Thiol-ene click derived structurally well-defined per(3,5-dimethyl)phenylcarbamoylated cationic cyclodextrin separation material for achiral and chiral chromatography.

In this work, a novel single sulfoether-bridged cationic per(3,5-dimethyl)phenylcarbamoylated-β-cyclodextrin separation material was prepared by thiol-ene click chemistry and characterized by using FTIR spectroscopy, solid-state 13 C NMR spectroscopy and elemental analysis, which confirmed the correct structure. The separation material exhibited a good achiral separation performance for benzene homologues and phenylamine analogs, especially o-xylene and m-xylene, and m-phenylenediamine and o-phenylenediamine can be discriminated by the (3,5-dimethyl)phenylcarbamoyl cyclodextrins. The chiral resolving ability of the separation material was evaluated by discriminating various isoxazolines, flavonoids, and β-blockers in reversed-phase high-performance liquid chromatography. For isoxazolines, the material showed the best chiral discrimination toward 3-aryl-5-(2-oxopyrrolidin-1-yl)-isoxazolines, where the resolution for 3ClPh-OPr  reached 6.03. For flavonoids, it exhibited more efficient separation to the ones with more hydrophobic substituents, with a resolution of 5.93 for 6-hydroxyflavanone. β-Blockers were also enantioseparated satisfactorily on the material. The as-prepared separation material is a good member of the thiol-ene click derived cyclodextrin stationary phase family.

[1]  E. Tesařová,et al.  Effect of Buffer Constituents on Retention and Separation in Achiral and Chiral HPLC Systems with β-Cyclodextrin-Based Stationary Phase , 2015, Chromatographia.

[2]  Zi-hui Meng,et al.  Preparation and chiral recognition of a mono[6A-N-1-(2-hydroxy)-phenylethylimino-6A-deoxy]-beta-cyclodextrin HPLC stationary phase. , 2008, Journal of chromatographic science.

[3]  T. Tan,et al.  Thiol-ene click chemistry derived cationic cyclodextrin chiral stationary phase and its enhanced separation performance in liquid chromatography. , 2014, Journal of chromatography. A.

[4]  Renhua Liu,et al.  Application of click chemistry on preparation of separation materials for liquid chromatography. , 2011, Chemical Society reviews.

[5]  Yong Wang,et al.  Chiral differentiation of novel isoxazoline derivatives on “clicked” thioether and triazole bridged cyclodextrin chiral stationary phases , 2014 .

[6]  Zhiming Zhou,et al.  Synthesis of ionic liquids functionalized β-cyclodextrin-bonded chiral stationary phases and their applications in high-performance liquid chromatography. , 2010, Analytica chimica acta.

[7]  Weihua Tang,et al.  Novel cyclodextrin chiral stationary phases for high performance liquid chromatography enantioseparation: effect of cyclodextrin type. , 2011, Journal of chromatography. A.

[8]  Xin Lu,et al.  Development and evaluation of new imidazolium-based zwitterionic stationary phases for hydrophilic interaction chromatography. , 2013, Journal of chromatography. A.

[9]  F. Stillinger,et al.  Molecular model for chirality phenomena. , 2016, The Journal of chemical physics.

[10]  Zhiming Zhou,et al.  Preparation of chiral oxazolinyl-functionalized β-cyclodextrin-bonded stationary phases and their enantioseparation performance in high-performance liquid chromatography. , 2016, Journal of separation science.

[11]  Xinmiao Liang,et al.  Preparation of novel beta-cyclodextrin chiral stationary phase based on click chemistry. , 2008, Journal of chromatography. A.

[12]  Timothy Thatt Yang Tan,et al.  "Click" preparation of hindered cyclodextrin chiral stationary phases and their efficient resolution in high performance liquid chromatography. , 2010, Journal of chromatography. A.

[13]  D. Armstrong,et al.  Separation of drug stereoisomers by the formation of beta-cyclodextrin inclusion complexes. , 1986, Science.

[14]  Jun Fan,et al.  Preparation and enantioseparation characteristics of a novel chiral stationary phase based on mono (6(A)-azido-6(A)-deoxy)-per(p-chlorophenylcarbamoylated) beta-cyclodextrin. , 2008, Journal of chromatography. A.

[15]  Weihua Tang,et al.  Per(3-chloro-4-methyl)phenylcarbamate cyclodextrin clicked stationary phase for chiral separation in multiple modes high-performance liquid chromatography. , 2016, Analytica chimica acta.

[16]  A. Shaabani,et al.  Evaluation of sulfated maltodextrin as a novel anionic chiral selector for the enantioseparation of basic chiral drugs by capillary electrophoresis , 2015, Electrophoresis.

[17]  S. Ng,et al.  Synthesis and application of mono-2A-azido-2A-deoxyperphenylcarbamoylated β-cyclodextrin and mono-2A-azido-2A-deoxyperacetylated β-cyclodextrin as chiral stationary phases for high-performance liquid chromatography , 2006 .

[18]  T. Ward,et al.  Chiral separations: a review of current topics and trends. , 2012, Analytical chemistry.

[19]  H. Blaser.  Chirality and its implications for the pharmaceutical industry , 2013, Rendiconti Lincei.

[20]  Yang Zhang,et al.  Engineering Thiol-Ene Click Chemistry for the Fabrication of Novel Structurally Well-Defined Multifunctional Cyclodextrin Separation Materials for Enhanced Enantioseparation. , 2016, Analytical chemistry.

[21]  Weihua Tang,et al.  Enantioseparation of isoxazolines with functionalized perphenylcarbamate cyclodextrin clicked chiral stationary phases in HPLC , 2017, Electrophoresis.

[22]  S. Ng,et al.  Sub-1-micron mesoporous silica particles functionalized with cyclodextrin derivative for rapid enantioseparations on ultra-high pressure liquid chromatography. , 2010, Journal of chromatography. A.

[23]  B. Noszál,et al.  Chiral separation of lenalidomide by liquid chromatography on polysaccharide-type stationary phases and by capillary electrophoresis using cyclodextrin selectors. , 2018, Journal of separation science.

[24]  Lan Zhang,et al.  One-pot preparation of glutathione-silica hybrid monolith for mixed-mode capillary liquid chromatography based on "thiol-ene" click chemistry. , 2014, Journal of chromatography. A.

[25]  G. Scriba.  Chiral recognition in separation science - an update. , 2016, Journal of chromatography. A.

[26]  Yong Wang,et al.  'Click' preparation of a novel 'native-phenylcarbamoylated' bilayer cyclodextrin stationary phase for enhanced chiral differentiation. , 2015, Journal of chromatography. A.

[27]  S. Ng,et al.  Application of Click‐chemistry‐based perphenylcarbamated β‐CD chiral stationary phase in CEC , 2009, Electrophoresis.

[28]  S. Ng,et al.  "Click" immobilized perphenylcarbamated and permethylated cyclodextrin stationary phases for chiral high-performance liquid chromatography application. , 2010, Journal of chromatography. A.

[29]  Weihua Tang,et al.  Evaluation of perphenylcarbamated cyclodextrin clicked chiral stationary phase for enantioseparations in reversed phase high performance liquid chromatography. , 2014, Journal of chromatography. A.

[30]  Weihua Tang,et al.  Novel β-cyclodextrin chiral stationary phases with different length spacers for normal-phase high performance liquid chromatography enantioseparation. , 2011, Journal of chromatography. A.

[31]  Lijun Ruan,et al.  A new single‐urea‐bound 3,5‐dimethylphenylcarbamoylated β‐cyclodextrin chiral stationary phase and its enhanced separation performance in normal‐phase liquid chromatography , 2018, Electrophoresis.

[32]  Yong Wang,et al.  Thioether bridged cationic cyclodextrin stationary phases: Effect of spacer length, selector concentration and rim functionalities on the enantioseparation. , 2016, Journal of chromatography. A.

[33]  M. Dąbrowska,et al.  Analytical approaches to determination of carnitine in biological materials, foods and dietary supplements. , 2014, Food chemistry.