Efficient enrichment and sensitive detection of polychlorinated biphenyls using nanoflower MIL-on-UiO as solid-phase microextraction fiber coating.

The sensitive detection of polychlorinated biphenyls (PCBs) is crucial for protecting the environment and human health. Herein, we constructed a Materials Institute Lavoisier 88B (MIL-88B)-on-University of Oslo 66 (UiO-66) composite (MIL-on-UiO) with a unique nanoflower morphology, in which highly stable UiO-66 is the precursor, with MIL-88B grown on its surface. MIL-on-UiO was used as a fiber coating for headspace solid-phase microextraction to enrich PCBs. Experimental results demonstrated that MIL-on-UiO provided better enrichment performance for PCBs than single components due to multiple interactions, including π-π stacking, halogen bonding, pore-filling, and steric hindrance effects. The method established using the MIL-on-UiO-based SPME fiber coating provided a good linear relationship in the range of 0.001-50 ng·mL-1, with limits of detection ranging from 0.0002 to 0.002 ng·mL-1 and enrichment factors between 3530 and 7420. In addition, the method was used to detect trace PCBs in water and orange juice achieving satisfactory recoveries (81%-111%).

Performance of Microsoft Azure Kinect DK as a tool for estimating human body segment lengths.

The Microsoft Kinect depth sensor, with its built-in software that automatically captures joint coordinates without markers, could be a potential tool for ergonomic studies. This study investigates the performance of Kinect in limb segment lengths using dual-energy X-ray absorptiometry (DXA) as a reference. Healthy children and adults (n = 76) were recruited for limb length measurements by Kinect and DXA. The results showed consistent ratios of arm, forearm, thigh, and leg lengths to height, which were 0.16, 0.14, 0.23, and 0.22 respectively, for both age groups and methods. Kinect exhibited perfect correlation among all limb lengths, indicating fixed proportions assumed by its algorithm. Comparing the two methods, there was a strong correlation (R = 0.850-0.985) and good to excellent agreement (ICC = 0.829-0.977), except for the right leg in adults, where agreement was slightly lower but still moderate (ICC = 0.712). The measurement bias between the methods ranged from - 1.455 to 0.536 cm. In conclusion, Kinect yields outcomes similar to DXA, indicating its potential utility as a tool for ergonomic studies. However, the built-in algorithm of Kinect assumes fixed limb proportions for individuals, which may not be ideal for studies focusing on investigating limb discrepancies or anatomical differences.

Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples.

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4'-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214-327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

MOF-derived porous carbon microspheres Ni@C-acid as solid-phase microextraction coating for extraction of polycyclic aromatic hydrocarbons from tea infusions.

The improvement of the stability and adsorption properties of materials on targets in sample pre-treatment has long been an objective. Extensive efforts have been made to achieve this goal. In this work, metal-organic framework Ni-MOF precursors were first synthesized by solvothermal method using polyvinylpyrrolidone (PVP) as an ideal templating agent, stabiliser and nanoparticle dispersant. After carbonization and acid washing, the nanoporous carbon microspheres material (Ni@C-acid) was obtained. Compared with the material without acid treatment (Ni@C), the specific surface area, pore volume, adsorption performance of Ni@C-acid were increased. Thanks to its excellent characteristics (high stability, abundant benzene rings), Ni@C-acid was used as fiber coatings in headspace solid-phase microextraction (HS-SPME) technology for extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The experimental parameters of extraction temperature, extraction time, agitation speed, desorption temperature, desorption time and sodium chloride (NaCl) concentration were studied. Under optimal experimental conditions, the wide linear range (0.01-30 ng mL-1), the good correlation coefficient (0.9916-0.9984), the low detection limit (0.003-0.011 ng mL-1), and the high enrichment factor (5273-13793) were obtained. The established method was successfully used for the detection of trace PAHs in actual tea infusions samples and satisfied recoveries ranging from 80.94-118.62 % were achieved. The present work provides a simple method for the preparation of highly stable and adsorbable porous carbon microsphere materials with potential applications in the extraction of environmental pollutants.

Three-dimensional rose-like zinc oxide fiber coating for simultaneous extraction of polychlorinated biphenyls and polycyclic aromatic hydrocarbons by headspace solid phase microextraction.

The three-dimensional (3D) rose-like zinc oxide (ZnO) material was prepared by a simple one-step CTAB-assisted hydrothermal strategy and used as a headspace solid-phase microextraction (HS-SPME) coating. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed by gas chromatography with flame ionization detector (GC-FID), and conclusively applied to ultrasensitive detection in lake and river water. Compared with one-dimensional (1D) pencil-like ZnO, the layer-by-layer petal-like structure could fully expose mass adsorption sites on the surface, which could significantly improve the adsorption. The enrichment factors with 7535-8595 for PCBs and 3855-7320 for PAHs were achieved. The established method provided a satisfactory linear range (0.005-30 ng·mL-1), coefficient (R2 > 0.9978), ultra-low limit detection (1-3 pg·mL-1), and long service life (≥ 150 times). The recoveries of 83.42-120.86 % were obtained in the real detection application of lake and river water. This work demonstrated that 3D rose-like ZnO with low cost, simple synthesis, fast extraction ability and high enrichment performance was an ideal coating material, which was hoped to enrich other compounds with similar structures with PCBs and PAHs.

Ionic liquid-modified UiO-66-NH2 as sorbent of dispersive solid-phase extraction for rapid adsorption and enrichment of benzoylurea insecticides.

Ionic liquid (IL)-modified UiO-66-NH2 composite was prepared and used as sorbent of dispersed solid-phase extraction (dSPE) for extracting trace benzoylurea insecticides (BUs) from complex environmental matrices. The IL in framework endowed the prepared material had electropositive characteristics, which can produce interaction with electron rich guest molecules, such as BUs. The high thermal and chemical stability of UiO-66-NH2/IL enabled it to be reused for 16 times without significant reduction in adsorption performance. Due to the multiple forces including π-π, hydrogen bonding, and fluorine-fluorine interaction, UiO-66-NH2/IL showed good adsorption performance, short adsorption time (20 s) and rapid desorption ability (60 s) for BUs. Under the optimal conditions, the method exhibited wide linear range (0.02-500 ng mL-1) with correlation coefficient (R2) not worse than 0.9928, high enrichment factor (252-300), and low detection limit (0.005-0.4 ng mL-1). The dispersed solid phase extraction coupling with high-performance liquid chromatography-diode array detector (dSPE-HPLC-DAD) was successfully used to detection of BUs in real environmental samples and satisfactory recoveries were obtained (80.5%±2.4-118%±3.2). The results indicated that UiO-66-NH2/IL composite can be a potential sorbent for the preconcentration of trace insecticides in environmental samples.

Confinement effect of ionic liquid: Improve of the extraction performance of parent metal organic framework for phthalates.

In order to better identify the hazards of pollutants, developing the analytical methods that can sensitively detect and precisely monitor the content of trace pollutants has been the constant pursuit. In this paper, a new solid phase microextraction coating-ionic liquid/metal organic framework (IL/MOF) was obtained through the IL-induced strategy and used for the solid phase microextraction (SPME) process. IL was introduced into metal-organic framework (MOF) cage based on the anion of ionic liquid could interact strongly with the zirconium nodes of UiO-66-NH2. The introduction of IL not only increased the stability of composite, the hydrophobicity of IL also changed the environment of MOF channel, providing the hydrophobic effect to the targets. The confinement effect of IL effectively improved the extraction performance of parent MOF and the extraction performance of synthesized IL/UiO-66-NH2 for phthalates (PAEs) were 1.3-3.0 times that of parent UiO-66-NH2. Thanks to the strong interaction force (hydrogen bonding interaction, π-π stacking, hydrophobic interaction force), the IL/UiO-66-NH2-coated fiber coupled with gas chromatography-mass spectrometer showed a wide linear ranges (1-5000 ng L-1) with good correlation (R2, 0.9855-0.9987), lower detection limit (0.2-0.4 ng L-1) and satisfactory recoveries (95.3-119.3%) for PAEs. This article is dedicated to provide another way to improve the extraction performance of material.

Construction of hierarchically porous metal-organic framework HP-UiO-66-30% for sensitive determination of benzoylurea insecticides.

Due to widespread application of benzoylurea insecticides (BUs) and its persistence in environment, the effective capture of benzoylurea insecticides residues in environment is an important issue of environmental safety monitoring. To obtain excellent adsorption performance, creating defective structure in metal-organic frameworks (MOFs) can be employed as the method for adjusting its properties. Zirconium(Ⅳ)-based MOF termed as UiO-66-30% was constructed with 2-aminoterephthalic acid (NH2-BDC) and terephthalic acid (H2BDC) as building blocks. After calcination and removal of thermal-sensitive ligand (NH2-BDC), hierarchically porous UiO-66-30% (HP-UiO-66-30%) with multistage pore structure and good stability was obtained. The unique structure of HP-UiO-66-30% endowed it to achieve instantaneous equilibrium (within 2 min) when it was used as a dispersed solid phase extraction (d-SPE) adsorbent to extract BUs from environmental samples, greatly reducing the operation time. A wide linear range (0.05-200 ng mL-1), good linearity (R2 ≥ 0.9980), low detection limits (0.01-0.03 ng mL-1) and quantification limits (0.05-0.1 ng mL-1) were obtained for BUs. In addition, the HP-UiO-66-30% material possessed the good reusability and the adsorption capacity did not change significantly over 16 adsorption-desorption cycles. Finally, the established dispersed solid phase extraction-high performance liquid chromatography-diode array detector (d-SPE-HPLC-DAD) method was successfully applied to determination of BUs residues in environmental soil samples. The results demonstrated that HP-UiO-66-30% was an excellent sorbent for extraction BUs from environmental samples.

Development and validation of a coagulation-related genes prognostic model for hepatocellular carcinoma.

BACKGROUND: Hepatocellular carcinoma (HCC) has a high incidence and mortality worldwide, which seriously threatens people's physical and mental health. Coagulation is closely related to the occurrence and development of HCC. Whether coagulation-related genes (CRGs) can be used as prognostic markers for HCC remains to be investigated. METHODS: Firstly, we identified differentially expressed coagulation-related genes of HCC and control samples in the datasets GSE54236, GSE102079, TCGA-LIHC, and Genecards database. Then, univariate Cox regression analysis, LASSO regression analysis, and multivariate Cox regression analysis were used to determine the key CRGs and establish the coagulation-related risk score (CRRS) prognostic model in the TCGA-LIHC dataset. The predictive capability of the CRRS model was evaluated by Kaplan-Meier survival analysis and ROC analysis. External validation was performed in the ICGC-LIRI-JP dataset. Besides, combining risk score and age, gender, grade, and stage, a nomogram was constructed to quantify the survival probability. We further analyzed the correlation between risk score and functional enrichment, pathway, and tumor immune microenvironment. RESULTS: We identified 5 key CRGs (FLVCR1, CENPE, LCAT, CYP2C9, and NQO1) and constructed the CRRS prognostic model. The overall survival (OS) of the high-risk group was shorter than that of the low-risk group. The AUC values for 1 -, 3 -, and 5-year OS in the TCGA dataset were 0.769, 0.691, and 0.674, respectively. The Cox analysis showed that CRRS was an independent prognostic factor for HCC. A nomogram established with risk score, age, gender, grade, and stage, has a better prognostic value for HCC patients. In the high-risk group, CD4+T cells memory resting, NK cells activated, and B cells naive were significantly lower. The expression levels of immune checkpoint genes in the high-risk group were generally higher than that in the low-risk group. CONCLUSIONS: The CRRS model has reliable predictive value for the prognosis of HCC patients.

Single-site bipyridine cobalt complexes covalently embedded into graphitic carbon nitride with excellent photocatalytic activity and selectivity towards CO2 reduction.

A combination of a semiconductor-based photosensitizer with molecular catalysts via covalent bonds is an effective way to utilize solar energy to reduce CO2 into value-added chemicals with high efficiency and selectivity. In this study, 2,2'-bpy-5,5'-dialdehyde functioned as organic ligands and were embedded into the skeleton of g-CN through imine bonds via thermal copolymerization. The introduction of 2,2'-bpy can not only chelate with earth-abundant Co as single-site catalytic centers but also can optimize the properties of original g-CN such as the enlarged specific surface area and extended visible light absorption range. The CO evolution rate of g-CN-bpy-Co can reach up to 106.3 µmol g-1 h-1 with a selectivity of 97% over proton reduction, which was 82-fold than that of g-CN-Co. The different coordination environments and valence states of cobalt were also studied simultaneously and the results showed that Co(II) exhibited superior catalytic activity towards Co(III). Control experiments demonstrated that the covalent linkage between g-CN and Co-2,2'-bpy plays a vital role in photocatalytic activity and selectivity. Besides, the CO generation rate demonstrated linear growth upon visible light irradiation up to 72 h and preferable recyclability. This research provides a new facile way to fabricate low-priced photocatalysts with high activity and selectivity and bridge homogeneous and heterogeneous catalysis.

Synthesis of spindle-like amino-modified Zn/Fe bimetallic metal-organic frameworks as sorbents for dispersive solid-phase extraction and preconcentration of phytohormoes in vegetable samples.

Amino-modified Zn/Fe bimetallic metal-organic frameworks (NH2-Zn/Fe-MIL-88) were synthesized using a one-step solvothermal method with FeCl3·6H2O and Zn(NO3)2·6H2O as metal salts and 2-aminoterephthalic acid as organic ligand. The morphology of NH2-Zn/Fe-MIL-88 can be regulated from octahedral-like to spindle-like with changing molar ratios of metal salts. Using NH2-Zn/Fe-MIL-88 as sorbent, a dispersive solid-phase extraction with putting sorbents into sample solution to extract targets was developed to preconcentrate phytohormones in vegetables. To study the extraction efficiency, a series of NH2-Zn/Fe-MIL-88s with varying molar ratios of metal salts were prepared. The results indicated that NH2-Zn/Fe-MIL-88(1) presented the highest extraction efficiency (82.6 %-98.1 %) to phytohormones among all prepared NH2-Zn/Fe-MIL-88(x). The limits of detection were calculated at 0.07-0.15 ng/mL. The adsorption isotherms and kinetic parameters of NH2-Zn/Fe-MIL-88 for phytohormones were conformed to Langmuir and pseudo-second-order models. The NH2-Zn/Fe-MIL-88 as sorbent combined with HPLC was applied to detect phytohormones in cucumber and tomato samples.

Comparison of ischemic stroke diagnosis models based on machine learning.

Background: The incidence, prevalence, and mortality of ischemic stroke (IS) continue to rise, resulting in a serious global disease burden. The prediction models have a great value in the early prediction and diagnosis of IS. Methods: The R software was used to screen the differentially expressed genes (DEGs) of IS and control samples in the datasets GSE16561, GSE58294, and GSE37587 and analyze DEGs for enrichment analysis. The feature genes of IS were obtained by several machine learning algorithms, including the least absolute shrinkage and selector operation (LASSO) logistic regression, the support vector machine-recursive feature elimination (SVM-RFE), and the Random Forest (RF). The IS diagnostic models were constructed based on transcriptomics by machine learning and artificial neural network (ANN). Results: A total of 69 DEGs, mainly involved in immune and inflammatory responses, were identified. The pathways enriched in the IS group were complement and coagulation cascades, lysosome, PPAR signaling pathway, regulation of autophagy, and toll-like receptor signaling pathway. The feature genes selected by LASSO, SVM-RFE, and RF were 17, 10, and 12, respectively. The area under the curve (AUC) of the LASSO model in the training dataset, GSE22255, and GSE195442 was 0.969, 0.890, and 1.000. The AUC of the SVM-RFE model was 0.957, 0.805, and 1.000, respectively. The AUC of the RF model was 0.947, 0.935, and 1.000, respectively. The models have good sensitivity, specificity, and accuracy. The AUC of the LASSO+ANN, SVM-RFE+ANN, and RF+ANN models was 1.000, 0.995, and 0.997, respectively, in the training dataset. However, the AUC of LASSO+ANN, SVM-RFE+ANN, and RF+ANN models was 0.688, 0.605, and 0.619, respectively, in the GSE22255 dataset. The AUC of the LASSO+ANN and RF+ANN models was 0.740 and 0.630, respectively, in the GSE195442 dataset. In the training dataset, the sensitivity, specificity, and accuracy of the LASSO+ANN model were 1.000, 1.000, and 1.000, respectively; of the SVM-RFE+ANN model were 0.946, 0.982, and 0.964, respectively; and of the RF+ANN model were 0.964, 1.000, and 0.982, respectively. In the test datasets, the sensitivity was very satisfactory; however, the specificity and accuracy were not good. Conclusion: The LASSO, SVM-RFE, and RF models have good prediction abilities. However, the ANN model is efficient at classifying positive samples and is unsuitable at classifying negative samples.

A Novel Ca-Modified Biochar for Efficient Recovery of Phosphorus from Aqueous Solution and Its Application as a Phosphorus Biofertilizer.

Recovery phosphorus (P) from P-contaminated wastewater is an efficient and environmentally friendly mean to prevent water pollution and alleviate the P shortage crisis. In this study, oyster shell as calcium sources and peanut shells as carbon sources (mass ratio 1:1) were used to prepare a novel Ca-modified biochar (OBC) via co-pyrolysis, and its potential application after P adsorption as a P biofertilizer for soil was also investigated. The results shown that OBC had a remarkable P adsorption capacity from wastewater in a wide range of pH 4−12. The maximum P adsorption capacity of OBC was about 168.2 mg/g with adsorbent dosage 1 g/L, which was about 27.6 times that of the unmodified biochar. The adsorption isotherm and kinetic data were better described by Langmuir isotherm model (R2 > 0.986) and the pseudo second-order model (R2 > 0.975), respectively. Characterization analysis of OBC before and after P adsorption by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and specific surface area and porosity analyzer (BET) indicated that the remarkable P adsorption capacity of OBC was mainly ascribed to chemical precipitation, electrostatic adsorption, and hydrogen bonding. Pot experiment results showed that OBC after P adsorption could significantly promote the germination and growth of Spinacia, which manifested that OBC after P adsorption exhibited a good ability to be reused as P fertilizer for soil.

Porous Hexagonal Boron Nitride as Solid-Phase Microextraction Coating Material for Extraction and Preconcentration of Polycyclic Aromatic Hydrocarbons from Soil Sample.

Sample pretreatment plays important role in the analysis and detection of trace pollutants in complex matrices, such as environmental and biological samples. The adsorption materials of sample pretreatment receive considerable attention, which has a significant effect on the sensitivity and selectivity of the analytical method. In this work, the porous hexagonal boron nitride (h-BN) was utilized as a coating material of solid-phase microextraction (SPME) to extract and preconcentrate polycyclic aromatic hydrocarbons (PAHs) prior to separation and detection with GC-FID. Attributed to the multiple interactions including hydrophobicity, hydrogen bonding and strong π-π interaction, the h-BN coating showed excellent extraction performance for PAHs. Under the optimal conditions, the method showed the linear relationship in the range of 0.1-50 ng mL-1 for acenaphthene, 0.05-50 ng mL-1 for pyrene, and 0.02-50 ng mL-1 for fluorene, phenanthrene and anthracene with a correlation coefficient (R2) not lower than 0.9910. The enrichment factors were achieved between 1526 and 4398 for PAHs with h-BN as SPME fiber coating. The detection limits were obtained in the range of 0.004-0.033 ng mL-1, which corresponds to 0.08-0.66 ng g-1 for soil. The method was successfully applied to analysis of real soil samples. The recoveries were determined between 78.0 and 120.0% for two soil samples. The results showed that h-BN material provided a promising alternative in sample pretreatment and analysis.

Poly(divinylbenzene) as a fiber coating for headspace solid-phase microextraction of polycyclic aromatic hydrocarbons from river water.

Porous polydivinylbenzene microspheres with high specific surface area were prepared by distillation-precipitation polymerization, and were used as the coating material in headspace solid phase microextraction for extracting polycyclic aromatic hydrocarbons. Compared with the other reported sorbents, PDVB exhibits lower cost and higher extraction efficiency, and the enrichment factors can reach 5963-16 720.

Preparation of multivariate zirconia metal-organic frameworks for highly efficient adsorption of endocrine disrupting compounds.

Owing to their structural and functional tunability, the preparation of multivariate metal-organic frameworks (MTV-MOFs) and investigation of their potential application has become a hot topic in fields of environment and energy. To achieve more adsorption and removal performance, a series of multivariate Zr-MOFs (TCPP@MOF-808s) were prepared via mixed-ligands strategy for the first time. The morphology, as well as adsorption and removal properties of TCPP@MOF-808s can be controlled by adjusting ratio of the linkers. 57%TCPP@MOF-808 could provide ideal appearance with excellent stability. By using 57%TCPP@MOF-808 as sorbent, a dispersive solid-phase extraction (dSPE) was developed for extraction of endocrine disrupting compounds (EDCs) including BPA, 17ß-E2, 17α-E2, E1, and HEX from environmental water prior to HPLC analysis. The pseudo-second-order model can describe the adsorption kinetic data well. Using Langmuir isotherm model, the maximum adsorption capacities of BPA, 17ß-E2, 17α-E2, and E1 were calculated as 94.34, 104.17, 109.89, and 121.95 mg·g-1, respectively. The LODs for the analysis of EDCs with HPLC-DAD by using 57%TCPP@MOF-808 as sorbent were achieved in the range of 0.01-0.03 ng·mL-1. The recoveries were obtained in the range of 74.63-98.00%. Enrichment factors were calculated in the range of 146-312. This work provides an effective strategy for design and preparation of multifunctional nanomaterials to improve their potential applications in the detection of environmental pollutants.

Enhanced transport of heavy metal ions by low-molecular-weight organic acids in saturated porous media: Link complex stability constants to heavy metal mobility.

Environment-ubiquitous low-molecular-weight organic acids (LMWOAs) can interact with heavy metal ions and thus affect their mobility in subsurface aquifers. Herein, the effects of LMWOAs (including acetic acid, tartaric acid, malonic acid, oxalic acid, and citric acid) on the mobility of heavy metal ions (including Cd2+, Zn2+, Ni2+, Mn2+, and Co2+) in porous media were investigated to reveal the role of the stability constants of metal-LMWOA complexes in the mobility of heavy metal ions in porous media. The results showed that the mobility of different metal ions followed the order of Cd2+ < Zn2+ < Ni2+ < Mn2+ < Co2+ despite of LMWOAs-free or LMWOAs-addition. For each heavy metal, all the organic acids enhanced its transport by forming stable non-adsorbing metal-LMWOA complexes and the enhanced ability followed the order of citric acid > oxalic acid > malonic acid > tartaric acid > acetic acid. An interesting finding was that there was a significantly positive correlation between the enhanced abilities of LMWOAs to metal mobility and the complex stability constants (log K) (R2 = 0.801-0.961, p < 0.05), indicating that the complex stability of metal-LMWOA was the dominant factor responsible for the enhanced transport of heavy metal ions. Meanwhile, the linear slope indicated the intensity of enhancement of LMWOAs on heavy metal mobility was heavy metal type-dependent. This study proposed that the complex stability of metal-LMWOA could be an indicator to quantify and predict the impact of LMWOAs on the mobility of heavy metals.

Nitrogen-rich carbon nitride as solid-phase microextraction fiber coating for high-efficient pretreatment of polychlorinated biphenyls from environmental samples.

A two-dimensional nitrogen-rich carbon nitrogen (C3N5) material was prepared via a facile high temperature thermal polymerization. For the first time, the C3N5 was used as fiber coating of solid-phase microextraction (SPME) to extract and preconcentrate polychlorinated biphenyls (PCBs) before gas chromatography (GC) analysis. The X-ray diffraction, N2 adsorption-desorption, Fourier transform-infrared spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy were performed to investigate structure, functional groups, thermal stability, bonding type, element composition, and atomic ratio of C3N5. The two-dimensional planar stacking structure was further verified by scanning electron microscopy and transmission electron microscopy. Five PCBs including PCB-4, PCB-12, PCB-29, PCB-52 and PCB-101 were selected as targets to evaluate performance of SPME fiber. Under the optimal conditions, the method showed a good linear range from 0.01 to 1000 ng/mL with the correlation coefficients (R2) higher than 0.9990. Enrichment factors of the method were obtained from 2045 to 3080. The limits of detection (LODs, S/N = 3) and limits of quantification (LOQs, S/N = 10) were calculated as 0.0031-0.0111 ng/mL and 0.01-0.05 ng/mL, respectively. The precisions of intra-day and inter-day were obtained with the relative standard deviations (RSDs) at 1.5-6.6% and 0.8-6.9%, respectively. The fiber-to-fiber producibility was achieved with RSDs ranged from 3.5% to 11.4%. The method was applied to detect PCBs in river water and soil samples. The contents were calculated at 0.040-0.147 ng/mL in water and 0.520-3.218 ng/g in soil. The C3N5 as SPME fiber coating material may be applied to extract and preconcentrate other environmental pollutants which have similar chemical structures with PCBs.

Fabrication of stable multivariate metal-organic frameworks with excellent adsorption performance toward bisphenols from environmental samples.

As a type of environmental endocrine disrupting chemicals, bisphenols (BPs) have a certain embryonic toxicity and teratogenicity, which can significantly increase the risks of breast cancer, prostate cancer, leukemia and other cancers. In this work, stable multivariate metal-organic frameworks (UiO-66-NH2/TCPPx) were synthesized via in situ one-pot method and used as miniaturized dispersive solid-phase extraction (dµSPE) sorbents for extraction of trace BPs from environmental samples. The phase purity, crystal morphology and physical properties of UiO-66-NH2/TCPPx samples were varied by adjusting the mass ratio of TCPP. The extraction performance of UiO-66-NH2/TCPPx samples were investigated and UiO-66-NH2/TCPP1.0 exhibited the highest adsorption efficiency. Besides, UiO-66-NH2/TCPP1.0 possessed excellent recycling stability for the adsorption and desorption of BPs more than 20 cycles. The experimental parameters including amount of adsorbent, adsorption time, sample solution pH, temperature, desorption time and desorption solvents which affecting the efficiency of dµSPE were studied, respectively. Good linearity (R2 > 0.9992) in range of 0.1-200 ng mL-1 was obtained. The detection limits (S/N = 3) and quantification limits (S/N = 10) were achieved at 0.03-0.08 ng mL-1 and 0.1-0.5 ng mL-1, respectively. The relative standard deviations (RSDs) of intra-day and inter-day ranged from 2.5 to 5.5% and 1.1-6.8%. Enrichment factors were calculated in the range of 303-338. The obtained recoveries of bisphenol F (BPF), bisphenol A (BPA), bisphenol B (BPB) and bisphenol AF (BPAF) were 81.26-91.03% (RSDs = 0.96-6.47%), 82.2-97.27% (RSDs = 0.45-6.15%), 87.56-97.26% (RSDs = 1.1-6.22%) and 82.2-100.8% (RSDs = 0.46-4.07%). The UiO-66-NH2/TCPP1.0 can be employed as potential dµSPE sorbents for the enrichment of trace BPs in the environmental samples.

MIL-101(Fe)-derived magnetic porous carbon as sorbent for stir bar sorptive-dispersive microextraction of sulfonamides.

Using MIL-101(Fe) as the source of carbon and Fe, a magnetic porous carbon (MPC) material with Fe3C nanoparticles encapsulated in porous carbon was prepared through one-pot pyrolysis under N2 atmosphere. With MPC as adsorption material, a stir bar sorptive-dispersive microextraction (SBSDME) method was proposed to extract and preconcentrate sulfonamides (SAs) prior to HPLC-DAD determination. To investigate their extraction ability, different MPC materials were prepared under different carbonization temperatures (600, 700, 800, 900, and 1000 °C). The material prepared under 900 °C (MPC-900) exhibited the highest extraction ability for SAs. The as-prepared MPC materials were also characterized by Raman spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, zeta potential, and other techniques. The main parameters that affect extraction were systematically studied. Under optimal conditions, favorable linearity (R2 ≥ 0.9938) and detection limits (0.02-0.04 ng mL-1) of sulfonamides were obtained. The average recoveries for spiked milk and lake water samples ranged from 76.9 to 109% and from 75.4 to 118% with RSDs of 3.10-9.63% and 1.71-11.3%, respectively. Sulfameter and sulfisoxazole were detected in milk sample. Sulfisoxazole was detected in the lake water sample. The MPC-900 material demonstrated excellent reusability. It can be reused 24 times with peak areas having no obvious decline. The method can be applied to extract ultra-trace compounds in complex sample matrices. Schematic presentation of a stir bar sorptive-dispersive microextraction (SBSDME) by using magnetic porous carbon (MPC) composites as sorbent combined with high-performance liquid chromatography for sensitive analysis of sulfonamides in milk and lake water samples.