Promoting capillary microextraction of six organic nitrogen pesticides in water samples using versatile ZIF-8 hybrid monolithic column.

Because of rapid industrialization and agriculturalization, solving the pressing problems of environment pollution, especially water and food quality, requires innovative solutions. In this paper, a novel and versatile metal-organic framework (ZIF-8)-hybrid monolithic column (ZIF-HMC) was prepared for in-tube solid-phase microextraction (IT-SPME) of organic nitrogen pesticides (ONPs). The prepared monolithic columns had superior adsorption sites, high porosity, excellent permeability, and ideal specific surface area based on Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Thermal Field Emission Scanning Electron Microscopy (SEM), Energy Dispersive Spectrometry (EDS), X-ray Photoelectron Spectroscopy (XPS), and N2 adsorption-desorption. The ZIF-HMC contained a large number of nitrogen and oxygen atoms, benzene rings and ZIF-8, which could synergistically promote the adsorption efficiency of ONPs through multiple interactions, such as hydrogen bonding, π-π accumulation, hydrophobic interactions, cation-π interactions, and pore adsorption by MOFs. Under the optimal conditions, a simple, efficient, and sensitive method for the analysis of six organic pesticides in environmental water samples was developed by using the ZIF-HMC as the extraction medium coupled with high performance liquid chromatography-ultraviolet (HPLC-UV). The method had a wide linear range (0.63-1000 µg L-1), a low detection limit (0.19-1.91 µg L-1) and satisfactory recoveries (87.4 %-110.2 %), the linear correlation coefficient was (R2) 0.9972-0.9995 and the relative standard deviation (RSD) was less than 2.64 %. The study had demonstrated the potential application of the developed method for the enrichment and analysis of organic pesticides in complex matrices of environmental samples, as well as the feasibility of MOFs materials for IT-SPME sample preparation.

Forming Homogeneous Three-Dimensional Structures from Discrete Silica Microspheres Using Sub/Supercritical Water.

A novel technique for producing highly uniform structures from silica microspheres has been developed and tested. It is based on exploiting the temperature- and pressure-dependent solvent properties of sub/supercritical water toward silicon dioxide. The initial concept aimed to create a "hybrid" capillary chromatographic column on the border between a packed and a monolithic column that would combine the benefits of both. The resultant method that integrates dissolution and coalescence in a continuous process enabled the production of a range of permeable columns with high efficiency and varying sizes. Their internal structures were examined using scanning electron microscopy and characterized using microHPLC chromatography. The structures produced using this method may have diverse applications beyond the scope of analytical chemistry. They prove useful in scenarios where high pressure is necessary because of the high hydraulic resistance of small particles and/or the passing medium with a high flow rate. A simple test of a bridged-microsphere monolithic column and a discrete microsphere-packed column, both after chemical modification to the C18 stationary phase, indicated superior performance of the new type of monolithic columns.

Polymeric monolithic columns based on natural wood for rapid purification of targeted protein.

With multiscale hierarchical structure, wood is suitable for a range of high-value applications, especially as a chromatographic matrix. Here, we have aimed to provide a weak anion-exchange polymeric monolithic column based on natural wood with high permeability and stability for effectively separating the targeted protein. The wood-polymeric monolithic column was synthesized by in situ polymerization of glycidyl methacrylate and ethylene glycol dimethacrylate in wood, and coupled with diethylaminoethyl hydrochloride. The wood-polymeric monolithic column can be integrated with fast-protein liquid chromatography for large-scale protein purification. According to the results, the wood-polymeric monolithic column showed high hydrophilicity, permeability and stability. Separation experiments verified that the wood-polymeric monolithic column could purify the targeted protein (spike protein of SARS-COV-2 and ovalbumin) from the mixed proteins by ion exchange, and the static adsorption capacity was 33.04 mg mL-1 and the dynamic adsorption capacity was 24.51 mg mL-1. In addition, the wood-polymerized monolithic column had good stability, and a negligible decrease in the dynamic adsorption capacity after 20 cycles. This wood-polymerized monolithic column can provide a novel, efficient, and green matrix for monolithic chromatographic columns.

A new approach towards highly sensitive detection of endogenous N-acetylaspartic acid, N-acetylglutamic acid, and N-acetylaspartylglutamic acid in brain tissues based on strong anion exchange monolith microextraction coupled with UHPLC-MS/MS.

A novel in-tube solid-phase microextraction coupled with an ultra-high performance liquid chromatography-mass spectrometry method has been established for simultaneous quantification of three crucial brain biomarkers N-acetylaspartic acid (NAA), N-acetylglutamic acid (NAG), and N-acetylaspartylglutamic acid (NAAG). A polymer monolith with quaternary ammonium as the functional group was designed and exhibited efficient enrichment of target analytes through strong anion exchange interaction. Under the optimized conditions, the proposed method displayed wide linear ranges (0.1-80 nM for NAA and NAG, 0.2-160 nM for NAAG) with good precision (RSDs were lower than 15%) and low limits of detection (0.019-0.052 nM), which is by far the most sensitive approach for NAA, NAG, and NAAG determination. Furthermore, this approach has been applied to measure the target analytes in mouse brain samples, and endogenous NAA, NAG, and NAAG were successfully detected and quantified from only around 5 mg of cerebral cortex, cerebellum, and hippocampus. Compared with existing methods, the newly developed method in the current study provides highest sensitivity and lowest sample consumption for NAA, NAG, and NAAG measurements, which would potentially be utilized in determining and tracking these meaningful brain biomarkers in diseases or treatment processes, benefiting the investigations of pathophysiology and treatment of brain disorders.

Quantitative determination of amphetamine-type stimulants in sewage and urine by hybrid monolithic column solid-phase microextraction coupled with UPLC-QTRAP MS/MS.

A needle-solid-phase microextraction (SPME) method based on hybrid monolithic column (HMC) was proposed for simultaneous separation and extraction of seven amphetamine-type stimulants (ATSs) (amphetamine, methamphetamine, cathinone, methcathinone, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, and 3,4-methylenedioxyethylamphetamine), combining with ultra-performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometer (UPLC-QTRAP MS/MS). Thiol functionalized HMC (T-HMC) showed high extraction efficiency and excellent elution results towards target analytes, among three kinds of single/bi-functionalized HMCs. Various parameters of SPME operation and analytical performance were investigated systematically. The adsorption mechanism of T-HMC to ATSs was also discussed and explained as a mixed mode of electrostatic and hydrophobic interactions. Under the optimum experimental conditions, the proposed T-HMC needle-SPME-UPLC-QTRAP MS/MS method was rapid and convenient with good accuracy, low sample consumption, high sensitivity and strong anti-interference ability. This method was successfully applied to quantitative determination of seven trace ATSs in complex sewage and urine samples. In view of abundant types of HMCs, the needle-SPME based on functional HMC also had the potential to selectively separating and enriching other tract new psychoactive substances in complex matrices, and could provide a reliable tool for drug monitoring, especially in applications for forensic analysis and drug abuse.

Continuous-Flow System for Methylene Blue Removal Using a Green and Cost-Effective Starch Single-Rod Column.

A continuous-flow system based on a green and cost-effective monolithic starch cryogel column was successfully developed for removing methylene blue (MB). The proposed column exhibited high removal efficiency (up to 99.9%) and adsorption capacity (25.4 mg·g-1) for synthetic and real samples with an adsorbent cost of USD 0.02. The influence of various operation parameters, including the flow rate, initial concentration, column height, and temperature, on the MB removal efficiency was examined and reported. The MB removal efficiency remained >99% in the presence of potential interferences, highlighting the good performance of the cryogel column. The Yoon-Nelson dynamic model explained the MB adsorption better than the Bohart-Adams model, as indicated by the higher R2 values (R2 = 0.9890-0.9999) exhibited by the former and current trends of its parameters. The MB removal efficiency of the cryogel column remained at 62.7% after three reuse cycles. The wastewater containing MB collected from a local batik-production community enterprise in Phuket, Thailand was applied to the proposed continuous-flow system under optimum conditions, and results indicated that 99.7% of the MB present in 2.4 L of wastewater was removed. These results validate the excellent application potential of the cryogel column for the continuous-flow adsorption of MB. This study will facilitate future industrial applications and process designs of the continuous-flow system.

Emerging Developments in Separation Techniques and Analysis of Chiral Pharmaceuticals.

Chiral separation, the process of isolating enantiomers from a racemic mixture, holds paramount importance in diverse scientific disciplines. Using chiral separation methods like chromatography and electrophoresis, enantiomers can be isolated and characterized. This study emphasizes the significance of chiral separation in drug development, quality control, environmental analysis, and chemical synthesis, facilitating improved therapeutic outcomes, regulatory compliance, and enhanced industrial processes. Capillary electrophoresis (CE) has emerged as a powerful technique for the analysis of chiral drugs. This review also highlights the significance of CE in chiral drug analysis, emphasizing its high separation efficiency, rapid analysis times, and compatibility with other detection techniques. High-performance liquid chromatography (HPLC) has become a vital technique for chiral drugs analysis. Through the utilization of a chiral stationary phase, HPLC separates enantiomers based on their differential interactions, allowing for the quantification of individual enantiomeric concentrations. This study also emphasizes the significance of HPLC in chiral drug analysis, highlighting its excellent resolution, sensitivity, and applicability. The resolution and enantiomeric analysis of nonsteroidal anti-inflammatory drugs (NSAIDs) hold great importance due to their chiral nature and potential variations in pharmacological effects. Several studies have emphasized the significance of resolving and analyzing the enantiomers of NSAIDs. Enantiomeric analysis provides critical insights into the pharmacokinetics, pharmacodynamics, and potential interactions of NSAIDs, aiding in drug design, optimization, and personalized medicine for improved therapeutic outcomes and patient safety. Microfluidics systems have revolutionized chiral separation, offering miniaturization, precise fluid control, and high throughput. Integration of microscale channels and techniques provides a promising platform for on-chip chiral analysis in pharmaceuticals and analytical chemistry. Their applications in techniques such as high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) offer improved resolution and faster analysis times, making them valuable tools for enantiomeric analysis in pharmaceutical, environmental, and biomedical research.

Removal of amoxicillin via chromatographic monolithic columns: comparison between batch and continuous fixed bed.

This study presented a hydrophobic interaction-based poly(HEMA-MATrp) monolithic chromatographic column (MCC) to remove amoxicillin from aqueous solutions. In addition to their porous structure, monolithic-filled columns offer superior properties without loss of performance, which is one of the points that make them unique. The specific surface area of the monolithic column synthesized by the bulk polymerization of 2-hydroxyethyl methacrylate and N-Methacryloyl-L-tryptophan. Also, poly(HEMA-MATrp) MCC has been characterized via FTIR, SEM, and elemental analysis. According to BET analysis, the specific surface area of the poly(HEMA-MATrp) monolithic chromatographic column (MCC) is 14.2 mg/g. The adsorption and desorption of amoxicillin in an aqueous solution were investigated comparatively in both continuous fixed bed and batch adsorption. The highest adsorption value of amoxicillin was determined at pH 7 in the presence of PBS as 62.11 mg/g. The appropriate adsorption isotherm for the adsorption of amoxicillin was Langmuir, and the reaction kinetics was pseudo-second-order. No significant loss was observed for the adsorption capacity of poly(HEMA-MATrp) MCC after the 5 cycles of adsorption-desorption studies. Also, the loss for the adsorption capacity of the monolithic column is just %5.2 after 6-month storage, proving the reusability and storability of the monolithic column.

Three-dimensional porous wood monolithic columns for efficient purification of spike glycoprotein of SARS-CoV-2.

Considerable research has been devoted to finding a cost-effective chromatographic matrix with efficient adsorption and high throughput. Wood exhibits complex micro-network structures that make it a powerful contender for a novel environment-friendly chromatographic matrix material. We demonstrate a novel strategy to manufacture a wood monolithic column, which chemically modified the wood and imported diethyl aminoethyl, diethylamine, and amino groups. This wood monolithic column can maintain fully monolithic column performances and highly selective to spike glycoprotein of SARS-CoV-2 by ion exchange force. The wood monolithic column was evaluated by static adsorption, dynamic adsorption, and frontal analysis. The results showed that the static adsorption capacity of the wood monolithic column with 2-diethylaminoethylchloride hydrochloride for bovine serum albumin was 14.72 mg/g, and the adsorption process was chemisorption. In addition, it retained 80 % adsorption capacity after 110 repeated adsorption-elution cycles.

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.

Chemiluminescence Biosensor for the Determination of Cardiac Troponin I (cTnI).

Cardiac vascular diseases, especially acute myocardial infarction (AMI), are one of the leading causes of death worldwide. Therefore cardio-specific biomarkers such as cardiac troponin I (cTnI) play an essential role in the field of diagnostics. In order to enable rapid and accurate measurement of cTnI with the potential of online measurements, a chemiluminescence-based immunosensor is presented as a proof of concept. A flow cell was designed and combined with a sensitive CMOS camera allowing sensitive optical readout. In addition, a microfluidic setup was established, which achieved selective and quasi-online cTnI determination within ten minutes. The sensor was tested with recombinant cTnI in phosphate buffer and demonstrated cTnI measurements in the concentration range of 2-25 µg/L. With the optimized system, a limit of detection (LoD) of 0.6 µg/L (23 pmol/L) was achieved. Furthermore, the selectivity of the immunosensor was investigated with other recombinant proteins, such as cTnT, and cTnC, at a level of 16 µg/L. No cross-reactivity could be observed. Measurements with diluted blood plasma and serum resulted in an LoD of 60 µg/L (2.4 nmol/L) and 70 µg/L (2.9 nmol/L), respectively.

Methacrylate bonded covalent organic framework monolithic column online coupling with high-performance liquid chromatography for analysis of trace estrogens in food.

Covalent organic frameworks (COFs) are a burgeoning class of crystalline porous materials with unique properties and have been considered as a promising functional extraction medium in sample pretreatment. In this study, a new methacrylate-bonded COF (TpTh-MA) was well designed and synthesized via the aldehyde-amine condensation reaction, and the TpTh-MA was incorporated into poly (ethylene dimethacrylate) porous monolith by a facile polymerization reaction inside capillary to prepare a novel TpTh-MA monolithic column. The fabricated TpTh-MA monolithic column was characterized with scanning electron microscope, Fourier transform infrared spectrometer, X-ray diffraction, and N2 adsorption-desorption experiments. Then, the homogeneous porous structure, good permeability and high mechanical stability of TpTh-MA monolithic column was used as separation and enrichment media of capillary microextraction, which was coupled with high-performance liquid chromatography fluorescence detection for online enrichment and analysis of trace estrogens. The main experimental parameters influencing the extraction efficiency were systematically investigated. The adsorption mechanism for three estrogens was also explored and discussed based on hydrophobic effect, π-π affinity and hydrogen bonding interaction, which contributed to its strong recognition affinity to target compounds. The enrichment factors of the TpTh-MA monolithic column micro extraction method for the three estrogens were 107-114, indicating a significant preconcentration ability. Under optimal conditions, a new online analysis method was developed and exhibited good sensitivity and wide linearity range of 0.25-100.0 µg·L-1 with a coefficient of determination (R2) higher than 0.9990 and a low limit of detection with 0.05-0.07 µg·L-1. The method was successfully applied for online analysis of three estrogens of milk and shrimp samples and the recoveries obtained from spiking experiments were in range of 81.4-113% and 77.9-111%, with the relative standard deviations of 2.6-7.9% and 2.1-8.3% (n = 5), respectively. The results revealed the great potential for the application of the COFs-bonded monolithic column in the field of sample pretreatment.

A benzenesulfonic acid-modified organic polymer monolithic column with reversed-phase/hydrophilic bifunctional selectivity for capillary electrochromatography.

Here, a styrene-based polymer monolithic column poly(VBS-co-TAT-co-AHM) with reversed-phase/hydrophilic interaction liquid chromatography (RPLC/HILIC) bifunctional separation mode was successfully prepared for capillary electrochromatography by the in situ polymerization of sodium p-styrene sulfonate (VBS) with cross-linkers 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) and 1,3,5-triacryloylhexahydro-1,3,5-triazine (TAT). The preparation conditions of the monolith were optimized. The morphology and formation of the poly(VBS-co-TAT-co-AHM) monolith were confirmed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). The separation performances of the monolith were evaluated systematically. It should be noted that the incorporation of VBS functional monomer can provide π-π interactions, hydrophilic interactions, and ion-exchange interactions. Hence, the prepared poly(VBS-co-TAT-co-AHM) monolith can achieve efficient separation of thiourea compounds, benzene series, phenol compounds, aniline compounds and sulfonamides in RPLC or HILIC separation mode. The largest theoretical plate number for N,N'-dimethylthiourea reached 1.7 × 105 plates/m. In addition, the poly(VBS-co-TAT-co-AHM) monolithic column showed excellent reproducibility and stability. This novel monolithic column has great application value and potential in capillary electrochromatography (CEC).

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.

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.

Preparation of poly(N-vinylpyrrolidone-co-pentaerythritol triacrylate) monolithic column for hydrophilic interaction chromatography.

A method for the preparation of poly(N-vinylpyrrolidone-co-pentaerythritol triacrylate copolymerization)-based monolithic capillary column was reported for the separation of polar small molecular weight compounds with nano-liquid chromatography in hydrophilic interaction chromatography mode. The monolithic columns were prepared by in situ copolymerization of N-vinylpyrrolidone and a cross-linker pentaerythritol triacrylate in a binary porogenic agent consisting of methanol and water. The composition of the polymerization solution was systematically optimized in terms of column permeability, theoretical plate number, asymmetric factor, and retention factor. A typical hydrophilic chromatography retention mechanism was observed with a mobile phase composed of a high content of organic solvent. The preparation method is simple and robust, the precursor N-vinylpyrrolidone is chemically stable, cheap, and easily available. The N-vinylpyrrolidone-based hydrophilic interaction chromatography stationary phase displays satisfactory separation selectivity for a range of polar test analytes, including benzoic acid derivatives, nucleosides, and phenols.

Fabrication and application of Zn5 functionalized copolymer monolithic column for pipette tip micro-solid phase extraction of 4 polycyclic aromatic hydrocarbons in edible oil.

The contamination of polycyclic aromatic hydrocarbons (PAHs) in edible oil is a health threat. Thus, trace analysis of PAHs is of high necessity. Based on the efficient adsorption of PAHs on Zn5 metal cluster, a Zn5 functionalized copolymer monolithic column was rationally designed for pipette tip micro-solid phase extraction (µ-SPE). The modified Zn5 improved the adsorption selectivity and capacity of the monolith for naphthalene, phenanthrene, fluoranthene and pyrene. Chemical doping and copolymerization stabilized the monolith with a long life. Under optimal extraction conditions, a µ-SPE-high performance liquid chromatography with ultraviolet detector method was established for the detection of 4 PAHs in edible oils. The method yielded detection ranges of 0.15-250 µg L-1 (R2 > 0.997), detection limits of 0.050-1.5 µg L-1, satisfactory recoveries (86.3-101.5 %), and high precisions (RSDs < 7.9 %). The results indicated that the Zn5 functionalized copolymer monolithic column was an ideal separation medium for the detection of PAHs residues in edible oils.

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.

N, N'-methylene bisacrylamide/divinyl benzene based-highly cross-linked hybrid monolithic column: Production and its applications for powerful capture of four chlorophenols.

In this paper, the role of the halogen bond in capillary monolithic column microextraction was explored for the first time. Benzene-1,3,5-tricarbohydrazide (BTH) was synthesized as a functional monomer, N, N'-methylene bisacrylamide (MBA) and divinyl benzene (DVB) were used as cross-linking agents, the hybrid monolithic column of poly (BTH-co-DVB-co-MBA) was prepared using methanol and polyethylene glycol as pore-forming agents and azodiisobutyronitrile as the initiator. Due to the existence of BTH, a large number of nitrogen atoms (Lewis base) were introduced into the monolithic column, which could form a halogen bond with chlorine-containing organic pollutants and enhance its adsorption performance. Based on the monolithic column, a sensitive and environment-friendly solid-phase microextraction technology was studied. The monolithic column was integrated with high-performance liquid chromatography (HPLC) to extract and detect four kinds of chlorophenol in real water samples. Under best conditions, the method showed excellent extraction ability and linearity, with a linear correlation coefficient of 0.9958-0.9987, a low detection limit (LOD) of 0.04-0.23 µg L-1 (S/N = 3), and relative standard deviation (RSD) less than 3.09%. The recovery rate was kept between 87.30% and 123.00%, and the RSD was less than 3.83%, which indicated that the column had powerful capture performance, high precision, and strong anti-matrix interference ability in the real sample, and had potential application value in practical work.

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.