOI: 10.3724/SP.J.1123.2015.09013 Abstract ( 520 )   [Full Text(HTML)] () PDF (820KB) ( 111 )   This article summarizes five characteristics of chiral countercurrent chromatography (CCC). The progress of chiral countercurrent chromatography is introduced. In the high speed countercurrent chromatography, the chiral selectors such as amino acid derivatives, cyclodextrin derivatives, chiral organic acid, polysaccharide and bovine serum albumin (BSA) are reviewed.

Articles

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Preparation and enantioseparation property of novel amylose-based chiral stationary phases for high performance liquid chromatography SHEN Jun, LI Geng, LI Ping, YANG Chao, LIU Shuangyan, OKAMOTO Yoshio 2016, 34 (1):  50-56.  DOI: 10.3724/SP.J.1123.2015.10015 Abstract ( 471 )   [Full Text(HTML)] () PDF (860KB) ( 118 )   Five new amylose derivatives, namely amylose 2-benzoate-3-(4-chlorophenylcarbamate)-6-(3,5-dimethylphenylcarbamate), amylose 2-benzoate-3-(4-chlorophenylcarbamate)-6-(3,5-dichlorophenylcarbamate), amylose 2-benzoate-3,6-bis(4-chlorophenylcarbamate), amylose 2-(4-chlorobenzoate)-3,6-bis(4-chlorophenylcarbamate) and amylose 2-(4-chlorobenzoate)-3,6-biscyclohexylcarbamate, were synthesized by a series of regioselective process. These derivatives were then coated on the surface of aminopropyl silica gels, and used as chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC). These derivatives were characterized by 1H-nuclear magnetic resonance (1H-NMR) and Fourier transform infrared (FT-IR) spectroscopies, and their chiral recognition abilities were evaluated using nine racemates by HPLC. Compared with other amylose derivatives, some racemates were better resolved on the new CSPs. The obtained results indicate that the property and position of substituents at 2-, 3- and 6-positions of glucose unit have great influence on the chiral recognition abilities of the amylose derivatives.

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Enantioseparation of ferroence derivatives with high performance liquid chromatography XU Feng, WAN Xiaolong, WANG Junfeng, KANG Jingwu 2016, 34 (1):  57-61.  DOI: 10.3724/SP.J.1123.2015.10002 Abstract ( 513 )   [Full Text(HTML)] () PDF (819KB) ( 78 )   The method for the enantioseparation of ferroence derivatives, four derivatives with single chirality and three derivatives with double chiralities containing centre and face chirality, on chiral stationary phases, namely Chiralpak IC (cellulose-tris(3,5-dichlorobenzene carbamate)) and Chiralpak IE3 (amylose-tris(3,5-dichlorobenzene carbamate)), was investigated. We found that the three derivatives of the four chiral ferroence derivatives with single chirality can be baseline separated on Chiralpak IE3; another one can be baseline separated on Chiralpak IC. Meanwhile, the three chiral ferroence derivatives with double chiralities can be baseline separated on Chiralpak IC. The research shows that the both kinds of chiral stationary phases exhibited high enantiomeric recognition capability to the enantiomers of the chiral ferroence derivatives. This two chiral stationary phases exhibited complementary selectivities in the enantioseparation of chiral ferroence derivatives. This study provides a reference method for the enantioseparation of chiral ferroence derivatives.

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Separation mechanism of chiral stationary phase based on quinine and crown ether for the direct stereoselective separation of amino acids WU Haixia, WANG Dongqiang, ZHAO Jianchao, KE Yanxiong, LIANG Xinmiao 2016, 34 (1):  62-67.  DOI: 10.3724/SP.J.1123.2015.07015 Abstract ( 696 )   [Full Text(HTML)] () PDF (1029KB) ( 112 )   A novel chiral stationary phase combining quinine and crown ether (QN-CR CSP) was developed to separate amino acid enantiomers. This CSP showed good enantioselectivity for some amino acids. Since the synergistic effect of ion exchange and complexation in chiral recognition of amino acids, a new adsorption isotherm was built. Using the method of frontal analysis by characteristic point (FACP), the adsorption isotherms of tryptophan (Trp) under different mobile phase conditions were determined and fitted the proposed adsorption isotherm model well. With the increase of the competition between metal cationic and amino to crown ether, the equilibrium constant of complexing adsorption was found increased. The chiral separation ability was decreased. The adsorption isotherm improved the understanding of the retention behavior of amino acids on QN-CR CSP, which was also benefit to optimize the structure of the stationary phase.

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Enantioseparation of metalaxyl racemate by simulated moving bed chromatography CHEN Tao, CHEN Xiange, XU Junye, FAN Jun, YU Ying, ZHANG Weiguang 2016, 34 (1):  68-73.  DOI: 10.3724/SP.J.1123.2015.10024 Abstract ( 556 )   [Full Text(HTML)] () PDF (883KB) ( 88 )   Due to some advantages such as high precision, high efficiency and low consumption of organic solvents, chromatographic separation technique by simulated moving bed (SMB) has attracted considerable attention in the past decades. Herein, the enantioseparation of metalaxyl racemate on EnantioPak OD columns has been carried out by SMB chromatography with the mixture of hexane-ethanol (70 : 30, v/v). The elution order of two metalaxyl enantiomers under current chromatographic conditions was determined by HPLC with the optical rotation detector. Then, the influence of running parameters, such as the concentration, flow rate and switch time on the resolution of metalaxyl racemate has been studied in detail. In addition, the separation results from SMB and the preparative chromatography have been compared under the same concentrations. The results showed that the retention of S-(+)-metalaxyl was weaker than R-(-)-metalaxyl and S-(+)-metalaxyl was eluted first. Most importantly, metalaxyl racemate was well separated by SMB chromatography under linear or non-linear conditions, and the purity of each enantiomer product was over 99%. Furthermore, the amount separated by SMB was much more than by the preparative chromatography with racemate concentration of 15 mg/mL, and the mobile phase consumption was one-ninth of the latter. In brief, these results provide us important information for the future development of large-scale chromatographic separation of metalaxyl enantiomers.

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Preparation and chiral recognition ability of chiral stationary phase based on immobilized polyacrylamide derivative SONG Jiafeng, FENG Siwei, XU Xiaodong, LIU Lijia, SONG Chaokun, WEN Xiaokun, CHEN Jinyong, LI Fangkun, OKAMOTO Yoshio 2016, 34 (1):  74-79.  DOI: 10.3724/SP.J.1123.2015.10036 Abstract ( 561 )   [Full Text(HTML)] () PDF (1039KB) ( 88 )   High performance liquid chromatography (HPLC) has been widely considered as the most effective way for the separation and preparation of optically pure enantiomers. In the resolution by HPLC, the separation ability of a column strongly depends on the properties of a chiral stationary phase (CSP). Among many CSPs, the immobilized CSPs, which are becoming one of the most important kinds of CSPs, have the advantages of good solvent durability and enormous method flexibility. In this work, a novel optically active acrylamide derivative (S)-APACP was synthesized by two-step reactions, and its chemical structure was characterized by 1H NMR. The polyacrylamide derivatives were immobilized on silica gel by three-step reactions to prepare immobilized CSPs, and the immobilization amount of the polymers was tested by thermogravimetric analysis. The chiral recognition ability of the immobilized CSPs was evaluated by HPLC, and the effects of Lewis acid and mobile phase on the chiral recognition ability were investigated. The results showed that APACP polymer was successfully immobilized on silica gel to prepare immobilized-type CSP with better solvent durability, and the amount of immobilized polymer was 10.2% to 11.8%. The immobilized-type CSP showed good chiral recognition ability for several enantiomers.

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Separation of enantiomers by supercritical fluid chromatography on polysaccharide derivative- based chiral stationary phases LI Dongyan, WU Xi, HAO Fangli, YANG Yang, CHEN Xiaoming 2016, 34 (1):  80-84.  DOI: 10.3724/SP.J.1123.2015.10039 Abstract ( 609 )   [Full Text(HTML)] () PDF (827KB) ( 142 )   Eleven kinds of chiral compounds have been well separated within 10 min on polysaccharide derivative-based chiral stationary phases named Chiralpak IA, IB, IC, ID, IE and IF by supercritical fluid chromatography (SFC). The chiral recognition of these chiral compounds has demonstrated good complementary enantioselectivities of the six chiral columns, which were proved to be useful for chiral SFC. Both the elution time and enantioselectivies could be significantly affected by the modifier types and their concentrations, such as methanol, ethanol and isopropanol, which should be optimized during the experiments. In addition, the solvent versatility of the immobilized chiral stationary phase on the optimization of the chiral separation was helpful.

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Enantioseparation of 2-phenylcarboxylic acid esters by capillary gas chromatography SHI Xueyan, LIU Feipeng, BIAN Qinghua 2016, 34 (1):  85-88.  DOI: 10.3724/SP.J.1123.2015.06044 Abstract ( 391 )   [Full Text(HTML)] () PDF (788KB) ( 79 )   Chiral 2-arylcarboxylic acid derivatives are important intermediates for preparing 2-arylcarboxylic acids, which are non-steroidal anti-inflammatory drugs (NSAIDs). In order to separate 2-phenylcarboxylic acid ester enantiomers by capillary gas chromatography (CGC), 2,6-di-O-pentyl-3-O-butyryl- β-cyclodextrin and 2,6-di-O-benzyl-3-O-heptanoyl- β-cyclodextrin were used as CGC chiral stationary phases, separately, and their enantioseparation abilities to enantiomers of methyl 2-phenylbutanoate, ethyl 2-phenylbutanoate, isopropyl 2-phenylbutanoate, methyl 2-phenylpropionate and cyclopentyl 2-phenylpropionate were examined. It was found that methyl 2-phenylbutanoate, methyl 2-phenylpropionate and cyclopentyl 2-phenylpropionate were successfully separated by using 2,6-di-O-pentyl-3-O-butyryl- β-cyclodextrin and 2,6-di-O-benzyl-3-O-heptanoyl- β-cyclodextrin as CGC chiral stationary phases, respectively. The enantiomer separation abilities of 2,6-di-O-pentyl-3-O-butyryl- β-cyclodextrin to the three pairs of 2-phenylcarboxylic acid esters tested are superior to those of 2,6-di-O-benzyl-3-O-heptanoyl- β-cyclodextrin.

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Preparation and enantioseparation performance of β-cyclodextrin-silica hybrid chiral stationary phases WANG Litao, DONG Shuqing, ZHANG Zhixin, WANG Yangjun, ZHANG Xiaoli, ZHANG Xia, ZHANG Pengyun, ZHAO Liang 2016, 34 (1):  89-95.  DOI: 10.3724/SP.J.1123.2015.06036 Abstract ( 509 )   [Full Text(HTML)] () PDF (3192KB) ( 121 )   A simple preparation method for β-cyclodextrin-silica hybrid chiral stationary phases was developed. Firstly, the β-cyclodextrin-silica derivative was synthesized by the reaction of 3-aminopropyltriethoxysilane and monochlorotriazinyl β-cyclodextrin under weak base condition. Spherical β-cyclodextrin-silica hybrid materials with β-cyclodextrin in the surface of pores by covalent bonding were prepared using 1,2-bis(triethoxysilyl) ethane and the β-cyclodextrin-silica derivative under the alkaline condition by one-step polymerization reaction. The β-Cyclodextrin-silica hybrid chiral stationary phases could be directly used as high performance liquid chromatographic packings after the template removal. The hybrid materials prepared in this paper possessed regular spherical morphology, good monodispersion, high specific surface area, good mechanical property, high chemical stability and simple preparation process. It combined the chiral recognition performance of β-cyclodextrin and the outstanding performance of organic-inorganic hybrid material. The effect of the composition, ratio and pH of mobile phase on chiral separation was investigated, and the best chiral separation conditions had been optimized. The baseline chiral separations for five chiral compounds were obtained under the optimal conditions. The results of enantioseparation showed that the hybrid chiral stationary phases had favorable chiral recognition ability. Compared with the traditional preparation process of chiral stationary phases, a new thought for new type of chiral stationary phase is provided by the present method in this paper.

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Preparation of phenylcarbamoylated β-cyclodextrin chiral stationary phases and the enantioseparation of flavonoids LIN Yuzhou, ZHOU Jie, TANG Jian, TANG Weihua 2016, 34 (1):  96-102.  DOI: 10.3724/SP.J.1123.2015.06038 Abstract ( 421 )   [Full Text(HTML)] () PDF (1858KB) ( 94 )   Cyclodextrin (CD) based chiral stationary phases (CSPs) have simulated great attention due to their unique chiral recognition ability. Functionalized cyclodextrins bonded silica gel as chiral stationary phases have been dramatically developed due to their chemical stability and solvent tolerability. To explore the functionalization of phenylcarbamoylated β-cyclodextrin CSPs on their enantioselectivities, 4-chloro-3-methylaniline and 5-chloro-2-methyl phenyl isocyanate were employed. Two CSPs have been thus developed by clicking the CD derivatives onto alkynylated silica support. They include per-4-chloro-3-methylphenylcarbamoylated β-cyclodextrin clicked CSP (CSP1) and per-5-chloro-2-methylphenylcarbamoylated β-cyclodextrin clicked CSP (CSP2), which have both electron-donating (methyl) and withdrawing (chlorine) groups in the phenylcarbamate moieties, but different locations. The CSPs were successfully characterized in terms of structure using nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and elementary analysis. Their enantioselectivities wereevaluated in reversed-phase high performance liquid chromatography (HPLC). The comparison study on the enantioseparation of nine flavonoids with the two CSPs demonstrates the higher enantioselectivities of CSP1 over CSP2, because of the different locations of electron-donating (methyl) and withdrawing (chlorine) groups in the phenylcarbamate moieties of CD derivatives. The baseline enantioseparations achieved in water/methanol as mobile phase offered great potential for the CSPs to be used in practical application.

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Separation and determination of optical isomers of phenylephrine by chiral ligand exchange capillary electrophoresis coupling with the promoting effect of ionic liquid YANG Simei, ZHANG Jiayao, LI Fei, HU Xufang, CAO Qiue 2016, 34 (1):  103-107.  DOI: 10.3724/SP.J.1123.2015.10013 Abstract ( 625 )   [Full Text(HTML)] () PDF (813KB) ( 108 )   A method for the separation and determination of optical isomers of phenylephrine was developed based on the promoting effect of non-chiral ionic liquid on chiral ligand-exchange capillary electrophoresis after the electrophoretic parameters were optimized systematically. R-phenylephrine and S-phenylephrine can be separated and determined effectively in 20 mmol/L Tris-H3PO4 buffer solution (pH 5.4) composed of 4.0 mmol/L Cu(Ⅱ), 8.0 mmol/L L-proline (L-Pro) and 15 mmol/L 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) with the applied voltage of 20 kV, capillary temperature of 25 ℃, detection wavelength of 254 nm, and injection of 5 s at 3447 Pa. The resolution of R- and S-phenylephrines was 1.42. The linear ranges for the determination of R-phenylephrine and S-phenylephrine were 12.5-150 mg/L and 15.0-150 mg/L, respectively. The method has been satisfactorily used for the determination of R-phenylephrine and S-phenylephrine in the spiked blood and urine samples. The spiked recoveries in the urine sample were in the range of 93.7%-108.2% with the RSDs lower than 3.18%(n=3), and the spiked recoveries in the blood sample were in the range of 91.4% and 113.1% with the RSDs lower than 4.82%(n=3).

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Enantioseparation behavior of chiral stationary phases AD, AS and OD LI Liqun, FAN Jun, ZHANG Jing, CHEN Xiaodong, WANG Tai, HE Jianfeng, ZHANG Weiguang 2016, 34 (1):  108-112.  DOI: 10.3724/SP.J.1123.2015.10035 Abstract ( 460 )   [Full Text(HTML)] () PDF (841KB) ( 83 )   Over the past decades, HPLC enantioseparation with chiral stationary phases (CSPs) has been widely applied in chiral analysis and preparation of new pharmaceuticals, pesticides, food, etc. Herein, enantioseparation of 20 chiral compounds have been carried out on three polysaccharide-based CSPs (EnantioPak AD, AS and OD) with normal phases by HPLC, separately. The influences of skeletal structure and the kinds of derivative groups on separation behaviors of these CSPs have been studied in detail. As results indicated, except for compound 13, the other compounds were baseline separated on EnantioPak AD, with most of resolution over 2.0; in addition, better separation for acidic or basic compounds was achieved through adding acidic/basic additives into the mobile phase of hexane-alcohol. For four aromatic alcohols (compounds 13-16), their retention in the EnantioPak AD column showed a weakening tendency with increase of carbon number in side chain group, and the reverse trend of their resolution was observed. Furthermore, EnantioPak AD showed much better separation performance for eight compounds (13-20) than the others. In short, these results have provided some references for further investigation of separation behavior and applications of polysaccharide-based CSPs.

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Single-handed helical framework material [{Cu(sala)}n] incorporated peramylated β-cyclodextrin for improving gas chromatography enantioseparation XIE Shengming, LIU Hong, YANG Jiangrong, AI Ping, YUAN Liming 2016, 34 (1):  113-118.  DOI: 10.3724/SP.J.1123.2015.08001 Abstract ( 525 )   [Full Text(HTML)] () PDF (6048KB) ( 153 )   Metal-organic frameworks (MOFs) as a new generation of functional molecular materials, have broad application prospects in enantioselective catalysis and chiral separation areas due to their unusual properties, such as high surface area, rich topologies, permanent microporous, availability of outer-surface modification and so on. A single-handed helical three-dimensional metal-organic framework material [{Cu(sala)}n] (H2sala=N-(2-hydroxybenzyl)-L-alanine) was incorporated with peramylated β-cyclodextrin for the preparation of novel capillary gas chromatography stationary phase. To investigate whether the use of a chiral MOF can enhance enantioseparation on peramylated β-cyclodextrin, three chiral columns were fabricated using different stationary phases for comparison, including column A ([{Cu(sala)}n]), column B (peramylated β-cyclodextrin) and column C ([{Cu(sala)}n]+peramylated β-cyclodextrin). The results of comparing the resolving abilities of the three columns for the same chiral compounds demonstrated that column C showed better enantioselectivity and higher resolution. The use of MOF [{Cu(sala)}n] can improve enantioseparation on peramylated β-cyclodextrin.