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.

Single-drop microextraction technique for the determination of antibiotics in environmental water.

Growing concerns related to antibiotic residues in environmental water have encouraged the development of rapid, sensitive, and accurate analytical methods. Single-drop microextraction has been recognized as an efficient approach for the isolation and preconcentration of several analytes from a complex sample matrix. Thus, single-drop microextraction techniques are cost-effective and less harmful to the environment, subscribing to green analytical chemistry principles. Herein, an overview and the current advances in single-drop microextraction for the determination of antibiotics in environmental water are presented were included. In particular, two main approaches used to perform single-drop microextraction (direct immersion-single-drop microextraction and headspace-single-drop microextraction) are reviewed. Furthermore, the impressive analytical features and future perspectives of single-drop microextraction are discussed in this review.

Utilization of ionic deep eutectic solvent as sustainable mobile phase additive in high-performance liquid chromatography for improving the separation of biogenic amines.

Biogenic amines are present in large quantities in fermented foods and are a key marker for assessing food safety. This paper proposes a novel method for high-performance liquid chromatography analysis of biogenic amines using deep eutectic solvent as a mobile phase additive. After screening eight synthetic deep eutectic solvents and comparing them with several common additives, deep eutectic solvents based on choline chloride and ethylene glycol showed significant effects in improving the separation of biogenic amines. A Box-Behnken design of 17 runs was used to screen and optimize the key chromatographic parameters, resulting in an expected composition of the mobile phase of 0.73% deep eutectic solvent, 65% acetonitrile, and a column temperature of 28°C. The proposed method exhibited excellent linearity (0.1-50 µg/ml, R2 ≥ 0.9987), limit of detection (0.007-0.031 µg/ml), precision (1.28%-5.34%) and accuracy (87.2%-110.6%). The method can be applied successfully to the separation and analysis of biogenic amines in cooking wine samples.

Growth of two-layer copolymer as the stationary phase with very high separation efficiency for separating peptides in capillary electrochromatography.

Open tubular CEC (OT-CEC) column with a very high separation efficiency was prepared for peptides separation. A pretreated silica-fused capillary was reacted with 3-(methacryloxy) propyltrimethoxysilane followed by vinylbenzyl chloride and divinylbenzene to produce first thin monolithic monolayer. The second copolymer layer was formed on thin monolithic monolayer of the capillary by reversible addition-fragmentation transfer polymerization of N-phenylacrylamide and styrene. The key parameters including buffer pH value and organic modifier were systematically evaluated to provide the optimal chromatographic condition. The resultant OT-CEC columns were validated by separating a synthetic mixture of peptides and cytochrome C tryptic digest in capillary electrochromatography. The number of theoretical plates as high as 2.4 million per column was achieved for synthetic mixture peptides. In addition, the fabricated OT-CEC column also resolved more than 18 high-efficiency digestion peptides from a mixture containing tryptic digest of cytochrome C. The column to column and inter- to intraday repeatabilities of OT-CEC column through RSD% were found better than 3.0%, exhibiting satisfactory stability and repeatability of the two-layer deposited OT-CEC column. The results reveal that the open tubular capillary column modified with two-layer copolymer shows the great prospect for the separation of proteins in capillary electrochromatography.

Hydrophilic deep eutectic solvents modified phenolic resin as tailored adsorbent for the extraction and determination of levofloxacin and ciprofloxacin from milk.

A reliable and efficient method for the simultaneous extraction and determination of antibiotics of ciprofloxacin and levofloxacin from milk was developed with solid phase extraction based on tailored adsorbent materials of deep eutectic solvents modified phenolic resin (DES-R-SPE). Six types of polyhydric alcohol-based hydrophilic DESs were prepared to modify the phenolic resin with the compositions of 3-aminophenol as a functional monomer, glyoxylic acid as a crosslinker, and polyethylene glycol 6000 as a porogen. And the prepared DES-Rs showed better extraction capacities for the target analytes than the unmodified phenolic resin because of more hydrogen bonding and electrostatic interactions supplied by DESs. The choline chloride-glycerol-based resin (DES1-R) with the highest adsorption amounts was selected and the adsorption behavior of it was studied with static adsorption and the dynamic adsorption performance; the adsorption process followed Freundlich isotherm (R2 ≥ 0.9337) and pseudo-second-order (R2 ≥ 0.9951). The present DES1-R-SPE method showed good linear range from 0.5 to100 µg mL-1 (R2 ≥ 0.9998), good recoveries of spiked milk samples (LEV, 96.7%; CIP, 101.5%), and satisfied repeatability for intra-day and inter-day (LEV, RSD≤5.4%; CIP, RSD≤4.6%).

Imidazole-modified C6 -chitosan derivatives used to extract ß-sitosterol from edible oil samples with a microwave-assisted solid phase extraction method.

ß-Sitosterol is a major bioactive constituent in plants with potent anticancer effects against many human cancer cells, but its bioavailability and therapeutic efficacy are limited by its poor solubility in water. In this study, C6 -imidazole chitosan, C6 -1-methylimidazole chitosan, C6 -1-ethylimidazole chitosan, C6 -1-vinylimidazole chitosan, C6 -1-allylimidazole chitosan, and C6 -1-butylimidazole chitosan were prepared to extract ß-sitosterol from edible oil samples via ultrasonic-assisted solid liquid extraction. The structures and properties of the newly synthesized products were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and elemental analysis. The extraction abilities of the derivatives were tested in the experiment with high-performance liquid chromatography (limit of detection 0.21 µg/g and limit of quantification 0.67 µg/g), and the % relative standard deviation (<3.25%) and recovery values of the prepared chitosan derivatives toward ß-sitosterol (average: 100.20%) were acceptable. The spiked interday and intraday recoveries of ß-sitosterol were 102.60 ± 2.78 and 103.90 ± 3.04%, respectively. The actual amounts of ß-sitosterol extracted from three real samples using C6 -imidazole chitosan according to the solid phase extraction method were 3302.40, 901.70, and 2045.60 mg/kg for corn oil, olive oil, and pea oil, respectively.

Deep eutectic solvents cross-linked molecularly imprinted chitosan microsphere for the micro-solid phase extraction of p-hydroxybenzoic acid from pear rind.

A visual, rapid, and sensitive micro-solid phase extraction method was developed for the detection of p-hydroxybenzoic acid using molecularly imprinted chitosan microspheres based on deep eutectic solvents, both as a functional monomer and template. The parameters were optimized by using the response surface methodology strategy. The extraction capacity of p-hydroxybenzoic acid from pear rind under the optimized conditions using response surface methodology was 46.32 mg/g, when the pH of the extract solution (2), extraction time (35 min), extraction temperature (30°C), and adsorbent dosage (2 mg). The molecularly imprinted chitosan microspheres produced higher selectivity and extraction capacity than the traditional materials.

Preparation of levofloxacin-imprinted nanoparticles using designed deep eutectic solvents for the selective removal of levofloxacin pollutants from environmental waste water.

A deep eutectic solvent (DES) was prepared from choline chloride (ChCl) and methacrylic acid (MAA) and used as an eco-friendly surfactant and functional monomer. The process of producing DES and its free energy of formation (ΔG = -37.225 kcal mol-1) were evaluated theoretically by density-functional theory. The designed DES (ChCl-MAA) was introduced as a novel eco-friendly functional monomer (MAA as the control group) during the preparation of levofloxacin-imprinted nanoparticles (LINs) based on molecular imprinting technology. The nanoparticles were characterized using a range of techniques. The nanoparticles were applied as an adsorbing material to the selective removal of levofloxacin from environmental waste water. The selective removal and adsorption capacity of the adsorbing material were evaluated by high-performance liquid chromatography. Based on the introduction of DES, DES-LINs had better adsorption capacity for levofloxacin than common LINs. This method had the simple operation, rapid adsorption and efficient decontamination.

Deep eutectic solvents skeleton typed molecularly imprinted chitosan microsphere coated magnetic graphene oxide for solid-phase microextraction of chlorophenols from environmental water.

Novel molecularly imprinted chitosan microspheres were prepared on the surface of magnetic graphene oxide, with deep eutectic solvents both as a functional monomer and template. The prepared molecularly imprinted chitosan microspheres-magnetic graphene oxide was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller surface area, thermogravimetric analysis were subsequently combined with solid-phase micro-extraction for simultaneous separation and enrichment of the extraction of chlorophenols from environmental water. Factors affecting the extraction efficiency of chlorophenols were optimized using response surface methodology. The actual extraction capacities under the optimal conditions (liquid to solid ratio = 3, cycles of adsorption/desorption = 5, 40°C extraction temperature, and extraction time for 35 min) were 86.90 mg/g. Compared to the traditional materials, the molecularly imprinted chitosan microspheres-magnetic graphene oxide produced higher selectivity and extraction capacity.

Multi-phase extraction of ephedrine from Pinellia ternata and herbal medicine using molecular imprinted polymer coated ionic liquid-based silica.

INTRODUCTION: Ephedrine is a typical compound found in lots of plant species that is used in several medicines for the treatment of asthma and bronchitis. However, excess amounts are harmful to humans, so it needs to be removed. OBJECTIVE: This study developed a multi-phase extraction (MPE) method with a molecular imprinted polymer (MIP) coated ionic liquid (IL)-based silica (SiO2 @IL@MIP) to simultaneously extract and separate ephedrine from Pinellia ternata, 10 medicines, and urine samples. METHODS: IL was immobilized on silica. Subsequently, the IL was combined with the functional monomer, followed by the addition of the crosslinker and template. The resulting sorbent was applied to the MPE, and the extraction, washing and elution solvents were evaluated. RESULTS: Fourier-transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) confirmed the synthesis of SiO2 @IL@MIP. A maximum adsorption amount of 5.76 mg/g was obtained at 30°C at a neutral pH. In MPE, 10.00 mL of methanol could extract all the ephedrine from Pinellia ternata. The interference was removed by washing with 4.00 mL of water, ethanol, and acetonitrile. Finally, 8.00 mL of methanol/acetic acid (99:1, v/v) was applied as the elution solvent. The following were extracted: 5.50 µg/g of ephedrine from Pinellia ternata, 0.00-46.50 µg/g from the 10 herbal medicines, and 68.70-102.80 µg/mL in the urine samples. CONCLUSION: The proposed method was applied successfully to the simultaneously extraction and separation of ephedrine from plants and medicines. These results are expected to provide important data for the development of new methods for the separation and purification of bioactive compounds.

Solid-Phase Extraction of Catechins from Green Tea with Deep Eutectic Solvent Immobilized Magnetic Molybdenum Disulfide Molecularly Imprinted Polymer.

A type of molecular-imprinted polymer with magnetic molybdenum disulfide as a base and deep eutectic solvent as a functional monomer (Fe3O4@MoS2@DES-MIP) was prepared with surface molecular imprinting method. It was applied as the adsorbent for the selective recognition and separation of (+)-catechin, (-)-epicatechin, (-)-epigallocatechin, (-)-epicatechin gallate, and (-)-epigallocatechin gallate in green tea in the process of magnetic solid-phase extraction (MSPE) combined with high-performance liquid chromatography (HPLC). The structure of Fe3O4@MoS2@DES-MIP was characterized by Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The adsorption properties and selective recognition ability on (-)-epigallocatechin gallate and the other four structural analogues were examined and compared. The results show that the polymer has excellent selective recognition ability for (-)-epigallocatechin gallate, and its adsorption capacity was much higher than that of structural analogues. The Fe3O4@MoS2@DES-MIP not only has the special recognition ability to template a molecule, but also can be separated by magnets with high separation efficiency and can be used in MSPE.

Preparation and evaluation of a green solvent-based molecularly imprinted monolithic column for the recognition of proteins by high-performance liquid chromatography.

A protein-based molecularly imprinted monolithic column was synthesized based on ionic liquids (ILs) and deep eutectic solvents (DESs) in a stainless steel column (50 mm × 4.6 mm id). An IL (1-allyl-3-butylimidazolium Br) and acrylamide were used as dual monomers. Another type of IL (1,2-bis [N,N'-vinylimidazolium] ethane bis Br) and N,N'-methylenebisacrylamide were used as dual cross-linking agents, and the DES (choline chloride : ethylene glycol 1 : 2) was used as a porogen in the preparation of a monolithic polymer. Bovine serum albumin (BSA) and lysozyme (Lyz), which differ greatly in molecular size, isoelectric point, and charge, were selected for imprinting templates to evaluate the recognition property of the green solvent-based MIP monolithic column. Some important factors, such as template-monomer molar ratio, total monomer concentration, and cross-linking density, were investigated systematically. Under optimal conditions, the MIP monolithic column obtained showed higher binding affinity for the templates than its corresponding non-imprinted (NIP) monolithic column.

Preparation of two-dimensional magnetic molecularly imprinted polymers based on boron nitride and a deep eutectic solvent for the selective recognition of flavonoids.

New types of two-dimensional (2D) boron nitride (BN) were developed as a 2D scaffold material. After modification with ternary deep eutectic solvents (DES, ChCl-caffeic acid-ethylene glycol), the processed BN was applied to the preparation of magnetic molecularly imprinted polymers (MMIPs). In the polymerization of MMIPs, DESs and hydrophobic Fe3O4 magnetite were applied as the functional monomer and magnetically susceptible component, respectively. A 2D ellipsoid material was formed successfully by polymerization on the surface of the processed BN. The proposed 2D-MMIPs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and nitrogen sorption analysis techniques. The surface area of the 2D-MMIPs was increased using eco-friendly chemicals. The proposed 2D-MMIPs had a 2D oblate structure and a large surface area. The 2D-MMIPs were used for the preconcentration of flavonoids from Ginkgo biloba leaf extracts. High performance liquid chromatography-ultraviolet analysis revealed that the 2D-MMIPs have higher recoveries for the flavonoids (quercetin 96.8%, isorhamnetin 93.6% and kaempferol 94.8%) in Ginkgo biloba leaves than common MMIPs.

Synthesis and characterization of deep eutectic solvents (five hydrophilic and three hydrophobic), and hydrophobic application for microextraction of environmental water samples.

Hydrophilic and hydrophobic deep eutectic solvents (DESs) as "green" solvents were applied in this study for the microextraction of environmental samples. A series of DESs (five hydrophilic and three hydrophobic) were synthesized and characterized by Fourier transform infrared spectroscopy. Physicochemical property parameters of eight DESs including water solubility, density, conductivity, and freezing point were assessed. Compared with the performance of five hydrophilic DESs in water phase, the three hydrophobic DESs were more suitable for application in dispersive liquid-liquid microextraction for the determination of sulfonamides in water sample. In dispersive liquid-liquid microextraction process, analytical parameters including type and volume of extraction solvent, extraction time, and pH of water sample were investigated. Under optimum conditions, 60 µL of hydrophobic DESs was used for extraction for 2 min in pH = 7.0 sample. The linear ranges were 0.05-5.0 µg/mL for the four sulfonamides with the correlation coefficients in the range of 0.9991-0.9999. The limits of detection were in the range of 0.0005-0.0009 µg/mL and the limits of quantification were in the range of 0.0019-0.0033 µg/mL. The recoveries of the analytes of the proposed method for the spiked samples were 80.17-93.5%, with the relative standard deviation less than 6.31%. The results indicated that three hydrophobic DESs showed commendable performance for extraction of sulfonamides, and hydrophobic DES-based microextraction method was successfully applied for monitoring sulfonamides in water samples. Graphical abstract.

Application of amino-based chitosan cyclodextrin derivatives for the extraction of catechins in green tea with high-performance liquid chromatography.

Chitosan derivatives have been studied widely, but poor solubility in water restricts their applications. In this study, four types of amine-based chitosan derivatives were prepared and modified further with beta-cyclodextrin. The sequential microextraction of catechins ((+)-catechin and (-)-epigallocatechin gallate) from green tea powder by an optimized solid-phase extraction method using these four derivatives was investigated. The optimal conditions for the extraction of catechins were 60°C for a 40 min extraction period. The purity and amount of each catechin were determined by high-performance liquid chromatography. The different amines strengthened the extraction capacity of chitosan. Among the four types of amines, ethylene diamine grafted chitosan beta-cyclodextrin had the highest extraction capacity to catechins. Therefore, this material was used in the extraction assay, and the standard curves of (+)-catechin and (-)-epigallocatechin gallate were linear over the concentration range, 0.25-500 µg/mL, after assaying five data points in duplicate. Solid-phase extraction with the amino-based chitosan beta-cyclodextrin system is a new application of chitosan, which has potential applications in the extraction of bioactive compounds from plant materials or the removal of different impurities from specific extracts.

Simultaneous determination of levofloxacin and ciprofloxacin in human urine by ionic-liquid-based, dual-template molecularly imprinted coated graphene oxide monolithic solid-phase extraction.

A novel method was developed to simultaneously determine the ciprofloxacin and levofloxacin levels in human urine using an ionic-liquid-based, dual-molecularly imprinted polymer-coated graphene oxide solid-phase extraction monolithic column coupled with high-performance liquid chromatography. The molecularly imprinted monolithic column was prepared using ciprofloxacin and levofloxacin as templates, 1-vinyl-3-ethylimidazolium bromide as the functional monomer, and graphene oxide as the core material. The resulting imprinted monoliths were characterized by scanning electron microscopy and fourier transform-infrared spectroscopy. The efficiency and capacity of the ionic-liquid-based imprinted monolithic column were investigated by varying the synthesis conditions (ciprofloxacin/levofloxacin ratio and template/functional monomer/cross-linker ratio). The solid-phase extraction process was optimized by changing the washing and eluting conditions. The results suggested that the proposed ionic-liquid-based molecularly imprinted solid-phase extraction monolithic-high-performance liquid chromatography method could separate ciprofloxacin and levofloxacin efficiently and simultaneously from human urine. The mean recoveries of ciprofloxacin and levofloxacin ranged from 89.2 to 93.8 and 86.7 to 94.6%, respectively. The intra- and interday relative standard deviation ranged from 0.9 to 3.2 and 0.8 to 2.9%, respectively. Under the optimized conditions, the recoveries of ciprofloxacin and levofloxacin were more than 93.8%.

Isolation of aristolochic acid I from herbal plant using molecular imprinted polymer composited ionic liquid-based zeolitic imidazolate framework-67.

Aristolochic acid I is a toxic compound found in the genus of Aristolochia plants, which are commonly used as herbal cough treatment medicines. To remove the aristolochic acid I in extract efficiently and selectively, a molecularly imprinted polymer composed of ethylimidazole ionic liquid-based zeolitic imidazolate framework-67 was synthesized and used as the adsorbent. Under the conditions optimized by the software design expert, the sorbent showed highest adsorption amount of 34.25 mg/g in methanol/water (95:5, v/v) at 39°C for 138 min. The sorbent was then applied to solid phase extraction to isolate aristolochic acid I from the extract of the herbal plant Fibraurea Recisa Pierre. 0.043 mg/g of aristolochic acid I was obtained after the loading, washing, and elution processes. The limit of detection of 2.41 × 10-5  mg/mL and good recoveries provided evidence for the accuracy of this method.

Preparation of deep eutectic solvent-based hexagonal boron nitride-molecularly imprinted polymer nanoparticles for solid phase extraction of flavonoids.

Hexagonal boron nitride (h-BN) is introduced as a 2D scaffold during the preparation of molecularly imprinted polymers (MIPs). The MIPs were prepared from deep eutectic solvents (DES) or from DES containing h-BN, crosslinking agent (ethylene glycoldimethacrylate), initiator (AIBN), porogen (methanol), and template (quercetin). The recognition site of the monomer is protected by the hydrogen bond of the DES before the MIP is polymerized. The formation of the final MIP was analyzed theoretically using density-functional theory. The nanoparticles were characterized by scanning electron microscopy, nitrogen sorption analysis, thermogravimetry and Fourier transform infrared spectroscopy. The introduction of h-BN resulted in an increase in the surface area of the nanoparticles. They were applied as a solid phase extraction sorbent for the extraction of flavonoids (specifically of quercetin, isorhamnetin and kaempferol) from Ginkgo biloba leaves. Following extraction with ethanol, they were quantified by HPLC. The new sorbent has distinctly improved recognition capability for flavonoids compared to conventional MIP nanoparticles. Graphical abstractDeep eutectic solvent (DES)-based molecularly imprinted polymer (MIP) was polymerized on the surface of hexagonal boron nitride (h-BN). The h-BN-MIP nanoparticles were applied as a solid phase extraction sorbent for the specific recognition of flavonoids.

Application of Natural Deep Eutectic Solvents in the Extraction of Quercetin from Vegetables.

Quercetin is a phytochemical with disease prevention and health promotion activities that has attracted significant research attention. In this study, choline chloride and betaine-based natural deep eutectic solvents were prepared using a heating method. Their physical and chemical properties were also tested. Then, they were applied to extract quercetin from onion and broccoli with ultrasonic-assisted solid liquid method coupled with HPLC. Three factors (temperature, amount, and time) were considered for the optimization of the extraction assays. In the optimal conditions, the extraction recoveries were 88.91-98.99%, 88.45-99.01%, and 89.56-98.74% for quercetin, isorhamnetin, and kaempferol. Tailor-made natural deep eutectic solvents could be applied as sustainable and safe extraction media for biochemical applications.

Molecular imprinted polymers based on magnetic chitosan with different deep eutectic solvent monomers for the selective separation of catechins in black tea.

Two types of molecular-imprinted polymers-based magnetic chitosan with facile deep eutectic solvent-functional monomers (Fe3 O4 -CTS@DES-MIPs) were synthesized and applied as adsorbents in magnetic solid-phase extraction (MSPE) for the selective recognition and separation of (+)-catechin, (-)-epicatechin, and (-)-epigallocatechin gallate in black tea. The obtained Fe3 O4 -CTS@DES-MIPs were characterized by Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The selective recognition ability was examined by adsorption experiments. The actual amounts of (+)-catechin, (-)-epicatechin, and (-)-epigallocatechin gallate extracted from black tea using Fe3 O4 -CTS@DES-MIPs by the MSPE method were 13.10, 6.32, and 8.76 mg/g, respectively. In addition, the magnetic Fe3 O4 -CTS@DES-MIPs showed outstanding recognition and selectivity. Therefore, it can be used to separate bioactive compounds from black tea. The new-type of DES adopted as the functional monomer in this paper provides a new perspective for the recognition and separation of bioactive compounds.