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

Abstract

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 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.

Nanocarriers and Their Loading Strategies

“…In most cases, the host molecules are cyclic molecules having a hydrophobic inner cavity and a hydrophilic rim, such as cyclodextrins (CD), cucurbiturils, or calixarenes. Among them, the family of CD macrocycles is most widely studied, with diverse applications in catalysis, separation, food, and biomedicine …”

Preparation and evaluation of partially‐substituted 3‐chloro‐4‐methylphenylcarbamate‐β‐cyclodextrin bonded silica particles as chiral stationary phase for multi‐mode HPLC

“…Among the three positional isomers of nitroaniline, the o ‐nitroaniline was eluted first under IPA/hexane mobile phase conditions (as demonstrated in Figure B), however, m ‐nitroaniline was eluted first under methanol/water mobile phase conditions (as shown in Table ). This indicates the main separation mechanisms can be different on the CMP‐CD‐HPS‐packed column under different modes of mobile phase conditions . The results also suggested that the solutes which are not separable under one mobile phase mode could be separated under the other mobile phase mode on the new type of CMP‐CD‐HPS‐packed column.…”

“…Therefore, the main enantioseparation mechanism appears to be formation of a host‐guest inclusion complex in which the hydrophobic portion of the solute is included in the β‐CD cavity and the substituted 3‐chloro‐4‐methylphenylcarbamate moieties can provide additional interactions, e.g., dipolar‐dipolar interaction and pi‐pi interaction, etc. with the solute . Furthermore, the stable chiral ether spacer linking to the secondary hydroxyl site of β‐CD in the CMP‐CD‐HPS can provide extra steric interaction for the solute enantiomer to enter the β‐CD cavity via the wider torus rim.…”

“…Development of new chiral stationary phases (CSPs) possessing high enantioselectivity for efficient chiral separations of chiral drug compounds is still an active and important field in HPLC . Due to the special spatial structure and properties of native β‐cyclodextrin (β‐CD) and its derivatives, the β‐CD‐based CSPs play important roles in the separation of chiral drugs . Owing to the different sizes of the primary and secondary openings of the cyclodextrin, the orientation of cyclodextrin can significantly affect the separation ability .…”

Stereoisomer separation of flavanones and flavanone‐7‐O‐glycosides by means of nanoliquid chromatography employing derivatized β‐cyclodextrins as mobile‐phase additive

“…Recent works tested the performance of various novel carbamoyl-functionalized cyclodextrin CSPs for sets of model compounds of various structures, including simple flavonoids, such as hesperetin and naringenin [10]. Particularly, a novel single sulfoether-bridged cationic per(3,5dimethyl)phenylcarbamoylated-β-cyclodextrin separation material was prepared by thiolene click chemistry was developed achieving the enantioseparation of naringenin and hesperetin [11]. A new stilbene diamido-bridged bis(βcyclodextrin)-bonded CSP was synthesized allowing a better enantioseparation of flavanones, including naringin and hesperidin, compared to native β-cyclodextrin [12].…”