Applications of nuclear magnetic resonance spectroscopy for the understanding of enantiomer separation mechanisms in capillary electrophoresis

Salgado, Antonio; Chankvetadze, Bezhan

doi:10.1016/j.chroma.2016.08.060

Cited by 51 publications

(49 citation statements)

References 115 publications

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“…Several noncovalent interactions underlie recognition processes like HBs, π‐π and hydrophobic interactions, dipole‐dipole stacking, van der Waals and dispersion forces. On one hand, the fact that CDs can be studied in solution allowed NMR to give a great contribution to understand their recognition mechanism . On the other hand, the complexity of the possible recognition pattern which governs inclusion, or external contacts, makes molecular modelling a versatile tool also in this case.…”

Section: Cyclodextrinsmentioning

confidence: 99%

“…Using CDs as chiral selector in CE allows chiral recognition mechanisms to be studied in solution by spectroscopic methods and separation techniques under similar conditions . Recently, interesting investigations of the complexation between CDs and enantiomers have been published, which were performed by means of a multidisciplinary approach based on the use of CE, NMR and molecular simulations (Table ).…”

Section: Cyclodextrinsmentioning

confidence: 99%

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Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

et al. 2019

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Liquid‐phase enantioseparations have been fruitfully applied in several fields of science. Various applications along with technical and theoretical advancements contributed to increase significantly the knowledge in this area. Nowadays, chromatographic techniques, in particular HPLC on chiral stationary phase, are considered as mature technologies. In the last thirty years, CE has been also recognized as one of the most versatile technique for analytical scale separation of enantiomers. Despite the huge number of papers published in these fields, understanding mechanistic details of the stereoselective interaction between selector and selectand is still an open issue, in particular for high‐molecular weight chiral selectors like polysaccharide derivatives. With the ever growing improvement of computer facilities, hardware and software, computational techniques have become a basic tool in enantioseparation science. In this field, molecular docking and dynamics simulations proved to be extremely adaptable to model and visualize at molecular level the spatial proximity of interacting molecules in order to predict retention, selectivity, enantiomer elution order, and profile noncovalent interaction patterns underlying the recognition process. On this basis, topics and trends in using docking and molecular dynamics as theoretical complement of experimental LC and CE chiral separations are described herein. The basic concepts of these computational strategies and seminal studies performed over time are presented, with a specific focus on literature published between 2015 and November 2018. A systematic compilation of all published literature has not been attempted.

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Section: Cyclodextrinsmentioning

confidence: 99%

Section: Cyclodextrinsmentioning

confidence: 99%

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

et al. 2019

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“…Although liquid chromatography is the predominant technique in chiral analysis, CE has also several advantages in this field, due to its low solvent and analyte consumption, high efficiency, and rapid analysis time. Moreover, the combination of CE with other techniques, especially NMR spectroscopy and theoretical calculations can help gain insight into the spatial structure and stoichiometry of diastereomeric selector‐selectand complexes and offer valuable information upon the chiral discrimination process . The aim of the present study was to develop, optimize and validate a fast and cost‐effective CE method for the enantiomeric quality control of R ‐RAS using CDs as chiral selector.…”

Section: Introductionmentioning

confidence: 99%

Chiral separation of rasagiline using sulfobutylether‐β‐cyclodextrin: capillary electrophoresis, NMR and molecular modeling study

et al. 2019

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Pressure‐assisted stereospecific capillary electrophoresis method was developed for the determination of enantiomeric purity of the antiparkinsonian agent (R)‐rasagiline. The optimized method, 50 mM glycine‐HCl buffer pH 2, supplied with 30 mM sulfobutylether‐β‐cyclodextrin, at 35°C, applying 12 kV in reversed polarity, and –8 mbar pressure (vacuum), short‐end injection with ‐25 mbar × 2 s, was successful for baseline separation of rasagiline enantiomers (Rs = 3.5 ± 0.1) in a short analysis time. The method was validated according to current guidelines and proved to be reliable, linear, precise and accurate for determination of 0.15% S‐enantiomer as chiral impurity in R‐rasagiline sample, as well as quantification of the eutomer. Method application was tested on a commercial tablet formulation. Determination of spatial structure of diastereomeric associates was based on 1H and 2D ROESY NMR, indicating that the aromatic moiety of the molecule can enter the cyclodextrin cavity. NMR titration and molecular modeling revealed that S‐rasagiline formed a more stable inclusion complex with sulfobutylether‐β‐cyclodextrin, than its antipode, which is in agreement with electrophoretic results.

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“…Thus, by resorting to Overhauser effect (NOE)‐based experiments, it is possible to obtain information on the spatial proximities of hydrogen atoms of both the selector and the analyte. Moreover, NMR analyses permit to mimic the solution state in which enantioseparations by CE are performed . Some works reported the use of 19 F NMR spectroscopy of a mixture of racemic Mosher's acid sodium salt and chiral ionic liquids in common NMR solvents in order to evaluate the chiral recognition properties of chiral ionic liquids allowing a quantitative comparison of the strength of the recognition properties between chiral ionic liquids and a racemic substrate .…”

Section: Introductionmentioning

confidence: 99%

Nuclear magnetic resonance to study the interactions acting in the enantiomeric separation of homocysteine by capillary electrophoresis with a dual system of γ‐cyclodextrin and the chiral ionic liquid EtCholNTf₂

et al. 2019

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The enantiomeric separation of 9‐fluorenylmethoxycarbonyl chloride (FMOC)‐homocysteine (Hcy) by CE was investigated using γ‐CD and the chiral ionic liquid (R)‐(1‐hydroxybutan‐2‐yl)(trimethyl)azanium‐bis(trifluoromethanesulfon)imidate (also called (R)‐N,N,N‐trimethyl‐2‐aminobutanol‐bis(trifluoromethane‐sulfon)imidate) (EtCholNTf2) as chiral selectors. Using 2 mM γ‐CD and 5 mM EtCholNTf2 in 50 mM borate buffer (pH 9), FMOC‐Hcy enantiomers were separated with a resolution value of 3.8. A reversal in the enantiomer migration order in comparison with the single use of γ‐CD in the separation buffer was obtained. Then, NMR experiments were carried out to elucidate the interactions taking place in the enantiomeric separation of FMOC‐Hcy. NMR analyses highlighted the formation of an inclusion complex since the hydrophobic group of FMOC‐Hcy was inserted into the γ‐CD cavity. Moreover, interactions between EtCholNTf2 and γ‐CD were also observed, suggesting that the chiral ionic liquid would also enter the cavity of the γ‐CD.

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Applications of nuclear magnetic resonance spectroscopy for the understanding of enantiomer separation mechanisms in capillary electrophoresis

Cited by 51 publications

References 115 publications

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

Chiral separation of rasagiline using sulfobutylether‐β‐cyclodextrin: capillary electrophoresis, NMR and molecular modeling study

Nuclear magnetic resonance to study the interactions acting in the enantiomeric separation of homocysteine by capillary electrophoresis with a dual system of γ‐cyclodextrin and the chiral ionic liquid EtCholNTf₂

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Applications of nuclear magnetic resonance spectroscopy for the understanding of enantiomer separation mechanisms in capillary electrophoresis

Cited by 51 publications

References 115 publications

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

Chiral separation of rasagiline using sulfobutylether‐β‐cyclodextrin: capillary electrophoresis, NMR and molecular modeling study

Nuclear magnetic resonance to study the interactions acting in the enantiomeric separation of homocysteine by capillary electrophoresis with a dual system of γ‐cyclodextrin and the chiral ionic liquid EtCholNTf2

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Product

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About

Nuclear magnetic resonance to study the interactions acting in the enantiomeric separation of homocysteine by capillary electrophoresis with a dual system of γ‐cyclodextrin and the chiral ionic liquid EtCholNTf₂