Ultra-thin FeCoNi-LDH hollow nanoflower as solid-phase microextraction coating for targeted capture of six pesticides by electrostatic adsorption.

Pesticides are common pollutants that cause detriment to the ecological environmental safety and health of human due to their toxicity, volatility and bioaccumulation. In this work, an ultra-thin polymetallic layered double hydroxide (FeCoNi-LDH) with hollow nanoflower structure composite was synthesized using ZIF-67 as a self-sacrificial template, which was used as solid-phase microextraction (SPME) coating for the targeted capture pesticides, which could be combined with high-performance liquid chromatography (HPLC) to sensitive inspection pesticides in real water samples. Orthogonal experimental design (OAD) was applied to ensure the best SPME condition. Additionally, the adsorption properties were evaluated by chemical thermodynamics and kinetics. Under the optimized conditions, high adsorption capacity was obtained (117.0-21.5 mg g-1). A wide linear range (0.020-1000.0 µg L-1), low detection limit (0.008-0.172 µg L-1) and excellent reproducibility were obtained under the established method. This research provided a new strategy for designing hollow materials with multiple cations for the adsorption of anion or organic pollutants.

One-step solvent thermal synthesis of 3D networked MOF composites for preparation of an ultrasensitive chemosensor for hydroquinone and catechol.

Pharmaceuticals and personal care products (PPCPs) have a significant impact on the environment and human health, due to their sometimes toxic and carcinogenic characteristics. Therefore, an innovative chemosensor was constructed for ultrasensitive determination of two typical PCCPs (hydroquinone (HQ) and catechol (CC)) in several minutes. The homemade chemosensor (UiO-67@GO/MWCNTs) consisted of MOF(UiO-67), graphene oxide (GO), and multi-walled carbon nanotubes (MWCNTs) composites; it was a networked, structurally sparse, porosity-rich, homogeneous octahedral composite, and had ultra-high electrical conductivity, which provided lots of active adsorption sites, promote charge transfer, and enrich lots of molecules to be measured in a few minutes. The prepared electrochemical sensor showed good long-term stability, applicability, reproducibility, and immunity to interference for the determination of HQ and CC, with a wide linear range of response of 5.0 ~ 940 µM for both HQ and CC, and a low limit of detection with satisfactory recoveries. In addition, a new strategy of using MOF composites as the basis for electrochemical determination of organic small molecules was established, and a new platform was constructed for the quantitative determination of organic small molecules in various environmental samples.

Controlled construction of 2D hierarchical core-shell ZnO/MnO2 nanosheets on Nitinol fiber with enhanced adsorption performance for selective solid-phase microextraction of trace polycyclic aromatic hydrocarbons in water samples.

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) are an important class of potentially toxic persistent organic pollutants in environmental water. Their concentrations are usually too low to allow for direct determination with analytical instruments, and the preconcentration is required prior to instrumental analysis. Solid phase microextraction (SPME) is considered as a high-performance green sample preparation technique for volatile and non-volatile organic compounds due to its high enrichment factor. In fact, the nature of SPME coatings governs the adsorption performance. Therefore, more efforts have devoted to the controlled construction of novel long-life SPME fibers with enhanced adsorption performance and improved adsorption selectivity. RESULTS: 2D hierarchical core-shell ZnO/MnO2 nanosheets (NSs) were constructed on a Nitinol (NiTi) fiber substrate by layer-by-layer assembly for enhanced and selective SPME of PAHs. Firstly, hexagonal ZnO NSs were electrodeposited on the NiTi substrate. Subsequently smaller secondary MnO2 NSs were uniformly grown on the surface of ZnO NSs by a facile hydrothermal oxidation process. ZnO NSs were well protected by the chemically stable MnO2 shell, making the coating highly durable and efficient for SPME application. Meanwhile, the ZnO/MnO2 NSs coating demonstrated superior adsorption performance for PAHs. After the optimization of SPME conditions, the proposed SPME-HPLC-UV method exhibited good analytical performance for preconcentrating and determining trace PAHs with wide linear ranges (0.03-200 µg L-1) and low LODs (0.005-0.112 µg L-1) as well as good repeatability (1.4%-6.9%) and fiber-to-fiber reproducibility (5.3%-7.1%). Moreover, the proposed method showed good precision and recovery in the preconcentration and determination of target PAHs in real water samples. SIGNIFICANCE: As compared with representative commercially available fibers, the NiTi@ZnO/MnO2 NSs fiber showed enhanced adsorption efficiency and improved adsorption selectivity for PAHs. The constructed fiber can be used as an alternative to commercial fibers for the adsorption and preconcentration of target PAHs in the environmental water samples. Moreover, the preparation strategy is expected to provide new insights into the precisely controlled construction of the efficient and stable core-shell bimetallic oxide nanostructures on the superielastic NiTi-based fibers.

A novel top-down strategy for in situ construction of vertically oriented hexagonal NiCr LDHs nanosheet arrays with intercalated sulfate ions on Nichrome fiber for selective solid-phase microextraction of phenolic compounds in water samples.

BACKGROUND: Phenolic compounds (PCs) are a class of polar aromatic pollutants with high toxicity in environmental water. Generally the efficient sample preparation is essential for the quantification of ultra-trace target PCs in real water sample before appropriative instrumental analysis. SPME is a convenient, solvent-free and time-saving miniaturized technique and has been recognized as a green alternative to conventional extraction techniques. In SPME, however, commercial fused-silica fibers are limited to the fragility, operation temperature, extraction capacity and selectivity as well as lifetime. Therefore, the development of new SPME fibers is always needed to overcome such limitations. RESULTS: We presented a novel top-down strategy for in situ construction of vertically oriented hexagonal sulfate intercalated NiCr layered double hydroxide nanosheet arrays (NiCr LDHs-SO4 NSAs) on the Nichrome (NiCr) substrate by hydrothermal treatment in NaOH solution containing (NH4)2S2O8. The results showed that much shorter hydrothermal time was needed for the construction of NiCr@NiCr LDHs-SO4 NSAs fiber in the presence of (NH4)2S2O8. Moreover, the unique NiCr LDHs-SO4 NSAs coating offered open access structure, and thereby more available surface area for adsorption. The resulting fiber exhibited better extraction efficiency for phenolic compounds (PCs), faster mass transfer rate, higher mechanical stability, and longer service life than original NiCr@NiCr LDHs NSs fiber and typical commercially fused-silica fibers. After optimizing conditions, the SPME-HPLC-UV method demonstrated a linear range from 0.05 µg L-1 to 200 µg L-1 with LODs of 0.015-0.156 µg L-1 (S/N = 3) and LOQs of 0.048-0.498 µg L-1 (S/N = 10), as well as good repeatability (3.06%-5.22%) and fiber-to-fiber reproducibility (4.32%-6.49%). SIGNIFICANCE: The developed SPME-HPLC-UV method with the constructed fiber was applied to the preconcentration and detection of different types of PCs in real water samples, showing satisfactory recoveries ranging from 86.20% to 107.8% with RSDs of 3.18%-6.69%. This study provides a new strategy for in situ construction of bimetallic hydroxides and their derived nanocomposite coatings on the NiCr fiber substrate in practical SPME application.

[Progress in preparation of hollow nanomaterials and their application to sample pretreatment].

Sample pretreatment technology plays a vital role in the analysis of complex samples and is key to the entire analytical process. Its main purpose is to separate the substance to be measured from the sample matrix or interfering substances in the sample and to achieve a state in which the instrument can be analyzed and detected. Traditional sample pretreatment techniques include liquid-liquid extraction, liquid-solid extraction, precipitation separation, solvent volatilization-rotary evaporation, filtration, and centrifugation. However, the applications of these methods are limited by their low extraction efficiency, complicated operation, long time consumption, unstable recovery, use of large amounts of organic solvents, and large error rates. Several new sample pretreatment techniques, including solid-phase extraction, magnetic solid-phase extraction, solid-phase microextraction, and dispersive solid-phase extraction, have been developed and rapidly applied to various fields to overcome the shortcomings of traditional sample pretreatment methods. However, the development of adsorbent materials with high selectivity and enrichment capability remains a challenge in sample pretreatment technology, in which adsorbents with excellent adsorption performance are crucial. In recent years, various nanomaterials with remarkable properties have been introduced and applied to sample pretreatment, and numerous nano-extraction materials with diverse functions and high selectivity and enrichment capability have been developed. Hollow nanomaterials are nanoparticles with large voids in their solid shells. Owing to their advantageous properties, which include a large effective surface area, abundant internal space, low density, variety of preparation methods, structural and functional tailorability, short mass transmission path, and high carrying capacity, hollow nanomaterials show great application potential in sample pretreatment. The extraction mechanism of these materials is based on the synergistic effects of π-π stacking, electrostatic, hydrogen-bonding, and hydrophobic interactions to achieve the efficient separation and enrichment of the target analytes. Given their noteworthy physicochemical properties, hollow nanomaterials have gained wide attention in various research fields and are considered a research frontier in the field of materials science. Changing the structure or surface properties of the core and shell can lead to various hollow nanomaterials with unique properties. Such changes can create synergy between the physicochemical properties and structural function of the original core-shell material, leading to novel materials with superior performance compared with the starting materials and broad application prospects in sample pretreatment. Nevertheless, only a few hollow nanomaterials with diverse structures and functions are currently used for sample pretreatment, and their adsorption capacity for target analytes is often unsatisfactory. Consequently, enhancing the adsorption selectivity of these materials toward various analytes is the most important step in sample pretreatment. First, hollow nanomaterials with a large specific surface area and suitable pore size can be designed to achieve the specific adsorption of target analytes of varying sizes. The combination of hollow nanomaterials with other materials presenting desirable adsorption properties could also lead to synergistic effects and enhance the performance of composite hollow nanomaterials. In addition, more green methods to prepare hollow nanomaterials with outstanding selectivity can be explored to achieve the superior adsorption of a specific target analyte. Efforts to synthesize hollow nanomaterials have been met with great success, but the available synthesis methods still suffer from complicated steps, high costs, relatively harsh conditions, and the use of highly toxic substances. This paper summarizes the main types of hollow nanomaterials, their synthesis methods, and research progress on sample pretreatment technologies (solid-phase extraction, solid-phase microextraction, magnetic solid-phase extraction, and dispersive solid-phase extraction) and describes the challenges encountered in the synthesis of hollow nanomaterials. The applications and developments of hollow nanomaterials in sample pretreatment are also discussed.

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.

[Efficient enrichment of pesticides from environmental water samples by cobalt-nickel double metal hydroxide nanocage/multiwalled carbon nanotube composites].

Pesticides are widely used in agriculture to increase grain yields and prevent crop diseases and insect pests. However, pesticides pose a serious threat to ecosystems and human health owing to their high toxicity and persistence. Therefore, it is imperative to establish an efficient and sensitive detection method for pesticides in water samples. Rapid and accurate detection of trace pesticides in environmental water samples has been a challenge because of complex matrix effects and trace concentrations. Appropriate sample pretreatment is a critical step for the effective extraction of analytes and removal of interferences, and the development and design of novel and stable nanomaterial adsorbents is key to continuous innovation in sample pretreatment technology. In recent years, carboxylated multiwalled carbon nanotubes (MWCNTs-COOH) and layered double hydroxide (LDHs) have been widely used as new adsorbent materials for various pretreatment technologies because of their large specific surface area, good stability, and easy functionalization. Based on this background, MWCNTs-COOH and LDHs were combined to obtain a new efficient composite adsorbent, so that the synergistic effect of the individual components could be exploited in entirety. In this study, a zeolitic metal organic framework ZIF-67/multiwalled carbon nanotube (ZIF-67/MWCNTs) composite was prepared by a simple one-step method, and a cobalt-nickel double metal hydroxide/multiwalled carbon nanotube (CoNi-LDH/MWCNTs) hybrid material with a three-dimensional cage-like structure was synthesized by a solvothermal method using ZIF-67/MWCNTs as templates. The cage-like structure of the CoNi-LDH/MWCNTs composite, which is different from the traditional layered bimetallic hydroxide, could accelerate mass transfer. Given the excellent properties of the CoNi-LDH/MWCNTs composite, it was used as a solid-phase microextraction (SPME) coating for the efficient enrichment of six pesticides (chlorothalonil, tebuconazole, chlorpyrifos, butralin, deltamethrin, and pyridaben) and combined with high performance liquid chromatography-ultraviolet (HPLC-UV) detection for the determination of the six pesticides in real water samples. The prepared materials were characterized by scanning electron microscopy, electron dispersion spectroscopy, infrared spectroscopy, X-ray powder diffraction, and N2 adsorption/desorption. The results confirmed that the CoNi-LDH/MWCNTs composite was successfully synthesized, and that its surface area and pore volume were 281.4 m2/g and 0.49 cm3/g, respectively. An orthogonal array design was used to optimize the extraction conditions of SPME, including the extraction time, extraction temperature, stirring rate, salt effect, and desorption time. The optimal extraction conditions were as follows: extraction temperature, 40 ℃; extraction time, 30 min; stirring rate, 500 r/min; desorption time, 6 min; and salt (NaCl) mass concentration, 150 mg/L. Under optimal conditions, the method had a wide linear range (chlorothalonil: 0.015-200 µg/L, tebuconazole: 0.140-200 µg/L, chlorpyrifos: 0.250-200 µg/L, butralin: 0.077-200 µg/L, deltamethrin: 1.445-200 µg/L, pyridaben: 0.964-200 µg/L), low detection limit (0.004-0.434 µg/L), and good reproducibility. The relative standard deviations (RSDs) of single fiber and fiber-to-fiber were in the range of 0.5% to 5.7% and 0.5% to 4.8%, respectively. The spiked recoveries at two levels of 10.0 µg/L and 50.0 µg/L were in the range of 83.9%-108.2%, with RSDs less than 5.3%. Compared with other coated fibers (MWCNTs-COOH, ZIF-67, ZIF-67/MWCNTs, and silicone sealant), the CoNi-LDH/MWCNTs-coated fibers showed a better enrichment effect for pesticides, which was attributed to their high specific surface area and π-π interactions, hydrophobic interactions, cation-π interactions, and hydrogen bonding interactions between the CoNi-LDH/MWCNTs coating and the target analytes, which can enhance their ability to extract pesticides. The stability test on the SPME fibers revealed that after 128 cycles, the extraction efficiency of the CoNi-LDH/MWCNTs-coated fibers for the six pesticides decreased only slightly (< 10%), implying that the coated fibers had good stability and reusability. Therefore, this method can be used to detect pesticide residues in environmental water samples with high selectivity, sensitivity, and accuracy.

In situ anchor of multi-walled carbon nanotubes into iron-based metal-organic frameworks for enhanced adsorption of polycyclic aromatic hydrocarbons by magnetic solid-phase extraction.

In this work, a magnetic MIL-101(γ-Fe2O3)/MWCNTs composite derived from iron-based metal-organic frameworks (MIL-101(Fe)) with multi-walled carbon nanotubes (MWCNTs) was successfully synthesized by low-temperature calcination process. The composite was used as adsorbent of magnetic solid-phase extraction (MSPE) for enhanced and rapid enrichment of trace polycyclic aromatic hydrocarbons (PAHs) based on its strong π-π stacking interactions, hydrophobic and cationic-π stacking interactions. The pseudo-second-order kinetic model and Langmuir isotherm model could be applied to better describe the adsorption process. The maximum adsorption capacity for PAHs reached 93.9 mg g-1. In addition, the conditions of MSPE process were optimized by orthogonal array design (OAD). A MSPE-HPLC-UV method was established for the sensitive detection of PAHs in real water samples and exhibited wide linear range (0.05-1000 µg L-1), low detection limits (0.02-0.41 µg L-1) and high enrichment factors (44-169) for PAHs. The relative standard deviations (RSD) ranged from 0.8 to 4.0% and 1.2-7.2% for single batch and batch-to-batch, respectively, and the spiked recoveries at two levels of 10 and 50 µg L-1 ranged from 79.6 to 112% with RSD of less than 5.81%. The unique MWCNTs in situ anchor MIL-101(γ-Fe2O3) composite with an outstanding PAHs adsorption performance provides a new opportunity and promising application in removal of toxic pollutants.

Rapid and Selective 19F NMR-Based Sensors for Fingerprint Identification of Ribose.

Ribose plays an important role in the process of life. Excessive ribose in the human cerebrospinal fluid or urine can be used as an early diagnostic marker of leukoencephalopathy. Fluorinated phenylboronic acid combined with 19F NMR spectroscopy was a powerful method for molecular recognition. However, phenylboronic acid-based sensors for selective detection of ribose are rarely reported in the literature. In this study, the rapid and highly selective recognition of ribose was studied by 19F NMR and 2-fluorophenylboric acid. It was found that 2-fluoro-phenylboric acid was an appropriate 19F NMR-based sensor molecule for the determination of ribose under physiological conditions with high selectivity and robust anti-interference ability. When 2-fluorophenylboric acid was used for the detection of ribose in human urine without any sample pretreatment, a limit of detection of 78 µM was obtained at room temperature under given 19F NMR experimental conditions (400 MHz, 512 scans, ca. 12 min), which can well meet the needs of practical application.

Hydrothermal in situ growth and application of a novel flower-like phosphorous-doped titanium oxide nanoflakes on titanium alloy substrate for enhanced solid-phase microextraction of polycyclic aromatic hydrocarbons in water samples.

A novel flower-like phosphorous-doped titanium oxide nanocomposite coating was in situ grown on nickel-titanium alloy (NiTi) fiber by hydrothermal treatment in phosphoric acid solution. The experimental results demonstrated that phosphorous-doped titanium oxide nanoflakes (P-TiONFs) with an average thickness of 80 nm were formed on the NiTi fiber substrate in 0.1 mol L-1 H3PO4 at 150 °C for 6 h. Thereafter, the resulting P-TiONFs were used as SPME fiber coatings for the adsorption of typical aromatic analytes from environmental water samples, which were determined by HPLC-UV. These P-TiONFs exhibited good adsorption selectivity for hydrophobic PAHs. After optimizing microextraction conditions, linear responses were achieved in the ranges of 0.05-200 µg L-1 for the determination of PAHs with determination coefficients higher than 0.999. LODs (S/N = 3) ranged from 0.009 to 0.132 µg L-1, while LOQs (S/N = 10) ranged from 0.030 to 0.441 µg L-1. RSDs for intra-day and inter-day analyses with a single fiber varied from 4.46% to 5.56% and 5.14%-6.75%, respectively. The relative recoveries of 83.60%-119.0% were achieved for the determination of PAHs in real water samples spiked at the concentration levels of 5.0 µg L-1 and 10.0 µg L-1 with RSDs below 7.38%. In addition, the fibers exhibited no significant decrease in adsorption efficiency after being used 240 adsorption and desorption cycles. The proposed method was successfully applied to the selective enrichment and determination of target PAHs in different water samples.

Controllable in situ growth of novel octahedral TiO2 nanoparticles on nickel/titanium alloy fiber substrate for selective solid-phase microextraction of ultraviolet filters in water samples.

The nature and fabrication of fiber coatings with good adsorption capacity and selectivity play a decisive role in solid-phase microextraction (SPME). In this work, a novel SPME fiber was fabricated through hydrothermal in situ growth of octahedral TiO2 nanoparticles (TiO2NPs) on a superelastic nickel/titanium alloy (NiTi) wire substrate in acid solution. The resulting fiber coatings were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. Acid types, acid concentration as well as hydrothermal temperature and time were found to be effective route to manipulate the morphologies and composition of TiO2-based nanoflakes grown on the NiTi fiber substrates. At the concentration of 0.4 mol L-1 HCl as well as hydrothermal temperature of 150 °C and hydrothermal time of 12 h, TiO2NPs were in situ grown on the NiTi wire substrates. The obtained NiTi wire with the TiO2NPs coating (NiTi@TiO2NPs fiber) was employed to investigate the adsorption of some representative aromatic analytes in water samples coupling with high-performance liquid chromatography with UV detection (HPLC/UV). The results clearly demonstrate that the fiber exhibits good extraction selectivity for ultraviolet filters (UVFs). In view of good extraction selectivity for the selected UVFs, the key experimental parameters were optimized. Under the optimum conditions, the calibration curves were linear in the ranges of 0.05-100 µg L-1 with the correlation coefficients greater than 0.998. Limits of detection (LODs) were 0.007 to 0.064 µg L-1. Furthermore, the intra-day and inter-day repeatability of the proposed method with the single fiber varied from 4.3% to 6.1% and from 4.5% to 6.8%, respectively. The fiber-to-fiber reproducibility ranged from 5.8% to 8.2%. The developed SPME-HPLC/UV method was applied to selective preconcentration and sensitive determination of target UVFs from real water samples. Moreover, the fabricated fiber showed precisely controllable growth and 150 extraction and desorption cycles.

Development of a novel porous cobalt, phosphorus and nitrogen co-doped carbonaceous coating by phosphiding ZIF-67 grown on nitinol fiber for selective solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples.

The nature and fabrication of the fiber coatings with good adsorption capacity and selectivity play a decisive role in solid-phase microextraction (SPME). In this work, a facile strategy was proposed to fabricate a cobalt, phosphorus and nitrogen co-doped carbonaceous (Co-P-NC) coating on superelastic nitinol (NiTi) substrate as a binder-free fiber for SPME. In particular, direct electrochemical in situ growth of ZIF-67 crystals served as the N-containing carbon precursor and sacrificial template for subsequent controllable conversion of ZIF-67 into a novel porous Co-P-NC coating on the NiTi wire substrate via a phosphiding process in a N2 atmosphere. The obtained NiTi wire with the Co-P-NC coating (NiTi@Co-P-NC) was employed to investigate the adsorption of some representative aromatic analytes in water samples for the first time coupling with high-performance liquid chromatography with UV detection (HPLC/UV). The results proved that the resulting fiber showed superior adsorption selectivity for polycyclic aromatic hydrocarbons (PAHs). Therefore, the key parameters were further examined for the adsorption and preconcentration of PAHs. Under the obtained conditions, linear chromatographic responses were achieved over the concentration ranges of 0.03-100 µg L-1 with the correlation coefficients ranging from 0.9980 to 0.9991. Limits of detection (LODs) were between 0.007 and 0.149 µg L-1 (S/N = 3). The developed SPME-HPLC/UV method was applied to selective preconcentration and sensitive determination of PAHs in water. Moreover, this fiber had good fiber preparation reproducibility and presented 120 adsorption and desorption cycles at the same time in practical SPME application.

A facile molecularly imprinted column coupled to GC-MS/MS for sensitive and selective determination of polycyclic aromatic hydrocarbons and study on their migration in takeaway meal boxes.

The analysis of toxic and harmful substances in food has attracted significant attention. In this work, a molecularly imprinted column coupled to gas chromatography-triple quadrupole tandem mass spectrometry method (MIC-GC-MS/MS) method for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in takeaway meal boxes was established by comparing the extraction results of 16 PAHs with 5 different sample pretreatment techniques, and the effects of food types and storage conditions on the migration of PAHs was studied by migration test. The conditions of extraction and chromatography-mass spectrometry were optimized. The results showed that the linear ranges were in the wide range of 1-100 ng mL-1 for 16 PAHs, with the correlation coefficients (R) higher than 0.9983; the detection limits (LODs) and the limits of quantification (LOQs) were in the range of 0.08-0.42 µg kg-1 and 0.24-1.26 µg kg -1, respectively; the spiked recoveries at three levels of 10, 20, 30 µg kg-1 were in the range of 86.2%-107.7% with the relative standard deviation (RSD) less than 7.8%. Therefore, this method had high sensitivity and good reproducibility and was suitable for the determination of 16 PAHs in food contact materials. The migration test of PAHs showed that the migration amount of PAHs in takeaway meal boxes was closely related to food types, and the migration amount was positively correlated with contact temperature and contact time in a certain range.

Selective solid-phase microextraction of polycyclic aromatic hydrocarbons in water based on oriented phosphorus-containing titanium oxide nanofibers grown on titanium support prior to high-performance liquid chromatography with ultraviolet detection.

A novel solid-phase microextraction coating of phosphorous-containing titanium oxide composite was developed using titanium fiber as a support and a titanium source by hydrothermal oxidation in a phosphoric acid solution containing hydrogen peroxide. The morphology of the fiber coatings was controlled by the conditions of the hydrothermal oxidation reaction. The oriented nanofiber coating was employed to extract several types of representative aromatic analytes. The experimental results demonstrated that the as-prepared fiber exhibited excellent extraction efficiency toward polycyclic aromatic hydrocarbons. Combined with high-performance liquid chromatography with ultraviolet detection, main extraction conditions were optimized, including pH, ionic strength, extraction temperature, stirring rate, extraction time and desorption time. The established method presented good linearity from 0.05 to 200 µg/L with limit of detection ranging from 0.012 to 0.126 µg/L. This convenient and green procedure was suitable for the selective extraction and determination of typical polycyclic aromatic hydrocarbons in environmental water samples. The relative recoveries of 85.8-112% were obtained for the determination of target polycyclic aromatic hydrocarbons in water samples spiked with 5.0 and 15.0 µg/L. Moreover, the as-prepared fiber showed at least 210 extraction/desorption cycles due to its high mechanical and chemical stability.

Controllable growth of flower-like hierarchical CoNiO2 nanoflakes anchored on Nitinol fiber substrate with good selectivity for highly efficient solid-phase microextraction of polycyclic aromatic hydrocarbons in water.

The flower-like hierarchical cobalt nickel oxide nanoflakes (CoNiO2NFs) with a porous structure were fabricated on Nitinol (NiTi) fiber substrate by a hydrothermal reaction and subsequent annealing treatment. The morphology affected by the molar ratios of Ni to Co and counter ions in starting precursors as well as hydrothermal reaction temperature and time was investigated in detail. The obtained CoNiO2NFs coating exhibited outstanding performance for the selective extraction of PAHs. After optimizing the main parameters that affected extraction through orthogonal experiments, the developed method showed good linearity in the ranges of 0.05 µg L-1 - 200 µg L-1 with the determination coefficient >0.999. LODs were between 0.006 µg L-1 and 0.114 µg L-1, LOQs were in the ranges of 0.020-0.376 µg L-1 and RSDs were below 5.19% and 5.71% for intra-day and inter-day analyses, respectively. The developed method was successfully applied to selective enrichment and determination of target PAHs in real water samples. Moreover, the fabricated fiber exhibited high chemical and mechanical stability, and could withstand more than 260 extraction-desorption cycles without loss of its extraction efficiency.

Fabrication of octahedral GO/UiO-67@PtNPs nanocomposites as an electrochemical sensor for ultrasensitive recognition of arsenic (III) in Chinese Herbal Medicine.

The pharmacological research and detection of heavy metals of Chinese Herbal Medicines (CHMs) are important for environmental protection and human health. Here, a novel electrochemical sensor has been proposed for the detection of arsenic (As (Ⅲ)) in CHMs. The sensing system was constructed based on the octahedral GO/UiO-67@PtNPs composites, which had a porous structure with a large, unique surface area and was conducive to the adsorption and enrichment of As (Ⅲ). The oxygen-containing functional groups of GO immobilized As (Ⅲ) metal ions and its own electrical conductivity, and nanoparticles (PtNPs) have electrocatalytic effects on As (Ⅲ), which can accelerate electron transfer and increase the abundance of active sites. Under the optimized conditions, the homemade electrode showed excellent electrochemical properties, satisfactory linear range (2.7-40 nM), and a lower limit of detection (LOD, 0.42 nM). It might be low-cost, rapid, sensitive, and quantitatively identified of As (Ⅲ) in various environmental samples, especially in the medical field.

Rapid synthesis of graphite phase carbon nitride/zeolitic imidazolate framework-8 with hierarchical structure and its superior adsorption of polycyclic aromatic hydrocarbons from aqueous solution.

Graphite phase carbon nitride (g-C3N4) incorporating zeolitic imidazolate framework-8 (ZIF-8) nanocomposite (g-C3N4 /ZIF-8) with hierarchical structure was synthesized successfully by simple and rapid in situ growth method at room temperature. The composites were used as an adsorbent of solid-phase extraction (SPE) and the superior adsorptive removal of polycyclic aromatic hydrocarbons (PAHs) for the first time. Under several optimum conditions, the g-C3N4 /ZIF-8-SPE-HPLC-FLD method show low detection limits (0.006-3.41 µg L-1) and limit of quantification (0.02-11.3 µg L-1), wide linear ranges from 0.02 to 1000 µg L-1 for all compounds, correlation coefficients (r) of more than 0.9968, and satisfying reproducibility (relative standard deviations, RSDs < 4.0% for intra-day, RSDs < 8.3% for inter-day), the spiked recoveries at two levels of 10.0, 50.0 µg L-1 were in the range of 77.4%-114% with the RSDs less than 8.66%. In addition, the g-C3N4/ZIF-8 nanocomposites demonstrated excellent enrichment ability and extraction efficiency for PAHs compared with commercial adsorbents, which might since there were strong π-π stacking force, hydrophobic interaction, hydrogen bonding, and more adsorption sites compared with other adsorbents. Finally, the g-C3N4 /ZIF-8 based SPE method was combined with high-performance liquid chromatography (HPLC) to detect fifteen PAHs in environmental water samples successfully.

GaOOH-modified metal-organic frameworks UiO-66-NH2: Selective and sensitive sensing four heavy-metal ions in real wastewater by electrochemical method.

Heavy metal pollution in the environment poses a serious threat to the ecosystem and human health, which has attracted widespread attention. In this study, an octahedral structure composite composed of UiO-66-NH2 MOFs and semiconductor GaOOH materials has been prepared and used as electrode materials successfully. These composites can be used for the real-time and online determination of Cd2+, Cu2+, Hg2+, and Pb2+ in real water samples simultaneously or alone via an electrochemical method. Zr-MOF has a large and unique surface area that is beneficial to the adsorption and preconcentration of heavy metal ions. The experiment parameters such as pH, deposition potential, and deposition time were optimized. Under the optimized conditions, the electrochemical performances and practical applications of Zr-MOF composites modified electrode have been investigated, which shows excellent wider linear range and lower detection limit (LOD). The results demonstrated excellent selectivity, reproducibility, stability and applicability for the detection of four metal ions. These superior features stem from the synergistic reaction mechanism of UiO-66-NH2 and GaOOH. In addition, it has been established a new detection strategy for heavy metal ions through the form of metal-organic framework (MOF) composite in this work. It may provide a novel platform for the quantitative determination of heavy metal ions in various environmental samples.

Temperature and time-controlled hydrothermal growth and sorption selectivity of titania nanowires on titanium fiber for highly efficient solid-phase microextraction.

Two kinds of TiO2 nanowires (TiO2NWs) with different orientation were in-situ grown on Ti substrates by controlling temperature and time during the hydrothermal process. The adsorption performance was evaluated by using typical aromatic compounds as model analytes coupled to HPLC with UV detection. The results demonstrated that the TiO2NWs coating grown at higher temperature within longer time had better affinity towards PAHs. For this purpose, the key experimental factors affecting the adsorption performance of the TiO2NWs coating fabricated at 200 °C for 10 h were further investigated and optimized for the extraction of PAHs. Under the optimized conditions, the proposed method presented linear responses in the concentration ranges of 0.05 to 200 µg·L-1 PAHs with correlation coefficients more than 0.998. LODs (S/N=3) were 0.008 to 0.034 µg·L-1. Moreover, RSDs for the single fiber repeatability of the intra-day and the inter-day analyses were less than 5.6% (n=5) and 5.8%, respectively. RSDs for the fiber-to-fiber reproducibility were between 5.1% and 6.5%. Finally, the proposed method was successfully applied to the selective preconcentration and determination of trace PAHs in environmental water samples. In addition, The fabricated Ti fiber can be used at least 200 times due to its high mechanical and chemical stability.

A Bisboronic Acid Sensor for Ultra-High Selective Glucose Assay by 19F NMR Spectroscopy.

Glucose is a significant analyte both in biology and biomedical science, it is of great importance to selectively detect glucose both in body fluids and complex mixture. In this study, a simple 19F NMR based sensor was synthesized easily, which exhibited a high selectivity and robust anti-interference ability toward glucose detection both in a mixture containing up to 10 saccharides and human urine samples without any pretreatment. Combined with this sensor system, glucose could be well detected in human urine samples and the limit of detection was 0.41 mM by using a 400 MHz NMR spectrometer with 128 scans (ca. 4 min). This method had a potential for specific detection of glucose in complex mixture and diagnosis of diabetes mellitus related diseases in body fluid.