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.

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.

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.

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.

Highly efficient solid-phase microextraction of polycyclic aromatic hydrocarbons in water based on worm-like nickel-titanium oxide nanocomposites coating grown on a nickel-titanium alloy wire by low-voltage anodization.

A novel worm-like nickel-titanium oxide nanocomposite coating was directly grown on a nickel-titanium alloy wire by low-voltage electrochemical anodization in alkaline ethylene glycol and water solution. The in situ growth of nickel-titanium oxide nanocomposites greatly depended on the volume ratio of ethylene glycol to water and temperature. Coupled to high-performance liquid chromatography with UV detection by static desorption in the mobile phase, the adsorption performance of the as-prepared fiber was evaluated for solid-phase microextraction of representative environmental analytes in water. The results indicate that the as-prepared fiber exhibits higher extraction capability for polycyclic aromatic hydrocarbons than commercial polydimethylsiloxane and polyacrylate fibers. After optimizing the extraction parameters, the calibration graphs of the developed method was linear in the range of 0.05-200 µg/L with correlation coefficients above 0.998. Limit of detection ranged from 0.013 to 0.145 µg/L for seven target analytes. Relative standard deviations of intraday and interday analyses varied from 4.0 to 5.3% and from 4.7 to 6.3% with the single fiber, respectively. The relative recoveries of 84.4-109% were achieved for highly efficient enrichment and determination of target analytes in spiked river and snow water. Moreover, the as-prepared fiber can be used more than 200 times.

UiO series of metal-organic frameworks composites as advanced sorbents for the removal of heavy metal ions: Synthesis, applications and adsorption mechanism.

Heavy metal pollution has threatened the ecological environment and human health, therefore, effective removal of these toxic pollutants from various complex substrates is of great significance. So far, adsorption is still one of the most effective approaches. Metal-organic frameworks (MOFs), which are porous crystalline materials consisting of metal ions or metal clusters and organic ligands through coordination bonds. Due to their high surface area, porosity, as well as good chemical/thermal stability, the materials have recently attracted great attention in environmental analytical chemistry. This review mainly focused on the recent studies about the applications of UiO series MOFs and their composites as the emerging MOFs, which have been used effectively for the adsorption and removal of diverse heavy metal ions from a variety of environmental samples as novel adsorption materials. Moreover, an elaboration about UiO-MOFs and its composites including the synthetic methods and the applications of these materials in the removal of heavy metal ions were presented in detail. In addition, the adsorption characteristics and mechanism of UiO-MOFs as solid sorbents for heavy metal ions were discussed, including adsorption isotherms equation, adsorption thermodynamics, and kinetics. To this end, the developing trends of MOF-based composites for the removal of heavy metal ions had also prospected. This review will provide a new idea for the study of the adsorption mechanism of heavy metal ions on sorbents and the development of high-performance media for the efficient removal of pollutants in wastewater.

NiFe2O4-based magnetic covalent organic framework nanocomposites for the efficient adsorption of brominated flame retardants from water.

A new kind of NiFe2O4-based magnetic covalent organic framework nanocomposites (NiFe2O4@COFs) was fabricated through facile synthesis approach under room temperature. The NiFe2O4@COFs exhibited higher adsorption capacity for brominated flame retardants than carbon nanotube material based on hydrophobic interactions, π-π stacking interaction, and van der Waals forces. In addition, the adsorption isotherm and the kinetic model were more suitable for Langmuir and pseudo-second-order model, respectively. NiFe2O4-based magnetic covalent organic framework nanocomposites combined with HPLC-UV (absorption wavelength: 214 nm) technology has excellent adsorption performance, which exhibited low detection limits (0.03-1.9 µg L-1), wide linear range (0.11-1000 µg L-1), good recoveries (91.5-102%) with a relative standard deviation of less than 2.9%. Finally, the prepared magnetic material was successfully used asadsorbents of magnetic solid-phase extraction and applied to the determination of five BFRs from the real water samples. The adsorption and removal of BFRs by NiFe2O4@COFs from water samples.

Modulating the selectivity of solid-phase microextraction fibers based on morphological, compositional, and size-depended control of bimetallic oxide nanostructures grown on nickel-titanium alloy substrates.

Nickel-titanium oxide nanotubes (NiTiONTs), nanoparticles, and nanopores were in situ grown on NiTi fiber substrates by controlling anodization parameters. The adsorption performance of different bimetallic oxide nanostructures was evaluated using typical aromatic compounds including chlorophenols, phthalic acid esters, ultraviolet filters (UVFs), and polycyclic aromatic hydrocarbons (PAHs) coupled to HPLC-UV. The results clearly indicate that these NiTiO nanostructures show good extraction capability for UVFs and PAHs. The extraction performance of UVFs and PAHs greatly depends on the surface morphologies and sizes of the grown NiTiO nanostructures along with their elemental compositions. Compared with NiTiO nanoparticle and nanopore coatings, the longer well-aligned NiTiONT coating exhibits better extraction capability and selectivity for PAHs than for UVFs. Therefore, the extraction parameters of the NiTi@NiTiONT fiber for PAHs were investigated and optimized. Under optimized conditions, the proposed method was linear in the range 0.05-200 µg L-1 with correlation coefficients above 0.999. Limits of detection were between 0.008 and 0.124 µg L-1. Relative standard deviations (RSDs) of the intra-day and the inter-day analyses with the single fiber varied from 4.09 to 6.33%. RSDs for fiber-to-fiber reproducibility of the proposed method with five fibers prepared in different batches were between 5.75 and 7.43%. The applicability of the proposed method was investigated by the enrichment and determination of target PAHs in environmental water samples and relative recoveries of 84.5 ± 6.5 - 116 ± 7.8% were achieved. Notably, the prepared fiber was stable up to 250 times. Graphical abstract.

Mesostructured cellular foam solid-phase microextraction coating for the highly sensitive recognition of polychlorinated biphenyls in water samples.

We herein presented a mesoporous cellular foam solid-phase microextraction coating that showed highly sensitive recognition for weakly polarity polychlorinated biphenyls in water samples. The mesoporous cellular foam coater fiber was for the first time prepared by a simple sol-gel method. The main experimental parameters including extraction temperature, extraction time, desorption time, stirring rate, and ionic strength were investigated by high-efficiency orthogonal array design, a L16 (44 ) matrix was applied for the identification of optimized extraction parameters, and the optimized method was successfully applied to the analysis of environmental water sample. The novel mesoporous cellular foam coated fibers exhibited sensitive limits of detection (0.07-0.28 µg/L), wide linearity (5-3000 µg/L), and good reproducibility (3.5-8.3% for single fiber, and 4.9-8.7% for fiber-to-fiber) for polychlorinated biphenyls. The home-made coating was successfully used in the analysis of polychlorinated biphenyls in real environmental water samples. These results indicate that the synthesized mesoporous cellular foams are promising materials for adsorption and separation applications in sample pretreatment.

Tailoring the selectivity of titania nanowire arrays grown on titanium fibers by self-assembled modification of trichlorophenylsilane for solid-phase microextraction of polycyclic aromatic hydrocarbons.

The authors describe TiO2 nanowires (TiO2NWs) for solid-phase microextraction of polycyclic aromatic hydrocarbons (PAHs). Well-oriented TiO2NWs were in-situ grown on a titanium wire by a hydrothermal process. The TiO2NWs arrays are radially aligned on the curved titanium fiber substrate. They possess a large surface area and are readily accessible for subsequent self-assembly of trichlorophenylsilane via formation of Ti-O-Si bonds. The TiO2NWs coated fibers show good extraction selectivity for PAHs as shown for phenathrene, fluoranthene, pyrene and benzo[a]pyrene. Following desoption by mobile phases for HPLC analysis, the PAHs were quantified by HPLC with UV detection. The improved extraction capabilities and good selectivity are explained by synergistic hydrophobic and π stacking interactions between the phenyl moieties and the PAHs. Key parameters that affect the extraction performance of the fibers were optimized. The method has a linear response in the 0.1 to 200 µg·L-1 PAH concentration range. Limits of detection (at S/N = 3) range from 20 to 50 ng·L-1. Relative standard deviations (RSDs) for the single fiber repeatability are less than 7.3% (n = 5) and RSDs for the fiber-to-fiber reproducibility are below 8.1% (n = 5). The method was successfully applied to the selective preconcentration and determination of trace PAHs in spiked water samples. Graphical abstract Schematic presentation of fabrication and characterization of the Ti@TiO2NWs@Phenyl fiber. PAHs: polycyclic aromatic hydrocarbons; UVFs: ultraviolet filters; PAEs: phthalate acid esters; CPs: chlorophenols.

Determination of six benzotriazole ultraviolet filters in water and cosmetic samples by graphene sponge-based solid-phase extraction followed by high-performance liquid chromatography.

An approach for fabrication of graphene sponge (GS)-based solid-phase extraction (SPE) followed by high-performance liquid chromatography (HPLC) with ultraviolet detection (HPLC-UV) is proposed, which was applied to determine the six benzotriazole UV filters in water and cosmetic samples. Several extraction conditions including type of elution solvent, the volume of elution solvent, and salt effect were optimized. Under the optimum conditions, the GS-SPE-HPLC-UV method shows a low limit of detection (LOD, S/N = 3) of 0.02-0.08 µg L-1 for standard solution, limits of quantification (LOQ, S/N = 10) of 0.07-0.26 µg L-1 for standard solution, wide linear ranges from 20.0 to 1000 µg L-1 for all compounds for standard solution, correlation coefficients (r) of more than 0.999, except for 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV-P), and acceptable reproducibility (relative standard deviations, RSDs < 6.5% for intra-day, RSDs < 8.1% for inter-day). The satisfactory recoveries were obtained in the range 89-105% with RSDs lower than 9.8% at the three spiked levels of 20, 50, and 100 µg L-1. Every home-made GS-SPE cartridge can be reused for more than 60 cycles. The method is facile, low-cost, rapid, sensitive, and suitable for the determination of UV filters in water and cosmetics samples. Graphical abstract ᅟ.

Oriented ZnO nanoflakes on nickel-titanium alloy fibers for solid-phase microextraction of polychlorinated biphenyls and polycyclic aromatic hydrocarbons.

ZnO nanoflakes (ZnONFs) were electrochemically grown on a nickel-titanium alloy (NiTi) wire for use in solid-phase microextraction. Prior to the growth of ZnONFs, the NiTi wire was hydrothermally treated for in-situ growth of TiO2/NiO nanoflakes as a seeding base. The applied potential was used to control the dimensions of vertically oriented hexagonal ZnONFs. After annealing at 600 °C, the resulting fiber display fairly selective affinity for polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons. The fibers were applied to the preconcentration of PCBs which then were quantified by HPLC with UV detection. Compared to commercial polydimethylsiloxane coatings, the new coating displays high extraction capability, rapid extraction kinetics and superior cycling stability. This is assumed to be due to its high surface-to-volume ratio, double-sided open access structure, and enhanced structural stability. The assay excels by (a) a wide analytical range (0.10 to 200 µg L-1 of PCBs), (b) low limits of detection (20-17 ng L-1), and (c) low standard deviations for the single fiber repeatability (<9.8%) and for the fiber-to-fiber reproducibility (<7.5%). Satisfactory accuracy and precision were achieved when PCBs were determined by this method in spiked rain water, river water and wastewater samples. Graphical abstract ZnO nanoflakes were fabricated on a superelastic nickel-titanium alloy wire in desired orientation with enhanced extraction capability and good extraction selectivity. The fabricated fiber was suitable for the determination of PCBs in environmental water samples.

Electrophoretic deposition strategy for the fabrication of highly stable functionalized silica nanoparticle coatings onto nickel-titanium alloy wires for selective solid-phase microextraction.

A new strategy for the immobilization of phenyl-functionalized silica nanoparticles onto nickel-titanium alloy wires is presented. The homogeneous and compact silica nanoparticle coating was achieved on the hydrothermally treated nickel-titanium wires with large surface area by electrophoretic deposition, and followed by self-assembled modification of phenyltrichlorosilane. Coupled to high-performance liquid chromatography with ultraviolet detection, the extraction performance of the fabricated fiber was evaluated using typical aromatic compounds in direct-immersion mode of solid-phase microextraction. Due to its high extraction efficiency and good selectivity for ultraviolet filters, the novel fiber was employed to investigate the key factors affecting the extraction of ultraviolet filters. Under the optimized conditions, the proposed method presented linear ranges from 0.05 to 300 µg/L with correlation coefficients higher than 0.999 and limits of detection from 0.005 to 0.058 µg/L. Relative standard deviations were below 4.3 and 5.6% for intraday and interday analyses at the spiking level of 50 µg/L ultraviolet filters with the single fiber, respectively. The proposed method was successfully applied to the selective concentration and sensitive detection of target ultraviolet filters from environmental water samples. Furthermore, the developed fiber can be used at least 200 times, and fabricated in a precisely controllable manner.

Rapid in situ growth of oriented titanium-nickel oxide composite nanotubes arrays coated on a nitinol wire as a solid-phase microextraction fiber coupled to HPLC-UV.

An oriented titanium-nickel oxide composite nanotubes coating was in situ grown on a nitinol wire by direct electrochemical anodization in ethylene glycol with ammonium fluoride and water for the first time. The morphology and composition of the resulting coating showed that the anodized nitinol wire provided a titania-rich coating. The titanium-nickel oxide composite nanotubes coated fiber was used for solid-phase microextraction of different aromatic compounds coupled to high-performance liquid chromatography with UV detection. The titanium-nickel oxide composite nanotubes coating exhibited high extraction capability, good selectivity, and rapid mass transfer for weakly polar UV filters. Thereafter the important parameters affecting extraction efficiency were investigated for solid-phase microextraction of UV filters. Under the optimized conditions, the calibration curves were linear in the range of 0.1-300 µg/L for target UV filters with limits of detection of 0.019-0.082 µg/L. The intraday and interday precision of the proposed method with the single fiber were 5.3-7.2 and 5.9-7.9%, respectively, and the fiber-to-fiber reproducibility ranged from 6.3 to 8.9% for four fibers fabricated in different batches. Finally, its applicability was evaluated by the extraction and determination of target UV filters in environmental water samples.

3-D graphene-supported mesoporous SiO2 @Fe3 O4 composites for the analysis of pesticides in aqueous samples by magnetic solid-phase extraction with high-performance liquid chromatography.

Three-dimensional graphene-supported mesoporous silica@Fe3 O4 composites (mSiO2 @Fe3 O4 -G) were prepared by modifying mesoporous SiO2 -coated Fe3 O4 onto hydrophobic graphene nanosheets through a simple adsorption co-condensation method. The obtained composites possess unique properties of large surface area (332.9 m(2) /g), pore volume (0.68 cm(3) /g), highly open pore structure with uniform pore size (31.1 nm), as well as good magnetic separation properties. The adsorbent (mSiO2 @Fe3 O4 -G) was used for the magnetic solid-phase extraction of seven pesticides with benzene rings in different aqueous samples before high-performance liquid chromatography. The main parameters affecting the extraction such as adsorbent amount, volume of elution solvent, time of extraction and desorption, salt effect, oscillation rate were investigated. Under the optimal conditions, this method provided low limits of detection (S/N = 3, 0.525-3.30 µg/L) and good linearity (5.0-1000 µg/L, R(2) > 0.9954). Method validation proved the feasibility of the developed adsorbent, which has a high extraction efficiency and excellent enhancement performance for pesticides in this study. The proposed method was successfully applied to real aqueous samples, and satisfactory recoveries ranging from 77.5 to 113.6% with relative standard deviations within 9.7% were obtained.

A novel system of galangin-potassium permanganate-polyphosphoric acid for the determination of tryptophan and its chemiluminescence mechanism.

A novel galangin-potassium permanganate (KMnO4)-polyphosphoric acid (PPA) system was found to have an outstanding response to tryptophan (Trp). Trp determination using this KMnO4 -PPA system was enhanced significantly in the presence of galangin. A highly sensitive flow-injection chemiluminescence (CL) method to determine Trp was developed based on the CL reaction of galangin-KMnO4 -Trp in PPA media. The presence of galangin, a member of the flavonol class of flavonoid complexes, greatly increased the luminous intensity of Trp in KMnO4 -PPA systems. Under optimized conditions, Trp was determined in the 0.05-10 µg/mL range, with a detection limit (3σ) of 5.0 × 10(-3) µg/mL. The relative standard deviation (RSD) was 1.0% for 11 replicate determinations of 1.0 µg/mL Trp. Two synthetic samples were determined selectively with recoveries of 98.4-100.1% in the presence of other amino acids. The possible mechanism is summarized as follows: excited states of Mn(II)(*) and Mn(III(*) types are the main means of generating chemical luminescent species, and Trp concentration and luminescence intensity have a linear relationship, which enables quantitative analysis.

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.

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.

Yolk-shell MOF-on-MOF hybrid solid-phase microextraction coatings for efficient enrichment and detection of pesticides: Structural regulation cause performance differences.

Metal-organic frameworks (MOFs) based composites with different structure-activity relationships have been widely used in the field of organic pollutant adsorption and extraction. Here, two MOF-on-MOF composites with different structures (yolk-shell and core-shell) from homologous sources were prepared by a simple in-situ growth synthesis method and structural regulation. In order to verify the effect of composite structure on the extraction capacity, the adsorption performance of the yolk-shell structure (YS-NH2-UiO-66@CoZn-ZIF) and the core-shell structured (NH2-UiO-66@CoZn-ZIF) material were compared by using them as coating material of direct immersion solid-phase microextraction (DI-SPME) to enrich six pesticides in five matrices. The results showed that because of the unique hollow hierarchical structure, high specific surface area (930.68 m2 g-1), abundant and open active sites, and synergistic and complementary adsorption forces, YS-NH2-UiO-66@CoZn-ZIF composites had the maximum adsorption amount of 36.01-66.31 mg g-1 under the same experiment condition, which was 6.81%-34.26 % higher than that of NH2-UiO-66@CoZn-ZIF. In addition, the adsorption mechanism of the prepared materials was verified and elaborated through theoretical simulations and material characterization. Under the optimized conditions, the YS-NH2-UiO-66@CoZn-ZIF-coated SPME-HPLC-UV method had a wide linear range (0.241-500 µg L-1), a good linear correlation coefficient (R2 > 0.9988), a low detection limits (0.072-0.567 µg L-1, S/N = 3) and low quantification limits (0.241-1.891 µg L-1, S/N = 10). The relative standard deviations of individual fibers and different batches of fibers were 0.47-6.20 % and 0.22-2.48 %, respectively, and individual fibers could be recycled more than 104 times. This work provided a good synthetic route and comparative ideas for exploring the in-situ growth synthesis of yolk-shell composites with reasonable structure-activity relationships.

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.