Enantioseparation by zeolitic imidazolate framework-8-silica hybrid monolithic column with sulfobutylether-ß-cyclodextrin as a chiral additive in capillary electrochromatography.

A zeolitic imidazolate framework (ZIF)-8-silica hybrid monolithic column was prepared by one-step sol-gel method. The stationary phase in the monolithic column was characterized by Fourier-transform infrared spectra, X-ray diffraction, thermogravimetric analysis, nitrogen adsorption/desorption, and zeta potential. The results showed that ZIF-8-silica hybrid monolithic materials had abundant functional groups, good crystallinity, large specific surface area, and good thermal stability. A capillary electrochromatography (CEC) chiral separation system was for the first time constructed with ZIF-8-silica hybrid monolithic column and sulfobutylether-ß-cyclodextrin (SBE-ß-CD) as a chiral additive and was applied to separate the selected single and mixed chiral compounds (13 natural amino acids and 5 chiral pesticides). Under the optimized CEC conditions, all the single analytes achieved baseline separation with resolution of 2.14-5.94 and selectivity factor of 1.06-1.49 in less than 6 min, and the mixed amino acids with similar properties were also simultaneously enantioseparated (Rs ≥ 1.82). Relative standard deviations (RSDs) of migration time and column efficiency were lower than 4.26% and did not change significantly after 200 runs, evidencing excellent reproducibility and stability. These results demonstrate that the application of SBE-ß-CD as a chiral additive for ZIF-8-silica hybrid monolithic columns is a promising method for the separation of chiral compounds.

Chiral covalent organic framework-based open tubular capillary electrochromatography column for enantioseparation of selected amino acids and pesticides.

A novel chiral covalent organic framework (CCOF) was synthesized with an imine covalent organic framework TpBD (synthesized via Schiff-base reaction between phloroglucinol (Tp) and benzidine (BD)) modified using (1S)-(+)-10-camphorsulfonyl chloride as chiral ligand by chemical bonding method for the first time, and was characterized by X-ray diffraction, Fourier-transform infrared spectra, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption, thermogravimetry analysis, and zeta-potential. The results revealed that the CCOF had good crystallinity, high specific surface area and good thermal stability. Then, the CCOF was employed as stationary phase in open-tubular capillary electrochromatography (OT-CEC) column (the CCOF-bonded OT-CEC column) for enantioseparation of 21 single chiral compounds (12 natural amino acids including acidic, neutral and basic, 9 pesticides including herbicides, insecticides and fungicides) and simultaneous enantioseparation of mixture amino acids and pesticides with similar structures or properties. Under the optimized CEC conditions, all the analytes reached the baseline separation with high resolutions of 1.67-25.93 and selectivity factors of 1.06-3.49 in 8 min. Finally, the reproducibility and stability of the CCOF-bonded OT-CEC column were measured. Relative standard deviations (RSDs) of retention time and separation efficiency were 0.58-4.57% and 1.85-4.98%, and not obviously changed after 150 runs. These results demonstrate that COFs-modified OT-CEC explore a promising method to separate chiral compounds.

A chiral fluorescent COF prepared by post-synthesis modification for optosensing of imazamox enantiomers.

We report a post-synthesis modification for the preparation of a novel chiral fluorescent covalent organic framework (COF) for selective recognization of imazamox enantiomers. In this study, chiral COF was firstly synthesized via a Schiff-base reaction between 2,5-dihydroxyterephthalaldehyde (Dha) and 1,3,5-tris(4-aminophenyl)benzene (Tab) followed by a nucleophilic substitution using (1S)-(+)-10-camphorsulfonyl chloride as chiral modifier. The resulting regular spherical chiral COF Dha Tab not only presented the high optical efficiency, strong covalent bond structure, good crystallinity, large specific surface area but also showed the specific enantioselectivity and quick identification for imazamox enantiomers among five pesticide enantiomers (S/R-imazamox, acephate, acetochlor, propisochlor and metalaxyl). The detection limits for S- and R-imazamox were 4.20 µmol/L and 3.03 µmol/L, respectively. Meanwhile, the enantiomeric excess value (5.30 %) manifested that the chiral COF Dha Tab had the strong adsorption ability to imazamox enantiomers and more higher affinity for R-imazamox. This chiral fluorescent COF opened up a new way for the recognition of enantiomers.

Preparation of a zeolite imidazole skeleton-silica hybrid monolithic column for amino acid analysis via capillary electrochromatography.

We developed a novel, convenient and low-cost one-pot strategy for preparing a zeolitic imidazolate framework-8 (ZIF-8)-silica hybrid monolithic column by adding ZIF-8 directly to a polymer solution of the silica matrix. The simulated stationary phase and monolithic column prepared under optimal conditions were characterized using X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis nitrogen physisorption and zeta potential. The results obtained confirmed the successful introduction of ZIF-8 into the silica monolithic column, and the prepared monolithic column exhibited good permeability and physicochemical stability. A capillary electrochromatography method was developed based on a ZIF-8-silica hybrid monolithic column through which 15 mixed amino acids, 4 neutral compounds, 4 nipagin esters and 2 chlorinated fungicides were separated in 14, 5, 7 and 6 min, respectively, under optimal conditions. The relative standard deviations retention times and column efficiencies in run-to-run, day-to-day and column-to-column varied in the ranges of 1.90%-2.21%, 2.13%-2.51% and 3.08%-6.65%, respectively, which demonstrated that ZIF-8-silica hybrid monolithic column exhibited satisfactory reproducibility and stability. The incorporation of ZIF-8 into a silica monolithic column is a promising method for preparing novel monolithic columns composed of a metal-organic framework.