Two-dimensional chiral metal-organic framework nanosheets L-hyp-Ni/Fe@SiO2 composite for HPLC separation.

In this study, we have synthesised a chiral l-hyp-Ni/Fe@SiO2 composite as a chiral stationary phase (CSP) for high-performance liquid chromatography (HPLC) for the first time. This was achieved by coating two-dimensional (2D) chiral metal-organic framework nanosheets (MONs) l-hyp-Ni/Fe onto the surface of activated SiO2 microspheres using the "wrapped in net" method. The separation efficiency of the l-hyp-Ni/Fe chromatographic column was systematically evaluated in normal-phase HPLC (NP-HPLC) and reversed-phase HPLC (RP-HPLC) configurations, employing various racemates as analytes. The findings revealed that 16 chiral compounds were separated using NP-HPLC, and five were separated using RP-HPLC, encompassing alcohols, amines, ketones, esters, alkanes, ethers, amino acids and sulfoxides. Notably, the resolution (Rs) of nine chiral compounds exceeded 1.5, indicating baseline separation. Furthermore, the resolution performance of the l-hyp-Ni/Fe@SiO2-packed column was compared with that of Chiralpak AD-H. It was observed that certain enantiomers, which either could not be resolved or were inadequately separated on the Chiralpak AD-H column, attained separation on the 2D chiral MONs column. These findings suggest a complementary relationship between the two columns in racemate separation, with their combined application facilitating the resolution of a broader spectrum of chiral compounds. In addition, baseline separation was achieved for five positional isomers on the l-hyp-Ni/Fe@SiO2-packed column. The effects of the analyte mass and column temperature on the resolution were also examined. Moreover, during HPLC analysis, the l-hyp-Ni/Fe columns demonstrated commendable repeatability, stability and reproducibility in enantiomer separation. This research not only advances the utilisation of 2D chiral MONs as CSPs but also expands their applications in the separation sciences.

A hydroxyl-functionalized homochiral porous organic cage for gas chromatographic separations.

A hydroxyl-functionalized homochiral porous organic cage (POC) was synthesized and characterized by FTIR, NMR, thermogravimetric analysis (TGA), MALDI-TOF-MS, and elemental analysis. The synthesized homochiral POC was used as stationary phase to prepare a capillary gas chromatography (GC) column by a static coating method. The fabricated column shows excellent selectivity not only for the separation of positional isomers but also for the resolution of various racemates. Thirty-nine racemates have been resolved on the column, including alcohols, diols, halohydrocarbons, epoxides, esters, lactones, ketones, ethers, and organic acids. Compared to the commercial ß-DEX 120 column and previously reported chiral POCs (CC3-R, CC9, and CC10)-coated columns, there are 11, 10, 24, and 15 tested racemates that cannot be resolved on ß-DEX 120 column, CC3-R column, CC9 column, and CC10 column, respectively. This reveals that the fabricated column has prominent complementarity or superior separation performance to these columns in enantioseparation. Besides, the fabricated column can achieve some enantioseparations which are not possible using all previously reported chiral POC-based columns. Some positional isomers (xylenes, dichlorobenzenes, dibromobenzenes, nitrochlorobenzenes, and nitrobromobenzenes) were also separated with high-resolution values. The column exhibits good repeatability, reproducibility, and stability. The relative standard deviation (RSD) values of retention times were 0.03-0.18%, 0.11-0.92%, and 2.1-6.6% for run-to-run (n = 5), day-to-day (n = 5), and column-to-column (n = 3), respectively. The experimental results demonstrate the great potential of POCs for practical application in GC. Graphical Abstract A hydroxyl-functionalized homochiral porous organic cage was used as stationary phase for gas chromatography separation of racemates and positional isomers. The resolution of racemates mainly depended on hydrogen bonding, π-interaction, host-guest inclusion, steric fit, etc., while separation of positional isomers by shape-selective guest binding.

Formation, characterization and enzyme activity in water-in-hydrophobic ionic liquid microemulsion stabilized by mixed cationic/nonionic surfactants.

The phase behavior of the pseudo ternary system 1-tetradecyl-3-methylimidazolium bromide ([C14mim]Br)/Triton X-100/H2O/1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6) has been studied at 35°C. With the increase in the mole fraction of Triton X-100 in the mixed surfactants, the water solubilization capacity increases and the monophasic area enlarges. The H2O-in-[Bmim]PF6 (W/IL) microemulsion was identified via electrical conductivity measurement. The existence of bulk water in the W/IL microemulsion was demonstrated based on the change of the O-D vibration frequency with content of D2O added and confirmed using UV-vis technique with CoCl2 as probe. Laccase can be solubilized in the W/IL microemulsion and exhibits a catalytic activity. The interface of the W/IL microemulsion has an inhibitory effect on the expression of the laccase activity, and the inhibitory effect is varied with the molar ratio of the mixed surfactants.

Choline acetate enhanced the catalytic performance of Candida rogusa lipase in AOT reverse micelles.

Choline acetate is an ionic liquid composed of a kosmotropic anion and a chaotropic cation. According to Hofmeister series, a kosmotropic anion and/or a chaotropic cation could stabilize an enzyme, thereby facilitating the retention of the catalytic activity of the enzyme. In this work, we first report the influence of choline acetate on the activity and stability of lipase in AOT/water/isooctane reverse micelles. The indicator reaction is the lipase-catalyzed hydrolysis of 4-nitrophenyl butyrate. The results show that a low level of choline acetate does not affect the microstructure of the AOT reverse micelles, but the ionic liquid can improve the catalytic efficiency of lipase. Fluorescence spectra show that a high level of choline acetate has an impact on the conformation of lipase, so the activation is mainly due to the influence of choline acetate on the nucleophilicity of water. Infrared spectra demonstrate that choline acetate can form stronger hydrogen bonds with water surrounding lipase, and therefore enhance the nucleophilicity of the water, which makes it easier to attack the acyl enzyme intermediate, thereby increasing the activity of the lipase-catalyzed hydrolysis of the ester. A study on the stability of lipase in AOT reverse micelles indicates that the ionic liquid is able to maintain the activity of lipase to a certain extent. The effect of choline acetate is consistent with that predicted based on Hofmeister series.