ABSTRACT
The synthesis of mono-6-(3-methylimidazolium)-6-deoxyperphenylcarbamoyl-beta-cyclodextrin chloride (MPCCD) and its application in chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are being reported. This chiral selector is coated onto silica gel in different weight percentages (15, 20 and 35%, w/w) to obtain CSPs having different loading content. These new chiral stationary phases are tested using normal-phase HPLC for enantioseparation of racemic aromatic alcohols. Indeed, the enantiodiscrimination abilities of these CSPs are found to be influenced by the loading content of the chiral selector. Among the three columns (MPCCD-C15, MPCCD-C20 and MPCCD-C35), the best enantioseparation results are obtained using a column containing 20% (w/w) of MPCCD (MPCCD-C20). The resolution (R(s)) obtained for p-fluorophenylethanol, p-chlorophenylethanol, p-bromophenylethanol, p-iodophenylethanol and p-fluorophenyl-3-buten-1-ol using MPCCD-C20 ranges from 3.83 to 5.65. Good enantioseparation results are obtained for these analytes under SFC separation conditions using the MPCCD-C20 column.
Subject(s)
Chromatography, High Pressure Liquid/methods , Chromatography, Supercritical Fluid/methods , beta-Cyclodextrins/chemistry , beta-Cyclodextrins/chemical synthesis , Reproducibility of Results , StereoisomerismABSTRACT
A family of 6-mono(3-alkylimidazolium)-beta-cyclodextrins with one primary hydroxyl group replaced by an alkylimidazolium cation has been developed. The effect of alkyl substitutents on the enantioresolution ability of these single-isomer cyclodextrins towards dansyl amino acids has been studied by capillary electrophoresis. Systematical investigations on the effect of buffer pH and selector concentration on the enatioseparation show that chiral selectors with a shorter alkyl chain (R=C(n)H(2n+1), n
Subject(s)
Chemistry Techniques, Analytical/methods , Electrophoresis, Capillary/methods , Imidazoles/chemistry , beta-Cyclodextrins/chemistry , beta-Cyclodextrins/isolation & purification , Acetates/chemistry , Amino Acids/chemistry , Buffers , Electrolytes , Hydrogen-Ion Concentration , Models, Chemical , StereoisomerismABSTRACT
Several structurally well-defined perfunctionalised cyclodextrin chiral stationary phases (CD CSPs) for high performance liquid chromatography have been successfully prepared by immobilisation of perfunctionalised cyclodextrins on silica through urea linkage(s) using the Staudinger reaction. These CSPs show high chiral recognition efficiency and are utilised in the resolution of various types of racemic compounds. This paper reviews the development of sixteen perfunctionalised cyclodextrin-based CSPs, their preparation, and their application to enantioseparation of seventy-seven racemic compounds under a range of separation conditions.
Subject(s)
Cyclodextrins/chemistry , Silicon Dioxide/chemistry , Urea/chemistry , Chromatography, High Pressure Liquid/instrumentation , Chromatography, High Pressure Liquid/methods , Sensitivity and Specificity , Surface PropertiesABSTRACT
Two novel chiral stationary phases (CSPs) were prepared based upon the regioselective immobilizations of beta-cyclodextrin (beta-CD) at its C2 position to the silica support. The mono-2A-azido-2A-deoxyperphenylcarbamoylated beta-cyclodextrin and mono-2A-azido-2A-deoxyperacetylated beta-cyclodextrin were synthesized by selective tosylation and azidolysis followed by perfunctionalisation. The derivatised cyclodextrins were then immobilized onto the aminised silica gel via the Staudinger reaction to provide new chiral stationary phases. Their application to high-performance liquid chromatography (HPLC) enantioseparation of racemic compounds was demonstrated using beta-adrenergic blockers, flavonone compounds, benzodiazepinones, antihistamines and weakly protolytic compounds, of which good separations were achieved for some racemic compounds, for instance, bendroflumethiazide (Rs 6.26), oxazepam (Rs 5.99), temazepam (Rs 2.85) and althiazide (Rs 1.13) when compared with the corresponding CSPs where the beta-CD molecule was regioselectively immobilized at the C6 position. The enantiodiscriminatory properties of these CSPs were found to be affected by the orientation of the CD cavity under reversed-phase conditions, and also by the derivitising groups of the CD. The HPLC results inferred that the mono-6A-azido-6A-deoxyperphenylcarbamoylated CD CSP (CD bonded at C6 position to silica) exhibited slightly better chiral recognition ability than mono-2A-azido-2A-deoxyperphenylcarbamoylated CD CSP under the normal-phase and reversed-phase modes on the separation of 31 different racemic compounds and drugs. On the contrary, higher chiral recognition abilities were observed on the mono-2(A)-azido-2A-deoxyperacetylated CD CSP compared to mono-6A-azido-6A-deoxyperacetylated CD CSP.
Subject(s)
Chromatography, High Pressure Liquid/instrumentation , beta-Cyclodextrins/chemical synthesis , Alcohols/isolation & purification , Chromatography, High Pressure Liquid/methods , Pharmaceutical Preparations/isolation & purification , Silica Gel , Silicon Dioxide , StereoisomerismABSTRACT
A facile synthetic approach for mono-6-amino-6-deoxy-beta-cyclodextrin (beta-CD-NH2) was proposed. Its hydroxy chloride salt, mono-6-ammonium-6-deoxy-beta-cyclodextrin chloride (beta-CD-NH3Cl) was further prepared and used for the enantioseparation of various anionic and ampholytic analytes by capillary electrophoresis (CE). The effect of background electrolyte (BGE) pH and selector concentration on the enantioseparation was studied. Results showed that beta-CD-NH3Cl displayed powerful chiral resolution ability towards anionic analytes. In addition, baseline separation of a standard mixture consisting of eight acids was achieved within 35 min.
Subject(s)
Electrophoresis, Capillary/methods , Quaternary Ammonium Compounds/chemistry , beta-Cyclodextrins/chemistry , Magnetic Resonance Spectroscopy , Mass Spectrometry , StereoisomerismABSTRACT
A novel single-isomer positively charged beta-cyclodextrin (beta-CD), mono-6(A)-butylammonium-6(A)-deoxy-beta-cyclodextrin tosylate (BuAM-beta-CD), has been synthesized, characterized, and used for the enantioseparations of alpha-hydroxy acids, carboxylic acids, and ampholytic analytes by capillary electrophoresis in acidic aqueous background electrolytes. The effective mobilities of all studied analytes decreased with increasing concentration of CD. Satisfactory resolutions were obtained for alpha-hydroxy acids over a wide range of chiral selector concentration. The optimum CD concentration was lower than 5 mM for the carboxylic acids, while higher than 20 mM for alpha-hydroxy acids. Inclusion complexation in combination with ion pair interaction seemed to account for the chiral discrimination process. The hydrogen bonding may provide secondary contribution for the chiral resolution of alpha-hydroxy acids. In addition, BuAM-beta-CD was further proved to be an effective chiral selector for anionic analytes by the baseline enantioseparation of a six-acid mixture within 20 min.
Subject(s)
Buffers , Carboxylic Acids/isolation & purification , Electrophoresis, Capillary/methods , Hydroxy Acids/isolation & purification , beta-Cyclodextrins/chemistry , Hydrogen Bonding , Hydrogen-Ion Concentration , Stereoisomerism , beta-Cyclodextrins/chemical synthesisABSTRACT
A permanently positively charged single-isomer ß-CD, mono-6-N-allylammonium-6-deoxy-ß-CD chloride, ALAM-ß-CD, has been synthesized and successfully used as chiral selector in capillary electrophoresis for enantioseparation of amino acids and dansyl amino acids. The effects of pH, CD's concentration and capillary length on enantioseparation were studied in order to investigate its potential as chiral selector for acidic racemates. By increasing buffer's pH and CD's concentration, fairly robust separations were achieved. Good separations were also obtained with a shorter capillary. In addition, baseline enantiomeric separations of a mixture of six pairs of dansyl dl-amino acids were achieved under different pH conditions.
