Facile room-temperature synthesis of a spherical mesoporous covalent organic framework for capillary electrochromatography.

Herein, a spherical covalent organic framework COF TAPB-DMTP was facilely synthesized from 2,5-dimethoxyterephthalaldehyde (DMTP) and 1,3,5-tri-(4-aminophenyl)benzene (TAPB) as monomers. COF TAPB-DMTP with regular mesoporous and excellent mass transfer ability was first introduced into the capillary and immobilized on the inner wall of the capillary through a simple in situ growth method. Through various characterization results, COF TAPB-DMTP was successfully prepared and modified onto the capillary inner wall. The separation performance and potential of COF TAPB-DMTP modified capillary column was explored. The new developed COF modified column achieved a highly efficiency and selective separation between analytes with different properties, including halogeno benzenes, alkylbenzenes, phenols and sulfonamides. Satisfactory stability and reproducibility were observed on COF TAPB-DMTP modified columns. The intraday, interday and three batch columns relative standard deviations were all less than 1.85 % for the retention time. The separation performance of prepared column has no significant change after 90 continuous runs. Additionally, the COF TAPB-DMTP modified capillary column was successfully used for separation and detection of triazole antifungal drugs in human plasma, and the recoveries of three antifungal drugs (fluconazole, isavuconazole and posaconazole) in spiked samples were in the range of 98.6-100.8 %, 92.4-102.1 % and 99.9-107.5 %, respectively. This self-made column showed excellent application potential in chromatography separation science.

Multilayer coatings based on gold nanoparticles and polymers with bovine serum albumin as a functional layer for the chiral separation in capillary electrochromatography.

In this study, we developed physically adsorbed multi-layer coatings using poly-l-lysine or poly(diallyldimethylammonium chloride) and gold nanoparticles, which were functionalized with bovine serum albumin for the chiral separation in electrochromatography. The approach involves sequentially depositing positively charged polymers and negatively charged citrate-stabilized gold nanoparticles. By repeating this modification cycle, we created two- and four-layer coatings, which were sequentially functionalized with albumin forming three- and five-layer coatings that were finally applied for the separation of enantiomers of dl-tryptophan. The formed coatings exhibit stability across a pH range of 2-10 and feature a dense, uniform surface, as confirmed by scanning electron microscope images. The number of layers impacted nanoparticle deposition density, with five-layer coatings being denser than three-layer ones. Five-layer coatings enable baseline separation of dl-tryptophan enantiomers, whereas three-layer coatings require the presence of albumin in the background electrolyte for separation. Therefore, increasing the number of layers and gold nanoparticles density enhances albumin active center concentration on capillary walls, improving the separation of dl-tryptophan enantiomers. The five-layer coatings can be easily fabricated and possess good repeatability of analytes migration time.

Organic-silica hybrid monolithic sorbents for sample preparation techniques: A review on advances in synthesis, characterization, and applications.

Organic-silica hybrid monolithic materials have attracted considerable attention as potential stationary phases in separation science. These materials combine the advantages of organic polymer and silica-based monoliths, including easy preparation, lower back pressure, high permeability, excellent mechanical strength, thermal stability, and tunable surface chemistry with high surface area and selectivity. The outstanding chromatographic efficiency as stationary phase of hybrid monolithic capillary columns for capillary liquid chromatography and capillary electrochromatography has been reported in many papers. Organic-silica hybrid monolithic materials have also been extensively used in the field of sample preparation. Owing to their surface functionalities, these porous sorbents offer unique selectivity for pre-concentration of different analytes in the most complex matrixes by fast dynamic transport. These sorbents not only improve the analytical method sensitivity, but also introduce novelties in terms of extraction devices and instrument coupling strategies. The current review covers the period spanning from 2017 to 2023 and describes the properties of organic-inorganic hybrid monolithic materials, the present status of this technology and summarizes recent developments in their use as innovative sorbents for microextraction sample preparation techniques (solid phase microextraction with pipette tip, offline in-tube SPME, in-tube SPME online with LC, and in-tube SPME directly coupled with mass spectrometry). Aspects such as the synthesis methods (sol-gel process, one-pot approach, and polyhedral oligomeric silsesquioxanes-based procedure), characterization techniques, and strategies to improve extraction efficiency in various applications in different areas (environmental, food, bioanalysis, and proteomics) are also discussed.

Open tubular capillary electrochromatography with dual-responsive polymer as coating for separation of chromones.

Fabricating polymeric coatings that are responsive to multiple/dual stimuli is crucial and remains a major challenge in the development of highly efficient open tubular capillary electrochromatography (OT-CEC). In this study, a pH and temperature-responsive block copolymer, poly(styrene-maleic anhydride 2-dimethylamino ethyl methacrylate), P(St-MAn-DMAEMA), was designed and synthesized. Using P(St-MAn-DMAEMA) as the coating, an OT-CEC protocol was constructed for the analysis of chromones. The morphology and hydrophobicity-hydrophilicity of the polymeric coating could change via varying the environmental conditions, affecting the separation efficiency of OT-CEC. Interestingly, the best performance of OT-CEC was achieved at pH 9.7 and 45 °C via tuning the interactions between the coating and the analytes. Additionally, the proposed OT-CEC method exhibited a good linear range for the detection of the three test chromones from 10.0 to 100.0 µM, with all correlation coefficients (R2) >0.997. The coatings also had good stability and reusability. This work provides an approach for the preparation of new multiple-stimuli-responsive polymeric coatings for the establishment of OT-CEC systems.

In-situ immobilization of covalent organic frameworks as stationary phase for capillary electrochromatography.

A new kind of covalent organic framework (COF) was first utilized as an stationary phase for open-tubular electrochromatography (OT-CEC) by in situ synthesis immobilized method at room temperature. On the basis of our previous work, 4,4',4″-(1,3,5-Triazine-2,4,6-triyl)trianiline (TZ) and 2,5-bis(2-propyn-1-yloxy)-1,4-benzenedicarboxaldehyde (BPTA) were employed as building blocks for the synthesis of COF TZ-BPTA. The coated capillary and COF TZ-BPTA were characterized by scanning electron microscopy (SEM). Then, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) were also applied to characterize COF TZ-BPTA and the modified column. In SEM, it can be seen that COF TZ-BPTA was the spherical shape and the modified capillary was covered with globular particles equably. The COF TZ-BPTA coated column exhibited good separation resolution and efficiency towards two antiepileptic drugs and other kinds of small organic molecules involving alkylbenzene, sulfonamides, polycyclic aromatic hydrocarbon (PAH), parabens, amino acids and herbicides. The maximum column efficiency was over 2.8 × 105 plates·m-1. In addition, the precisions (RSDs) of the retention times for the alkylbenzenes of intra-day runs (n = 3), inter-day runs (n = 3) and column-to-column runs (n = 3) were all less than 1.70% and separation performance was without obvious change within 100 times run. In addition, the real sample was tested on COF TZ-BPTA coated column. Hence, COF TZ-BPTA showed great potential in the separation domain.

Three-dimensional fluorinated covalent organic frameworks coated capillary for the separation of fluoroquinolones by capillary electrochromatography.

In this work, a three-dimensional fluorinated covalent organic frameworks (3D FCOFs) JUC-515 was synthesized from tetra(4-aminophenyl)methane (TAM) and 2,3,5,6-tetrafluoroterephthalol (TFA) by an ionic liquid method. JUC-515 was introduced into the capillary column and bonded to the inner wall of the capillary column by chemical bonding. Through a variety of characterization results, JUC-515 was successfully synthesized and introduced into the capillary column. The effects of buffer solution concentration, organic additive content and pH of the buffer solution on the separation of fluoroquinolones (FQs) were investigated in detail. The JUC-515-coated capillary column showed good resolution (>1.5) and reproducibility. The relative standard deviations (RSDs) of the retention time for intraday, interday, column-to-column and interbatch precision were less than 0.88%, 2.45%, 2.74% and 3.32%, respectively. The RSDs of the peak area for intraday, interday, column-to-column and interbatch precision were less than 3.79%, 4.31%, 3.33% and 5.62%, respectively. The JUC-515-coated capillary column could be used no less than 150 times. The results showed that the JUC-515-coated capillary column had good separation performance. In addition, by separating fluorinated ß-phenylalanine analogs, ß-phenylalanine and trifluoromethyl ß-phenylalanine analogs, the separation mechanism based on fluorine interactions was discussed. In conclusion, JUC-515 had good potential as a stationary phase for capillary electrochromatography.

Enantiomeric analysis of drugs in water samples by using liquid-liquid microextraction and nano-liquid chromatography.

The nano-LC technique is increasingly used for both fast studies on enantiomeric analysis and test beds of novel stationary phases due to the small volumes involved and the short conditioning and analysis times. In this study, the enantioseparation of 10 drugs from different families was carried out by nano-LC, utilizing silica with immobilized amylose tris(3-chloro-5-methylphenylcarbamate) column. The effect on chiral separation caused by the addition of different salts to the mobile phase was evaluated. To simultaneously separate as many enantiomers as possible, the effect of buffer concentration in the mobile phase was studied, and, to increase the sensitivity, a liquid-liquid microextraction based on the use of isoamyl acetate as sustainable extraction solvent was applied to pre-concentrate four chiral drugs from tap and environmental waters, achieving satisfactory recoveries (>70%).

A chiral metal-organic framework synthesized by the mixture of chiral and non-chiral organic ligands for enantioseparation of drugs by open-tubular capillary electrochromatography.

A chiral metal-organic framework L-Histidine-Zeolitic imidazolate framework-67 (L-His-ZIF-67) was synthesized by the mixture of chiral organic ligand L-histidine and non-chiral organic ligand 2-methylimidazole directly, and to the author's knowledge, the chiral L-His-ZIF-67 coated capillary column we prepared has still not been reported to date in the field of capillary electrophoresis. This chiral metal-organic frameworks material was used as the chiral stationary phase for enantioseparation of drugs by open-tubular capillary electrochromatography. The separation conditions such as pH value, buffer concentration and proportion of organic modifier were optimized. Under optimal conditions, the established enantioseparation system achieved good separation effect, and the resolution of five chiral drugs: esmolol (7.93), nefopam (3.03), salbutamol (2.42), scopolamine (1.08) and sotalol (0.81). In addition, the chiral recognition mechanism of L-His-ZIF-67 was elucidated by a series of mechanism experiments, and the specific interaction force was preliminarily speculated.

Preparation of open tubular capillary column covalently coated with polystyrene sulfonate with 4,4'-Azobis(4-cyanopentanoyl chloride) as polymerization initiator for electrochromatographic separation of alkaloids, sulfonamides, and peptides.

An open tubular capillary electrochromatography column covalently bonded with polystyrene sulfonate was prepared via in situ polymerization using functionalized Azo-initiator 4,4'-Azobis(4-cyanopentanoyl chloride). Scanning electron, fluorescence, and atomic force microscopy techniques showed the formation of a relatively rough layer of polymer. In addition, -CN and C = O stretching vibrations from infrared spectroscopy proved the successful immobilization of the azo-initiator through covalent bonding and X-ray photoelectron spectroscopy confirmed the elemental composition of the formed polymer layer. The prepared column was found to be appropriate for small and medium-sized molecules separation. Compared to bare fused silica capillary column higher selectivity and resolution were obtained for the separation of alkaloids, sulfonamides, and peptides as a result of the electrostatic and pi-pi stacking interactions between the small organic molecules and the coated column without compromising the electroosmotic flow mobility. Separation efficiency was also increased compared to the bare capillary for the separation of alkaloids (about 1.5 times). Moreover, intraday, inter-day, intra-batch, and inter-batch relative standard deviation values of retention time and peak area of peptides were within 2% and 10%, respectively, indicating good repeatability of the column preparation procedure. The developed method for the covalent bonding of polymers through a functionalized azo-initiator could represent a promising stable method for the preparation of an open tubular column.

Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded Tris ligands for use in hydrophilic interaction capillary electrochromatography.

The facile preparation of a monolithic capillary column with surface bound polar ligands for use in hydrophilic interaction capillary electrochromatography is described. It involved the conversion of poly(carboxyethyl acrylate[CEA]-co-ethylene glycol dimethacrylate[EDMA]) precursor monolith (the so-called carboxy monolith) into a Tris bonded monolith by a post-polymerization functionalization process in the presence of a water soluble carbodiimide, namely N-(3-dimethylaminopropyl)-N´-ethylcarbodiimidehydrochloride. The carbodiimide assisted conversion, allowed the covalent attachment of the carboxyl group of the precursor monolith to the amino group of the Tris ligand via a stable amide linkage. This resulted in the formation of Tris poly(CEA-co-EDMA) monolith, which exhibited the typical retention behavior of hydrophilic interaction stationary phase when analyzing polar and slightly polar neutral or charged compounds. In fact, neutral polar species such as dimethylformamide, formamide and thiourea were retained in the order of increased polarity with acetonitrile rich mobile phase. Also, neutral p-nitrophenyl maltooligosaccharides (PNP-maltooligosaccharides) served as a polar homologous series for gauging the hydrophilicity of the Tris poly(CEA-co-EDMA) monolith, thus forming a versatile testing homologous series for other hydrophilic columns. Other polar anionic species (e.g., hydroxy benzoic acids and nucleotides) and weakly polar anionic compounds (e.g., dansyl amino acids and phenoxy acid herbicides) as well as polar weak bases namely nucleobases and nucleosides were used to probe the hydrophilic characters of the Tris poly(CEA-co-EDMA) monolith. The various polar and weakly polar compounds just mentioned revealed the wide potentiality of the hydrophilic interaction column under investigation.

In situ growth of imine-based covalent organic framework as stationary phase for high-efficiency electrochromatographic separation.

Design of the smart stationary phases, which can improve the separation efficiency is an essential work in the capillary electrochromatography (CEC). Owing to good excellent properties, covalent organic frameworks (COFs) have showed promising potential in the area of separation science. Here, a micro- and mesoporous COF TAPB-BTCA with adequate available interaction sites and outstanding mass transfer performance was first exploited as a stationary phase for high-efficiency in capillary electrochromatography. Through in situ growth approach, the COF TAPB-BTCA coated capillary column was facilely prepared at room temperature. The separation ability of the COF TAPB-BTCA coated capillary column was studied. The fabricated column showed high efficiency for the separation of six types of small molecular compounds, including alkylbenzenes, chlorobenzenes, phenols, parabens, vanillin and related phenolic compounds, and non-steroidal anti-inflammatory drugs (NSAIDs). The maximum theoretical plates reached up to 293,363 N/m for phloroglucinol, showing significantly improved column efficiency in comparison to previous reported COFs-based columns. In addition, the mass loadability for methylbenzene was achieved to 1.44 mg/mL. Also, excellent reproducibility and stability were obtained on the COF TAPB-BTCA coated columns. The relative standard deviations of intra-day (n = 3), inter-day (n = 3) and three batch tubes were all less than 2%, and no obvious change was presented in separation performance after the column was used 120 runs. This COF TAPB-BTCA-based stationary phase would be a promising candidate for high-efficiency chromatographic separation.

Lipase-based MIL-100(Fe) biocomposites as chiral stationary phase for high-efficiency capillary electrochromatographic enantioseparation.

A novel chiral porous column was fabricated by lipase immobilized MIL-100(Fe) biocomposites as chiral stationary phase through covalent coupling and applied to capillary electrochromatographic enantioseparation. MOF-based lipase biocomposites not only enhance stereoselective activities but also improve the stability and applicability of the enzyme. The functionalized porous columns were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. The performance of the porous column was evaluated by enantioseparating amino acid enantiomers, affording high resolution over 2.0. Besides, the enantio-resolutions of phenylephrine, phenylsuccinic acid, chloroquine, and zopiclone were also greater than 2.0. The relative standard deviations of run-to-run, intra-, and inter-day repeatability were within 4.0% in terms of resolution and retention time, exhibiting excellent stability of the column. Conceivably, the results show that MOF-based lipase composites as chiral stationary phase offer a highly efficient means for enantioseparation in capillary electrochromatography, attributing to the enhanced enantioselective activities of lipase by highly ordered frameworks.

Solid-phase microextraction with MIL-53(Al)-polymer monolithic column coupled to pressurized capillary electrochromatography for determination of chlorogenic acid and ferulic acid in sugarcane samples.

In this paper, a polymer monolithic column based on poly (Butyl methacrylate-co-ethylene glycol dimethacrylate) (poly (BMA-co-EDGMA)) doped with MIL-53(Al) metal-organic framework (MOF) was prepared using an in situ polymerization method. The characteristics of MIL-53(Al)-polymer monolithic column were studied through scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FT-IR), energy-dispersive spectroscopy (EDS), X-ray powder diffractometry (XRD), and nitrogen adsorption experiment. Due to its large surface area, the prepared MIL-53(Al)-polymer monolithic column has good permeability and high extraction efficiency. Using MIL-53(Al)-polymer monolithic column for solid-phase microextraction (SPME), coupled to pressurized capillary electrochromatography (pCEC), a method for the determination of trace chlorogenic acid and ferulic acid in sugarcane was established. Under optimized conditions, chlorogenic acid and ferulic acid have a good linear relationship (r ≥ 0.9965) within the concentration range of 50.0-500 µg/mL, the detection limit is 0.017 µg/mL, and the relative standard deviation (RSD) is less than 3.2%. The spike recoveries of chlorogenic acid and ferulic acid were 96.5% and 96.7%, respectively. The results indicate that the method is sensitive, practical, and convenient. It has been successfully applied to the separation and detection of trace organic phenolic compounds in sugarcane samples.

Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded (S)-(-)-1-(2-naphthyl) ethylamine ligands for use in chiral and achiral separations by capillary electrochromatography.

In this research report, the previously developed poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith (referred to as carboxy monolith) is further exploited in the preparation of a chiral stationary phase for enantiomeric separations. The carboxy monolith precursor was subjected to post polymerization functionalization (PPF) with the chiral selector (S)-(-)-1-(2-naphthyl) ethylamine (NAS) at room temperature in the presence of N, N´-dicyclohexylcarbodiimide (DCC) in chloroform. The DCC, which is an organic soluble carbodiimide, permits the linkage for the amine functionality of the chiral ligand NAS to the carboxy group of the monolithic surface forming a stable amide linkage. The NAS column thus obtained allowed not only enantiomeric separations in the RP mode via its chiral site but also the separation of nonpolar species via its achiral functionality offering both hydrophobic and π-π interactions for aromatic compounds such toluene derivatives and polyaromatic hydrocarbons. The dual interaction sites (e.g., chiral, and achiral) of the NAS present a convenient column for the separations of slightly polar and nonpolar chiral and achiral solutes in the RP mode.

Homomesoporous Metal-Organic Framework for High-Performance Electrochromatographic Separation.

Metal-organic frameworks (MOFs) have exhibited tremendous potential in the area of separation science. However, most of the developed MOF-based stationary phases contained only microporous structures and suffer from limited separation performance. Herein, homomesoporous MOFs with excellent mass transfer capability and strong thermodynamic interactions are first explored as the novel stationary phase for high-performance capillary electrochromatographic separations. As a proof of concept, noninterpenetrated mesoMOF-1 with uniform mesopore sizes (22.5 × 26.1 Å) and good stability was facilely grown on the inner surface of capillaries and applied as a homomesoporous MOF coating-based stationary phase for high-efficiency electrochromatographic separation. Seven types of analytes with different molecular dimensions were all baseline separated on a mesoMOF-1 coated column with high theoretical plate numbers and excellent repeatability, exhibiting significantly improved separation selectivity and column efficiency in comparison to a microporous HKUST-1 coated column. The maximum column efficiencies of the mesoMOF-1 coated column for substituted benzenes and halobenzenes reached up to 1.4 × 105 plates/m, and its mass loadability was also much higher than that of the HKUST-1 coated column. In addition, based on the analysis of adsorption kinetics and chromatographic retention behaviors, the interaction and retention mechanisms of different molecular-weight analytes on mesoMOF-1 coated stationary phases were systematically explored and disclosed in detail. These results indicate that the homomesoporous MOF-based stationary phase can effectively balance the kinetic diffusion (mass transfer capability) and thermodynamic interactions (the strength of adsorption interaction), having great potential for high-performance chromatographic separation.

Poly(carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith with bonded anthracenyl ligands for use in reversed-phase capillary electrochromatography based on hydrophobic and π-π interactions.

In this research report, the post polymerization functionalization (PPF) of a carboxyethyl acrylate (CEA)-co-ethylene glycol dimethacrylate (EDMA) [poly-CEA-co-EDMA)] precursor monolith with 2-aminoanthracene was carried out in the presence of an organic solvent soluble carbodiimide, namely N,N´-dicyclohexylcarbodiimide (DCC), yielding the so-called anthracenyl-poly-CEA-co-EDMA monolith. This novel monolith proved to be an excellent monolithic stationary for reversed-phase capillary electrochromatography (RP-CEC) with hydrophobic and π-π interactions of a wide range of nonpolar solutes including those bearing aryl functional groups in their structures such as polycyclic aromatic hydrocarbons (PAHs), toluene derivatives and aniline derivatives as well as solutes carrying in their structures electron withdrawing substituents such as dinitrophenyl-amino acids (DNP-AAs) and di-DNP-AAs. The retention behaviors of the just mentioned solutes obtained on the anthracenyl-poly-CEA-co-EDMA monolithic column were compared to those obtained on octadecyl-poly-CEA-co-EDMA monolithic column prepared from the same carboxy-precursor monolith. The results demonstrated the superiority of anthracenyl column over the octadecyl column for the separation and enhanced selectivity for aromatic solutes since it provides not only hydrophobic interactions but also π-π interactions with aromatic nonpolar solutes.

Synthesis of carbon dots-based covalent organic nanomaterial as stationary phase for open tubular capillary electrochromatography.

The transformation of zero-dimensional carbon dots (CDs) to cross-linked nanomaterials is rare. In this work, a novel carbon dots-based covalent organic nanomaterial (CON CDs-TAPB) consisted of 1,3,5-tris(4-aminophenyl)-benzene (TAPB) and carbon dots (CDs) through facile Schiff-base reaction was synthesized and then employed as a stationary phase for open-tubular capillary electrochromatography (OT-CEC). The CON CDs-TAPB and the CDs-TAPB coated column were characterized through Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), UV-spectra experiments and X-ray photoelectron spectroscopy (XPS). Thanks to CON CDs-TAPB unique structure and abundant accessibility and interaction sites, the prepared column exhibited a satisfactory separation ability towards analytes including parabens, phenolic compounds. Among all analytes, the highest column efficiency was over 1.6 × 105 plates·m-1. In addition, affording methylbenzene loading capacity of 156.9 pmole, surpassing most of those materials-based OT-CEC reported thus far. Thus, the prepared carbon dots-based covalent organic nanomaterial (CON CDs-TAPB) gave a potential as a stationary phase in the separation science.

Synthesis of multifunctional crown ether covalent organic nanospheres as stationary phase for capillary electrochromatography.

Crown ethers are macrocyclic polyether compounds containing multiple -oxo-methylene-structural units, which are often used for recognition of metal ions and ammonium ions. Inspired by the molecular design of rotaxanes, a novel covalent organic nanospheres material (CON ADBC-Tp) constructed by 4,4'-diaminodibenzo-18-crown-6 (ADBC) and 2,4,6-triformylphloroglucinol (Tp) was rationally designed as stationary phase for the separation of compounds containing imidazole structure. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) were carried out to confirm the morphology and composition of ADBC-Tp and ADBC-Tp modified capillary column. Thanks to the introduction of crown ether building ligands, the prepared capillary column exhibited excellent separation selectivity towards protonated imidazole structure, with benzimidazole and its 2-substituted derivatives as modal analytes. Moreover, separation of fungicides, nucleobases, short peptides and sulfanilamides were achieved on ADBC-Tp@capillary. The multifunctional ADBC-Tp@capillary with satisfactory reproducibility and stability gives great promise for separation science.

Determination of benzimidazoles in fruits by open-tubular capillary electrochromatography based on ionic liquids grafted covalent organic frameworks.

A novel capillary electrochromatography method has been developed for the simultaneous quantification of ten benzimidazole fungicides in fruits. Herein, covalent organic frameworks (COFs) and ionic liquids (ILs) were successfully introduced to prepare open-tubular capillary column to improve the loading capacity and separation performance. The parameters effecting the analytical performance including pH and concentration of running buffer, separation voltage and the addition of organic solvent were investigated systematically. Under the optimized conditions, the method allowed the baseline separation of ten benzimidazole fungicides, and showed a good linearity in the range of 3.5-200 µg kg-1 with the detection limits between 1.0 and 2.8 µg kg-1. The intraday and interday precisions for recoveries were lower than 7.9% and 12.2%, respectively. Intraday and interday precisions for their retention times were lower than 3.2% and 6.6%, respectively. Satisfactory recoveries for grape, pear and orange samples at two concentrations were obtained ranging from 85.0 to 95.9% with RSDs lower than 7.8%, demonstrating the potential applications of the open-tubular capillary electrochromatography method for trace benzimidazole fungicides analysis in fruits.

Carboxymethyl-ß-cyclodextrin and histidine-zeolitic imidazolate framework-8 used for enantioseparation of three basic drugs in open-tubular capillary electrochromatography.

Metal organic frameworks (MOFs) have drawn broad attention as a novel stationary phase due to their highly porous structure, modifiable pores, large specific surface areas, and satisfactory stability. In this paper, histidine-zeolitic imidazolate framework-8 (His-ZIF-8) synthesized at room temperature was physically coated to the internal surface of the capillary column and the carboxymethyl-ß-cyclodextrin (CM-ß-CD) as the chiral selector was chemically bonded to the His-ZIF-8@capillary column. The prepared CM-ß-CD@His-ZIF-8@capillary column was used for the enantioseparation of amlodipine, propranolol, and atenolol in capillary electrochromatography. In contrast to the CM-ß-CD@capillary column without His-ZIF-8, the CM-ß-CD@His-ZIF-8@capillary column reveals significantly improved enantiodiscrimination performance for amlodipine (Rs : 0 → 2.29), propranolol (Rs : 0 → 1.69), and atenolol (Rs : 0 → 0.79). His-ZIF-8 concentration, buffer pH, buffer concentration, and the proportion of organic modifier were evaluated in detail with enantiomerically separating chiral molecules. The repeatability of intraday, day-to-day, and column-to-column have been discussed; the result was preferable, and the relative standard deviation (RSD) of separation parameters was <6.7%.