Single-isomer carboxymethyl-γ-cyclodextrin as chiral resolving agent for capillary electrophoresis

Benkovics, Gábor; Fejős, Ida; Darcsi, András; Varga, Erzsébet; Fenyvesi, Éva; Sohajda, Tamás; Szente, Lajos; Béni, Szabolcs; Szemán, Julianna

doi:10.1016/j.chroma.2016.06.083

Cited by 34 publications

(18 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In order to characterize the host‐guest interactions at the molecular level and to get a deeper insight into the molecular interactions between the 6‐Me‐β‐CD and the MDPV enantiomers 1 H and 2D ROESY NMR experiments were performed according to previous works . The enantioselectivity of 6‐Me‐β‐CD was monitored at neutral pH, with racemic MDPV.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of the chiral selector heptakis(6‐O‐methyl)‐β‐cyclodextrin by phase‐transfer catalysis and hydrazine‐mediated transfer‐hydrogenation

et al. 2019

Self Cite

View full text Add to dashboard Cite

The exhaustive primary‐side alkylation of cyclodextrins has never been achieved directly. The undesired and simultaneous derivatization of the secondary hydroxyl moieties generates intricate isomeric mixtures that are challenging to purify, analyse and characterize. The aim of this study was to develop a chromatography‐free and up‐scalable strategy towards the preparation of per‐6‐O‐methylated cyclodextrin and to test the compound as potential chiral selector. The target molecule was prepared according to a five‐step synthesis by using methyltriphenylphosphonium bromide as catalyst under heterogeneous conditions. The removal of benzyl moieties, used as temporary secondary‐side protecting groups, was attained by applying hydrazine‐carbonate in the presence of Pd/C. All the intermediates were obtained in high yields, thoroughly characterized and their purity was assessed by ad‐hoc developed HPLC methods. The per‐6‐O‐methylated β‐cyclodextrin showed promising chiral recognition ability as background electrolyte additive in cyclodextrin‐modified capillary electrophoresis using the recreational drug methylene‐dioxypyrovalerone as model compound. Additionally, a model for the inclusion geometry between the single isomer host and the selected drug was developed based on the extensive 2D NMR analysis. The versatility of the proposed synthetic strategy opens the way to the industrial production of homogeneously primary‐alkylated cyclodextrins and to their wide application in chiral separation of various drugs.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of the chiral selector heptakis(6‐O‐methyl)‐β‐cyclodextrin by phase‐transfer catalysis and hydrazine‐mediated transfer‐hydrogenation

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…In order to get a deeper insight into the molecular interactions between the 2,6‐DIMEB and terbutaline enantiomers, 1 H and 2D ROESY NMR experiments were performed according to previous works . The enantioselectivity of 2,6‐DIMEB was monitored at acidic pH with racemic terbutaline.…”

Section: Resultsmentioning

confidence: 99%

“…Heptakis (2,3‐di‐ O ‐methyl)‐β‐cyclodextrin (2,3‐DIMEB) was prepared in three synthetic steps. Native BCD was regioselectively functionalized on primary hydroxyl groups with TBDMSi‐Cl in pyridine, then complete methylation of the secondary side was achieved under phase‐transfer catalysis conditions and mild removal of primary‐side protecting groups with ammonium bifluoride in methanol yielding the titled compound .…”

Section: Methodsmentioning

confidence: 99%

Comparative analysis of the full set of methylated β‐cyclodextrins as chiral selectors in capillary electrophoresis

et al. 2019

Self Cite

View full text Add to dashboard Cite

Comparative analysis of the full set of methylated ␤-cyclodextrins as chiral selectors in capillary electrophoresisThe chiral separation ability of the full library of methylated-␤-cyclodextrins towards pharmacologically significant racemic drugs including basic compounds was studied by chiral CE. The syntheses of all the methylated, single isomer ␤-cyclodextrins were revised and optimized and the aqueous solubility of the derivatives was unambiguously established. The three most relevant commercially available methylated isomeric mixtures were also included in the screening, so a total of ten various methylated CDs were investigated. The effects of the selector concentration on the enantiorecognition properties at acidic pH were investigated. Among the dimethylated ␤-cyclodextrins, the heptakis (2,6-di-Omethyl)-␤-cyclodextrin isomer (2,6-DIMEB) resulted to be the most versatile chiral selector. Terbutaline was selected as a model compound for the in-depth investigation of host-guest enantiodiscrimination ability. The association constants between the two terbutaline enantiomers and 2,6-DIMEB were determined in order to support that the enantioseparation is driven by differences is host-guest binding. The migration order of the enantiomers was confirmed by performing spiking experiments with the pure enantiomers. 1D and 2D NMR spectroscopy was applied to the 2,3-, and 2,6-DIMEB/terbutaline systems to rationalize at molecular level the different enantioseparation ability of the dimethylated ␤-cyclodextrin selectors.

show abstract

“…Therefore, obtaining a chiral monomer with high enantiopurity is of critical importance. For pharmacological research, efficient enantioseparation techniques are indispensable, such as high‐resolution gas chromatography (GC), high‐performance liquid chromatography (HPLC), capillary electrophoresis (CE), and so on.…”

Section: Introductionmentioning

confidence: 99%

A novel chiral inorganic mesoporous silica used as a stationary phase in GC

Yuan

et al. 2019

Chirality

View full text Add to dashboard Cite

Chiral mesoporous silica (CMS) has attracted widespread attention because of some unique properties, such as high surface area, uniformly structured nanoscale cavities, and excellent chemical and thermal stability. In this work, we report the utilization of a CMS as the stationary phase for the separation of racemates in gas chromatography (GC). A CMS‐coated capillary column was fabricated by a dynamic coating method. Eighteen racemates belonging to different classes of organic compounds were separated on this column, including chiral alcohols, aldehydes, ketones, organic acids, halohydrocarbons, alkenes, alcohol amines, epoxides, and amino acid derivatives. In addition, linear alkanes, alcohols, and aromatic hydrocarbons have also been resolved.

show abstract

Single-isomer carboxymethyl-γ-cyclodextrin as chiral resolving agent for capillary electrophoresis

Cited by 34 publications

References 32 publications

Synthesis of the chiral selector heptakis(6‐O‐methyl)‐β‐cyclodextrin by phase‐transfer catalysis and hydrazine‐mediated transfer‐hydrogenation

Synthesis of the chiral selector heptakis(6‐O‐methyl)‐β‐cyclodextrin by phase‐transfer catalysis and hydrazine‐mediated transfer‐hydrogenation

Comparative analysis of the full set of methylated β‐cyclodextrins as chiral selectors in capillary electrophoresis

A novel chiral inorganic mesoporous silica used as a stationary phase in GC

Contact Info

Product

Resources

About