Carboxyl-functionalized covalent organic frameworks for the extraction of malachite green and crystal violet in environmental water samples prior to quantification by high-performance liquid chromatography.

In this study, monodisperse, uniform, and spherical covalent organic frameworks (COFs) were synthesized using 1,3,5-tris (4-aminophenyl) benzene and 1,3,5-tricarboxaldehyde benzene at room temperature. Post-modification of 6-aminocaproic acid on the COFs yielded carboxyl-modified COFs (COFs-COOH). The modification enhanced the hydrophilicity and adsorption efficiencies of COFs-COOH for malachite green (MG) and crystal violet (CV). A COFs-COOH-based dispersive solid-phase extraction coupled with high-performance liquid chromatography was developed for the analysis of MG and CV. The method showed a linear range from 10 to 1000 ng/mL with detection limits of 1.82 and 0.70 ng/mL for MG and CV detection, respectively. The recoveries of MG and CV from water samples collected from fish farms and markets ranged from 91.63% to 107.10% with relative standard deviations below 5%. Reproducibility tests demonstrated that the adsorption efficiencies of COFs-COOH were maintained at above 85.86% over 15 cycles. The study verified the potential of COFs-COOH as sorbents for the enrichment and separation of triphenylmethane dyes from complex samples.

Controlled synthesis of sulfhydryl-dendritic mesoporous silica nanospheres for ultrafast extraction and sensitive analysis of organochlorine herbicides containing amide groups.

The distinctive morphology of dendritic mesoporous silica nanoparticles (DMSN) has recently attracted considerable attention in scientific community. However, synthesis of DMSN with well-defined structure and uniform size for ultrafast extraction of trace herbicide residues from environmental and food samples remains to be a compelling challenge. In this study, sulfhydryl functionalized dendritic mesoporous silica (SH-DMSN) was synthesized and the SH-DMSN showcases monodisperse microspheres with flower shape and precisely tailored and controllable pore sizes. This distinctive structural configuration accelerates mass transfer within the silica layer, resulting in heightened adsorption efficiencies. Furthermore, the particle sizes (455, 765, and 808) of the adsorbent can be meticulously fine-tuned by introducing distinct templates. Specifically, when the particle size is 765 nm, the optimized SH-DMSN exhibits a substantial specific surface area (691.32 m²/g), outstanding adsorption efficiencies (>90 %), remarkably swift adsorption and desorption kinetics (2 min and 3 min, respectively), and exceptional stability. The superior adsorption capabilities of this novel adsorbent, ranging from 481.65 to 1021.7 µg/g for organochlorine herbicides containing amide groups, can be attributed to the interplay of S-π interactions, halogen bonding, and electrostatic attraction interaction. These interactions involve the lone pair electrons of sulfhydryl and silanol groups with the π-electrons, halogen atoms and amide groups in herbicide molecules. This study not only offers a new perspective on advancing the practical utilization of dendritic mesoporous silica but also provides a pragmatic strategy for the separation and analysis of herbicides in diverse sample matrices.

Controllable synthesis of uniform flower-shaped covalent organic framework microspheres as absorbent for solid-phase extraction of trace 2,4-dichlorophenol.

Controllable synthesis of micro-flower covalent organic frameworks (MFCOFs) with controllable size, monodisperse, spherical, and beautiful flower shape was realized by using 2,5-diformylfuran (DFF) and p-phenylenediamine (p-PDA) as building blocks at room temperature. High-quality MFCOFs (5 - 7 µm) were synthesized by controlling the kind of solvent, amounts of monomers, catalyst content, and reaction time. The synthesized MFCOFs possessed uniform mesopores deriving from the intrinsic pores of frameworks and wide-distributed pores belonging to the gap between the petals. The MFCOFs-packed solid-phase extraction (SPE) column shows adsorption capacity of about 8.85 mg g-1 for 2,4-dichlorophenol (2,4-DCP). The MFCOF-based SPE combined with the HPLC method was established for the determination of 2,4-DCP in environmental water. The linear range of this method is 20-1000 ng mL-1 (R2 > 0.9994), and limit of detection (S/N = 3) is 10.9 ng mL-1. Spiked recoveries were 94.3-98.5% with relative standard deviations lower than 2.3%.

Magnetic porous carbon material derived from imine-linked covalent organic frameworks for magnetic solid phase extraction of trace chlorine-containing herbicides in soil.

Here, imine-linked covalent organic frameworks coated Fe3O4 microspheres were fabricated and employed as the self-template to prepare magnetic porous carbon material. The magnetic solid phase extraction (MSPE) performance of such magnetic covalent organic frameworks derived porous carbons (CMCOFs) were studied for the first time, and the improved MSPE performance was verified. The variations of chemical and material properties in the carbonization processes were studied, and it was found that the CMCOFs carbonated at 400°C exhibited highest adsorption efficiencies for chlorine-containing herbicides due to the formation of nitrile components at this stage. The CMCOFs retained high adsorption efficiencies (above 90 %) to chlorine-containing herbicides at wide pH range (3-12) and high salt concentration. The CMCOFs-based MSPE coupled with HPLC technique was in good potential for analysis of trace chlorine-containing herbicides in soil samples. Under the optimized conditions, this approach displayed short extraction and elution time (5 and 8 min) and low limits of detection (0.35-5.5 ng/mL) for chlorine-containing herbicides. The recoveries of spiked analytes and the relative standard deviations in real soil samples were 81.86 %-110.9 % and less than 5.92 %, respectively. This study provides an efficient method for the analysis of trace chlorine-containing herbicides in complex samples, as well as give some inspiration on material modulation by controlled carbonization to achieve improved sorption performances.

Amphiphilic polymers facilitated solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for direct extraction and analysis of zearalenone and zearalanone in corn juice samples.

In this work, amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions are demonstrated to be capable of direct extracting zearalenone and zearalanone in samples consisting of an oil-water emulsion system. Under optimal conditions, the maximum adsorption capacities for zearalenone and zearalanone are 17.27 and 13.26 mg/g. The adsorption is mainly attributed to π-π interaction, hydrophobic interaction, and hydrogen-bonding interaction for zearalenone and zearalanone. The adsorption isotherms reveal that the adsorption of zearalenone and zearalanone on amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions follows Freundlich model with multilayer and heterogeneous adsorption due to the presence of multiple kinds of adsorption sites. The relative recoveries of the spiked zearalenone and zearalanone in corn juice samples range from 85% to 93% with relative standard deviations lower than 3.52%. The results manifest the high efficiency of amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions for the adsorption and separation of analytes in the oil-water emulsion system. This study provides a new perspective on adsorbent engineering for the adsorption application in heterogeneous media.

Porous capillary monolithic column coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry for fast and effective separation and determination of estrogens.

In this work, a porous capillary monolithic column was simply prepared by in situ thiol-alkyne click polymerization of dipentaerythritol hexakis (3-mercaptopropionate) and dimethyl dipropargylmalonate in fused-silica capillary. The capillary monolithic column shows excellent permeability, high porosity, and thoiether-rich groups, thereby, a high-efficient capacity for trace estrogens from complex samples are obtained via electron-donor-acceptor π-π interaction and hydrophobic interaction. The highest adsorption efficiency for estrogens is achieved at pH = 7.0 with a flow rate of 0.200 mL min-1. The superior adsorption capacities of the as-prepared capillary column for eight estrogens range from 0.092 mg m-1 to 0.31 mg m-1. A simple, reliable, and sensitive method for the determination of eight estrogens in biological and environmental samples is developed using the monolithic polymer as in-tube solid-phase microextraction coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry (SPME-UPLC-MS/MS), and the total instrumental analysis time for the SPME-UPLC-MS/MS procedures was about 60 min per sample. The developed method shows a wide linear range (0.0500-5.00 µg L-1), and low limits of detection (5.34-9.63 ng L-1) for estrogens. The concentrations of estrogens in serum, urine, and pond water samples are found to be no more than 3.69, 0.741, and 1.04 µg L-1, respectively, and the satisfying recoveries for the eight estrogens range from 80.3% to 113% with relative standard deviations (n = 5) of 1.5-9.4%. The established method is highly potential for extraction and analysis of ultratrace target estrogens in complex matrices, such as biological and environmental samples.

Magnetic phenolic resin core-shell structure derived carbon microspheres for ultrafast magnetic solid-phase extraction of triazine herbicides.

In this study, monodisperse magnetic carbon microspheres were successfully synthesized through the carbonization of phenolic resin encapsulated Fe3 O4 core-shell structures. The magnetic carbon microspheres showed high performance in ultrafast extraction and separation of trace triazine herbicides from environmental water samples. Under optimized conditions, both the adsorption and desorption processes could be achieved in 2 min, and the maximum adsorption capacity for simazine and prometryn were 387.6 and 448.5 µg/g. Coupled with high-performance liquid chromatography-ultraviolet detection technology, the detection limit of triazine herbicides was in the range of 0.30-0.41 ng/mL. The mean recoveries ranged from 81.44 to 91.03% with relative standard deviations lower than 7.47%. The excellent magnetic solid-phase extraction performance indicates that magnetic carbon microspheres are promising candidate adsorbents for the fast analysis of environmental contaminants.

Wettability tunable metal organic framework functionalized high internal phase emulsion porous monoliths for fast solid-phase extraction and sensitive analysis of hydrophilic heterocyclic amines.

Surface wettability greatly influences the adsorptive, catalytic, and diffuse performances of a porous material. To realize the improved adsorption performance to hydrophilic heterocyclic amines (HAs), polymeric high internal phase emulsions (polyHIPEs) that can be tuned from hydrophobic to hydrophilic is synthesized by facilely regulating the amount of metal organic frameworks (MOFs). The water contact angle of the MOFs and polyHIPEs hybrids (MOFs@polyHIPEs) decreases from 133° to 0° as the amount of amide-modified MOFs increases from 0% to 10%. The hydrophilization of divinybenzene (DVB) based polyHIPEs by MOFs hybridization significantly enhances their adsorption performance and enables them to be suitable for the solid phase extraction (SPE) of hydrophilic HAs. Under the optimized conditions, the MOFs@polyHIPEs achieve adsorption capacities ranging from 42.89 to 86.71 µg/g for HAs through the π-π interaction and hydrogen bonding. The adsorption follows the pseudo-second-order kinetic model, and the nitrogen atoms in/on the imidazole ring are identified as the active adsorption sites for hydrogen bonding. This SPE method, along with HPLC-MS detection, provides detection limits of HAs as low as 0.00020-0.00040 ng/mL. This work offers a feasible strategy in tuning the surface wettability of polyHIPEs without post-modification to achieve high-efficiency enrichment and analysis of HAs.

Aptamer functionalized and reduced graphene oxide hybridized porous polymers SPE coupled with LC-MS for adsorption and detection of human α-thrombin.

In this study, reduced graphene oxide (rGO) hybridized high internal phase emulsions were developed and polymerized as porous carriers for aptamer (5'/5AmMC6/-AGT CCG TGG TAG GGC AGG TTG GGG TGA CT-3') modification to enrich human α-thrombin from serum. The structure and properties of the materials were confirmed by scanning electron microscope (SEM), Fourier transform infrared spectroscope (FT-IR), and X-ray photoelectron spectra (XPS). The adsorption ability and selectivity were studied and the thrombin was detected with liquid chromatography-mass spectrometry (LC-MS). The adsorption of thrombin onto the sorbent was achieved within 30 min and the desorption was realized using 5.0 mL of acetonitrile/water (80/20, v/v). The thrombin was quantified by LC-MS according to its characteristic peptide sequence of ELLESYIDGR.

Electrospun graphene oxide/MIL-101(Fe)/poly(acrylonitrile-co-maleic acid) nanofiber: A high-efficient and reusable integrated photocatalytic adsorbents for removal of dye pollutant from water samples.

The electrospun graphene oxide/MIL-101(Fe)/poly(acrylonitrile-co-maleic acid) nanofibers (E-spun GO/MIL-101(Fe)/PANCMA NFs) were fabricated by a facile electrospinning method and used as integrated photocatalytic adsorbents (IPAs) to remove dye pollutant from water samples. Compared with E-spun GO/PANCMA and E-spun MIL-101(Fe)/PANCMA NFs, the fabricated E-spun GO/MIL-101(Fe)/PANCMA NFs exhibited higher adsorption ability and excellent photocatalytic activity towards a model pollutant Rhodamine B (RhB). Under the optimized conditions, the as-prepared IPAs achieved almost complete adsorption of RhB within 15 min with the maximum adsorption capacity of 10.46 mg/g. Under visible-light irradiation, 93.7% of RhB in 20 mL water sample was degraded within 20 min, and the degradation kinetics of RhB fitted well with the first-order kinetic model. In addition, LC-MS analysis of the RhB degradation products confirmed the degradation pathways, and the generated •OH radicals played important roles in the degradation process. Importantly, the E-spun GO/MIL-101(Fe)/PANCMA NFs exhibited good reusability and could be reused for consecutive 20 cycles, which make them promising candidate materials in the field of industrial applications and environmental remediation.

Fabrication and application of a MIL-68(In)-NH2 incorporated high internal phase emulsion polymeric monolith as a solid phase extraction adsorbent in triazine herbicide residue analysis.

In this work, a metal-organic framework MIL-68(In)-NH2 incorporated high internal phase emulsion polymeric monolith (MIL-68(In)-NH2/polyHIPE) was prepared and applied as a solid phase extraction adsorbent for the extraction and detection of trace triazine herbicides in environmental water samples by coupling with HPLC-UV detection. The fabricated material showed good adsorption for simazine, prometryn, and prometon in water samples because of π-π interactions and hydrogen bonding interactions. Under optimal conditions, the maximum adsorption capacity of simazine, prometon and prometryn was 800 µg g-1, 800 µg g-1 and 6.01 mg g-1, respectively. The linearities were 10-800 ng mL-1 for simazine, prometon and prometryn. The limits of detection were 31-97 ng L-1, and the recoveries were 85.6-118.2% at four spiked levels with relative standard deviations lower than 5.0%. The method has a high sensitivity for the determination of three triazine herbicides in environmental water samples.

Recent advances in separation applications of polymerized high internal phase emulsions.

Polymerized high internal phase emulsions as highly porous adsorption materials have received increasing attention and wide applications in separation science in recent years due to their remarkable merits such as highly interconnected porosity, high permeability, good thermal and chemical stability, and tailorable chemistry. In this review, we attempt to introduce some strategies to utilize polymerized high internal phase emulsions for separation science, and highlight the recent advances made in the applications of polymerized high internal phase emulsions for diverse separation of small organic molecules, carbon dioxide, metal ions, proteins, and other interesting targets. Potential challenges and future perspectives for polymerized high internal phase emulsion research in the field of separation science are also speculated at the end of this review.

Preparation of porous polymers based on high internal phase emulsion for enrichment of estrogens in urine.

In this work, graphene oxide-hybridized high internal emulsion polymers with crosslinking and open-cell structure was prepared and applied for separation and enrichment of estrogens. The prepared graphene oxide-hybridized high internal emulsion polymer monoliths had hydrophobicity, porosity and stability, which were just obtained by one step in-situ emulsion polymerization of 2-ethylhexyl acrylate, glycidyl methacrylate, and divinylbenzene after doping with graphene oxide. Benefit from the advantages of its unique character, the graphene oxide-hybridized high internal emulsion polymers monolith with low background pressure (85 kPa) and high mechanical strength could be applied for efficient separation for trace estrogens in urine. Under the optimized condition, trace estrogens, including estrone, estradiol, and diethylstilbestrol in urine, were detected by high-performance liquid chromatography, all the sample preparation process were carried out in 15 min, the recovery rate was ranged from 85.0 to 106.0% and the relative standard deviation was less than 4.

Recent advances of ambient ionization mass spectrometry imaging in clinical research.

The structural information and spatial distribution of molecules in biological tissues are closely related to the potential molecular mechanisms of disease origin, transfer, and classification. Ambient ionization mass spectrometry imaging is an effective tool that provides molecular images while describing in situ information of biomolecules in complex samples, in which ionization occurs at atmospheric pressure with the samples being analyzed in the native state. Ambient ionization mass spectrometry imaging can directly analyze tissue samples at a fairly high resolution to obtain molecules in situ information on the tissue surface to identify pathological features associated with a disease, resulting in the wide applications in pharmacy, food science, botanical research, and especially clinical research. Herein, novel ambient ionization techniques, such as techniques based on spray and solid-liquid extraction, techniques based on plasma desorption, techniques based on laser desorption ablation, and techniques based on acoustic desorption were introduced, and the data processing of ambient ionization mass spectrometry imaging was briefly reviewed. Besides, we also highlight recent applications of this imaging technology in clinical researches and discuss the challenges in this imaging technology and the perspectives on the future of the clinical research.

Assembly and application advancement of organic-functionalized graphene-based materials: A review.

Owing to the remarkable physicochemical properties such as hydrophobicity, conductivity, elasticity, and light weight, graphene-based materials have emerged as one of the most appealing carbon allotropes in materials science and chemical engineering. Unfortunately, pristine graphene materials lack functional groups for further modification, severely hindering their practical applications. To render graphene materials with special characters for different applications, graphene oxide or reduced graphene oxide has been functionalized with different organic agents and assembled together, via covalent binding and various noncovalent forces such as π-π interaction, electrostatic interaction, and hydrogen bonding. In this review, we briefly discuss the state-of-the-art synthetic strategies and properties of organic-functionalized graphene-based materials, and then, present the prospective applications of organic-functionalized graphene-based materials in sample preparation.

A porous carbon absorbent based on high internal phase emulsion for separation and enrichment of trifluralin from soil.

A porous carbon absorbent was obtained by using high internal phase emulsions (HIPEs) polymerization followed by high temperature carbonization under nitrogen protection. Graphene oxide (GO) and silica nanoparticles were doped into the HIPEs to enhance the adsorption ability and reusability. Fourier infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were used for characterization and several parameters of separation and enrichment of trifluralin. The results showed that a hyper-crosslink framework material was obtained with abundant porous (pore size of about 30 µm) and a good adsorption and separation efficiency. The adsorption rate was up to 100% and trifluralin was completely eluted from the absorbent by 2.0 mL of an acetic acid-acetonitrile mixture. Graphical abstractSchematic representation of synthesis of porous carbon absorbent by GO and SiO2 doped HIPEs.POLYHIPES-GO&SiO2: Polymerized High Internal Phase Emulsions doped with Silica and Graphene oxide.

Electrospun reduced graphene oxide/TiO2/poly(acrylonitrile-co-maleic acid) composite nanofibers for efficient adsorption and photocatalytic removal of malachite green and leucomalachite green.

Electrospun reduced graphene oxide/TiO2/poly(acrylonitrile-co-maleic acid) composite nanofibers (E-spun RGO/TiO2/PANCMA NFs) were fabricated using electrospinning of the dispersive solution of PANCMA, GO and TiO2 followed by post-chemical reduction. The obtained composite nanofibers were compressed in a dialyzer and then used to absorb and degrade malachite green (MG) and leucomalachite green (LMG) from aqueous solution. Compared to the E-spun TiO2/PANCMA and GO/TiO2/PANCMA NFs, the E-spun RGO/TiO2/PANCMA NFs exhibited higher adsorption capacity and photocatalytic degradation ability. Under optimized conditions, 90.6% of MG and 93.7% of LMG from 50 mL aqueous sample solution were adsorbed on the RGO/TiO2/PANMA NFs (3.0 mg fibers) in 2.0 min, and subsequent the 91.4% and 95.2% of MG and LMG adsorbed on the NFs were degradated in 60 min under UV irradiation, respectively. In addition, the E-spun RGO/TiO2/PANMA NFs exhibited good reusability and could be reused in multiple cycles of operations for adsorption and photocatalytic degradation of MG and LMG. This work demonstrated that the electrospun composite nanofibers are promising materials for removal of pollutants from environmental water samples.

Development of sulfur doped carbon quantum dots for highly selective and sensitive fluorescent detection of Fe2+ and Fe3+ ions in oral ferrous gluconate samples.

Sulfur-doped carbon quantum dots (S-CQDs) with stable blue fluorescence were synthesized through a facile one-step hydrothermal method by using ascorbic acid and thioglycolic acid as carbon and sulfur sources. The prepared S-CQDs exhibited a sensitive and selective response to Fe3+ ions in comparison with Fe2+ and other metal ions, In the presence of adequate H2O2, Fe2+ was completely transformed to Fe3+ that is the determinable form of iron ions, and the difference in the change of the fluorescence intensity of S-CQDs before and after adding H2O2 was used for detection of Fe2+ and Fe3+ ions, respectively. Under the optimum experimental conditions, the fluorescence intensity of S-CQDs gradually decreased with increasing of Fe3+ concentration ranging from 0 to 200 µM. Good linearity was achieved over the range of 0-200 µM. The detection limit of the developed method was 0.050 µM for Fe3+. The recoveries of Fe2+ and Fe3+ spiked in real samples ranged from 98.2% to 112.4%. Finally, the proposed S-CQDs integrated with Fenton system was applied to the detection of Fe2+ and Fe3+ ions in oral ferrous gluconate samples, which presents potential applications in the speciation and determination of Fe2+ and Fe3+ ions in complex samples.

Novel porous carbon composites derived from a graphene-modified high-internal- phase emulsion for highly efficient separation and enrichment of triazine herbicides.

In this study, novel porous carbon composites were successfully prepared with graphene-modified high-internal-phase emulsions (HIPEs) via a simple process of polymerization followed by carbonization. The morphology of the macroporous composites was observed and the verification of structural and functional groups were verified by scanning electron microscopy (SEM), and other characterizations techniques including Fourier transform infrared (FI-IR), X-ray photoelectron spectroscopy (XPS) spectra and Raman spectroscopy. The prepared porous carbon composites were applied to farmland water for the simultaneous adsorption of triazine herbicides and the conditions of extraction and desorption were optimized. Due to the π-π interaction and hydrophobic interaction between triazine herbicides and carbon composites, the maximum adsorption capacity of simazine, prometon and prometryn were 33.4, 34.5 and 33.8 µg g-1, respectively. Adsorption and desorption of triazine herbicides can be achieved in 10 min, and high-speed mass transfer was observed. The calibration curves of three triazine herbicides were linear (R2 ≥0.9996) in the range from 25.0 to 500.0 ng mL-1. The LOD of three triazine herbicides by using the proposed SPE-HPLC-DAD method were 2.5-5.6 ng mL-1. All the results suggest that these materials may be useful for more efficient hazardous residue separations.

Magnetic stir cake sorptive extraction of trace tetracycline antibiotics in food samples: preparation of metal-organic framework-embedded polyHIPE monolithic composites, validation and application.

In this work, a novel Fe3O4@Cu3(btc)2-embedded polymerized high internal phase emulsion (Fe3O4@HKUST-1-polyHIPE) monolithic cake was synthesized, characterized and used as an adsorbent in the magnetic stir cake sorptive extraction (MSCSE) and determination of tetracycline antibiotics (TCs) in food samples by a combination of with high-performance liquid chromatography-fluorescence detection (HPLC-FLD). The prepared Fe3O4@HKUST-1-polyHIPE monolithic composites displayed a strong extraction ability and high column capacity due to enhanced interactions such as π-π interactions, hydrogen bonding, and electrostatic interactions. The extraction and desorption conditions were evaluated, and the calibration curves of four spiked TCs were linear (R2 ≥ 0.9991) in the range from 20 to 800 ng mL-1 for milk and egg samples, and 20 to 800 ng g-1 for chicken muscle and kidney samples. The limits of detection and the limits of quantification of the four TCs by using the proposed MSCSE-HPLC-FLD method were in the range of 1.9-4.6 and 5.5-13.9 ng mL-1 for milk and egg samples, and 1.8-3.7 and 5.3-13.0 ng g-1 for chicken muscle and kidney samples, respectively. The recoveries of the target TCs from spiked food samples were in the range from 86.6 to 110.7% with relative standard deviations lower than 7.0%. The proposed method was successfully applied for the determination of these four TCs in milk, egg, chicken muscle, and kidney samples.