In situ construction of Ag/Bi2O3/Bi5O7I heterojunction with Bi-MOF for enhance the photocatalytic efficiency of bisphenol A by facet-coupling and s-scheme structure.

In this study, Ag/Bi2O3/Bi5O7I with s-scheme heterostructures were successfully synthesized in situ by nano-silver modification of CUA-17 and halogenated hydrolysis.The growth rate of Bi2O3 crystals was effectively controlled by adjusting the doping amount of Ag, resulting in the formation of a facet-coupling heterojunctions. Through the investigation of the microstructure and compositional of catalysts, it has been confirmed that an intimate facet coupling between the Bi2O3 (120) facet and the Bi5O7I (312) facet, which provides robust support for charge transfer. Under visible light irradiation, the AgBOI.3 heterojunction photocatalyst exhibited an outstanding degradation rate of 98.2% for Bisphenol A (BPA) with excellent stability. Further characterization using optical, electrochemical, impedance spectroscopy, and electron spin resonance techniques revealed significantly enhanced efficiency in photogenerated charge separation and transfer, and confirming the s-scheme structure of the photocatalyst. Density functional theory calculations was employed to elucidate the mechanism of BPA degradation and the degradation pathway of BPA was investigated by LC-MS. Finally, the toxicity of the degradation intermediates was evaluated using T.E.S.T software.

Construction of dual Z-scheme Bi2WO6/g-C3N4/black phosphorus quantum dots composites for effective bisphenol A degradation.

In this work, a novel dual Z-scheme Bi2WO6/g-C3N4/black phosphorus quantum dots (Bi2WO6/g-C3N4/BPQDs) composites were fabricated and utilized towards photocatalytic degradation of bisphenol A (BPA) under visible-light irradiation. Optimizing the content of g-C3N4 and BPQDs in Bi2WO6/g-C3N4/BPQDs composites to a suitable mass ratio can enhance the visible-light harvesting capacity and increase the charge separation efficiency and the transfer rate of excited-state electrons and holes, resulting in much higher photocatalytic activity for BPA degradation (95.6%, at 20 mg/L in 120 min) than that of Bi2WO6 (63.7%), g-C3N4 (25.0%), BPQDs (8.5%), and Bi2WO6/g-C3N4 (79.6%), respectively. Radical trapping experiments indicated that photogenerated holes (h+) and superoxide radicals (•O2-) played crucial roles in photocatalytic BPA degradation. Further, the possible degradation pathway and photocatalytic mechanism was proposed by analyzing the BPA intermediates. This work also demonstrated that the Bi2WO6/g-C3N4/BPQDs as effective photocatalysts was stable and have promising potential to remove environmental contaminants from real water samples.

Vanadium carbide MXene: as a reductant for the synthesis of gold nanoparticles and its biosensing application.

Vanadium carbide MXene (V2C) acts as a new type of two-dimensional (2D) graphene-like transition metal material that has attracted research interest. V2C has been widely used in various fields due to its excellent physical and chemical properties. Herein, the self-assembled V2C@gold nanoparticles (V2C@AuNPs) are prepared by water bath process at 80 °C. With the addition of glutathione (GSH), the absorbance (Abs.) at 550 nm of V2C@AuNPs was decreased. Therefore, an optical sensor is developed to detect GSH based on the properties of V2C@AuNPs. Under the optimal conditions, the detection range is 1-32 µM and the detection limit is 0.099 µM. Furthermore, the proposed GSH sensor exhibits high sensitivity, high selectivity, strong stability, and excellent recovery. The work will expand the application of V2C in biosensing.

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.

Photoelectrochemical determination of cardiac troponin I based on rod-like g-C3N5@MnO2 heterostructure.

Rod-like graphite carbon nitride@MnO2 (R-g-C3N5@MnO2) heterostructure was prepared by in situ self-anchored growth of MnO2 nanosheet on the surface of R-g-C3N5. The synthesized R-g-C3N5@MnO2 heterostructure as photoactive material exhibited excellent photoelectrochemical (PEC) performance, and the prepared heterostructure-aptamer probe displayed sensitive PEC response to cTnI. Therefore, the PEC method was developed to detect cTnI based on the R-g-C3N5@MnO2 heterostructure. It was found that the linear response to cTnI was in the range 0.001-30 ng/mL under optimized conditions, and the detection limit of the proposed sensor was 0.3 pg/mL. The PEC method displays stable photocurrent response up to 8 cycles and exhibited outstanding selectivity and sensitivity. The PEC method was successfully applied to detect cTnI in serum samples. The recoveries of cTnI detection in serums reach 95.5-104%, and the relative standard deviations range from 3.20 to 4.45%.

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 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.

Transforming glucose into fluorescent graphene quantum dots via microwave radiation for sensitive detection of Al3+ ions based on aggregation-induced enhanced emission.

This paper initially describes a nanosensor for fluorescence detection of Al3+ ions by using graphene quantum dots (GQDs) that are synthesized via microwave-assisted single-step ring-closure condensation of glucose molecules. The one-pot synthesis strategy based on the microwave radiation could be finished in several minutes and no post-modification of the GQDs was required. In particular, the GQD nanoprobes showed a sensitive and specific fluorescence enhancement response to Al3+. The involved mechanism might be the Al3+-mediated aggregation of the GQDs leading to aggregation-induced enhanced emission (AIEE). Under optimal conditions, this new fluorescent nanosensor was able to quantitatively detect Al3+ in a linear concentration range of 0.4-500 µM. The limit of detection was estimated to be ∼59.8 nM according to the 3σ rule, which made it be among the most sensitive systems currently available for sensing the target ion. Moreover, satisfactory recovery results (ranging from 96.8 to 109.7%) of analyzing a set of real water examples additionally validated its accuracy for practical applications. Considering its simplicity, high sensitivity and specificity, low cost, and good reliability, the developed fluorescent nanosensing system for Al3+ holds great promise for broad uses in water safety, environmental monitoring, and waste management.

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.

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.

Reduced Graphene Oxide-Hybridized Polymeric High-Internal Phase Emulsions for Highly Efficient Removal of Polycyclic Aromatic Hydrocarbons from Water Matrix.

Reduced graphene oxide (RGO)-hybridized polymeric high-internal phase emulsions (RGO/polyHIPEs) with an open-cell structure and hydrophobicity have been successfully prepared using 2-ethylhexyl acrylate and ethylene glycol dimethacrylate as the monomer and the cross-linker, respectively. The adsorption mechanism and performance of this RGO/polyHIPEs to polycyclic aromatic hydrocarbons (PAHs) were investigated. Adsorption isotherms of PAHs on RGO/polyHIPEs show that the saturated adsorption capacity is 47.5 mg/g and the equilibrium time is 8 h. Cycling tests show that the adsorption capacity of RGO/polyHIPEs remains stable in 10 adsorption-desorption cycles without observable structure change in RGO/polyHIPEs. Moreover, the PAH residues in water samples after being purified by RGO/polyHIPEs are lower than the limit values in drinking water set by the European Food Safety Authority. These results demonstrate that the RGO/polyHIPEs have great potentiality in PAH removal and water purification.

Graphene oxide composites for magnetic solid-phase extraction of trace cytokinins in plant samples followed by liquid chromatography-tandem mass spectrometry.

In this work, an easy, effective, and sensitive method based on graphene oxide@silica@magnetite composites as adsorbent of magnetic solid-phase extraction combined with liquid chromatography and tandem mass spectrometry, was established and validated for the trace analysis of cytokinins in different plants. The prepared magnetic composite was characterized by infrared spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, and magnetic hysteresis. Under the optimized conditions, good linearities in the range of 0.5-100 ng/mL were obtained with the corresponding linear correlation coefficient >0.9989 for the investigated four cytokinins, and good sensitivity levels were achieved with low detection limits ranging from 93 to 120 pg/mL. The established magnetic solid-phase extraction with liquid chromatography and tandem mass spectrometry method has been validated in the separation and analysis of four cytokinins in plant samples with good recoveries between 78.9 and 97.3% for four cytokinins with the relative standard deviations lower than 13.5%.

An easily regenerable enzyme reactor prepared from polymerized high internal phase emulsions.

A large-scale high-efficient enzyme reactor based on polymerized high internal phase emulsion monolith (polyHIPE) was prepared. First, a porous cross-linked polyHIPE monolith was prepared by in-situ thermal polymerization of a high internal phase emulsion containing styrene, divinylbenzene and polyglutaraldehyde. The enzyme of TPCK-Trypsin was then immobilized on the monolithic polyHIPE. The performance of the resultant enzyme reactor was assessed according to the conversion ability of Nα-benzoyl-l-arginine ethyl ester to Nα-benzoyl-l-arginine, and the protein digestibility of bovine serum albumin (BSA) and cytochrome (Cyt-C). The results showed that the prepared enzyme reactor exhibited high enzyme immobilization efficiency and fast and easy-control protein digestibility. BSA and Cyt-C could be digested in 10 min with sequence coverage of 59% and 78%, respectively. The peptides and residual protein could be easily rinsed out from reactor and the reactor could be regenerated easily with 4 M HCl without any structure destruction. Properties of multiple interconnected chambers with good permeability, fast digestion facility and easily reproducibility indicated that the polyHIPE enzyme reactor was a good selector potentially applied in proteomics and catalysis areas.

Magnetic metal-organic framework MIL-100(Fe) microspheres for the magnetic solid-phase extraction of trace polycyclic aromatic hydrocarbons from water samples.

In this work, a magnetic metal-organic framework designated as MIL-100(Fe) was prepared and applied as a magnetic solid-phase extraction sorbent for the determination of trace polycyclic aromatic hydrocarbons in environmental water samples by coupling with high-performance liquid chromatography and fluorescence detection. The magnetic microspheres exhibited large surface areas and high extraction ability, making them excellent candidates as sorbents for enrichment of trace polycyclic aromatic hydrocarbons. Under the optimized experimental conditions, good sensitivity levels were achieved with low detection limits ranging from 32 to 2110 pg/mL and good linearities with correlation coefficients higher than 0.9990 for the investigated 13 polycyclic aromatic hydrocarbons. The proposed method has been validated in the analysis of real water samples with mean recoveries in the range of 81.4-126.9% at four spiked levels and the relative standard deviations in the range of 1.3-17.0%. The magnetic MIL-100(Fe) microspheres were stable enough for 150 extractions without a significant loss of extraction performance.

High-internal-phase-emulsion polymeric monolith coupled with liquid chromatography-electrospray tandem mass spectrometry for enrichment and sensitive detection of trace cytokinins in plant samples.

High-internal-phase-emulsion polymers (polyHIPEs) show great promise as solid-phase-extraction (SPE) materials because of the tremendous porosity and highly interconnected framework afforded by the high-internal-phase-emulsion (HIPE) technique. In this work, polyHIPE monolithic columns as novel SPE materials were prepared and applied to trace enrichment of cytokinins (CKs) from complex plant samples. The polyHIPE monoliths were synthesized via the in-situ polymerization of the continuous phase of a HIPE containing styrene (STY) and divinylbenzene (DVB) in a stainless column, and revealed highly efficient and selective enrichment ability for aromatic compounds. Under the optimized experimental conditions, a method using a monolithic polyHIPE column combined with liquid chromatography-electrospray tandem mass spectrometry (LC-MS-MS) was developed for the simultaneous extraction and sensitive determination of trans-zeatin (tZ), meta-topolin (mT), kinetin (K), and kinetin riboside (KR). The proposed method had good linearity, with correlation coefficients (R (2)) from 0.9957 to 0.9984, and low detection limits (LODs, S/N = 3) in the range 2.4-47 pg mL(-1) for the four CKs. The method was successfully applied to the determination of CKs in real plant samples, and obtained good recoveries ranging from 68.8 % to 103.0 % and relative standard deviations (RSDs) lower than 16 %.

Application of mercapto-silica polymerized high internal phase emulsions for the solid-phase extraction and preconcentration of trace lead(II).

A new class of solid-phase extraction column prepared with grafted mercapto-silica polymerized high internal phase emulsion particles was used for the preconcentration of trace lead. First, mercapto-silica polymerized high internal phase emulsion particles were synthesized by using high internal phase emulsion polymerization and carefully assembled in a polyethylene syringe column. The influences of various parameters including adsorption pH value, adsorption and desorption solvents, flow rate of the adsorption and desorption procedure were optimized, respectively, and the suitable uploading sample volumes, adsorption capacity, and reusability of solid phase extraction column were also investigated. Under the optimum conditions, Pb(2+) could be preconcentrated quantitatively over a wide pH range (2.0-5.0). In the presence of foreign ions, such as Na(+) , K(+) , Ca(2+) , Zn(2+) , Mg(2+) , Cu(2+) , Fe(2+) , Cd(2+) , Cl(-) and NO3 (-) , Pb(2+) could be recovered successfully. The prepared solid-phase extraction column performed with high stability and desirable durability, which allowed more than 100 replicate extractions without measurable changes of performance. The feasibility of the developed method was further validated by the extraction of Pb(2+) in rice samples. At three spiked levels of 40.0, 200 and 800 µg/kg, the average recoveries for Pb(2+) in rice samples ranged from 87.3 to 105.2%.

Development and validation of polymerized high internal phase emulsion monoliths coupled with HPLC and fluorescence detection for the determination of trace tetracycline antibiotics in environmental water samples.

A polymerized high internal phase emulsion monolith was used as a novel sorbent for solid-phase extraction coupled with high-performance liquid chromatography and fluorescence detection for the determination of oxytetracycline, tetracycline, doxycycline, and chlorotetracycline in environmental water samples. The polymerized high internal phase emulsion monolithic column was prepared by the in situ polymerization of the continuous phase of a high internal phase emulsion containing glycidyl methacrylate, styrene, and divinylbenzene in pipette tips, and then functionalized with iminodiacetic acid. The resulting monolith exhibited highly interconnected porosity and large surface areas, making it an excellent candidate as an solid-phase extraction sorbent for the enrichment of trace tetracycline antibiotics. Several factors affecting the extraction performance of polymerized high internal phase emulsion monoliths, including the pH of sample solution, the eluting solvents, the sample loading flow rate and volume, were investigated, respectively. Under the optimized conditions, the mean recoveries of oxytetracycline, tetracycline, doxycycline, and chlorotetracycline spiked in pond and farm wastewater samples ranged from 78.1 to 119.3% with relative standard deviation less than 15%. The detection limits (S/N = 3) of the proposed method were in the range of 51-137 pg/mL. This study demonstrated that the monolithic polymerized high internal phase emulsion would be promising solid-phase extraction sorbents in the extraction and proconcentration of trace analytes from complex samples.

Development of continuous microwave-assisted protein digestion with immobilized enzyme.

In this study, an easy and efficiency protein digestion method called continuous microwave-assisted protein digestion (cMAED) with immobilized enzyme was developed and applied for proteome analysis by LC-MS(n). Continuous microwave power outputting was specially designed and applied. Trypsin and bromelain were immobilized onto magnetic micropheres. To evaluate the method of cMAED, bovine serum albumin (BSA) and protein extracted from ginkgo nuts were used as model and real protein sample to verify the digestion efficiency of cMAED. Several conditions including continuous microwave power, the ratio of immobilized trypsin/BSA were optimized according to the analysis of peptide fragments by Tricine SDS-PAGE and LC-MS(n). Subsequently, the ginkgo protein was digested with the protocols of cMAED, MAED and conventional heating enzymatic digestion (HED) respectively and the LC-MS(n) profiles of the hydrolysate was compared. Results showed that cMAED combined with immobilized enzyme was a fast and efficient digestion method for protein digestion and microwave power tentatively affected the peptide producing. The cMAED method will be expanded for large-scale preparation of bioactive peptides and peptide analysis in biological and clinical research.