Moisture-resistant and green cyclodextrin metal-organic framework nanozyme based on cross-linkage for visible detection of cellular hydrogen peroxide.

A moisture-resistant and green cyclodextrin metal-organic framework (CD-MOF) nanosheet has been prepared via an one-pot antisolvent synthesis procedure. After the treatment of in situ chemical cross-linkage, the two-dimensional (2D) cross-linked CD-MOF exhibited both peroxidase (POD) and oxidase (OXD) enzymatic activities, as well as hydrolytic stability. On the basis of its POD mimics function, the proof-of-concept biosensors were constructed to realize the colorimetric detection for H2O2 and glucose, respectively. In vitro cytotoxicity experiments showed that the 2D cross-linked CD-MOF nanozymes still maintained excellent biocompatibility even at a concentration reaching up to several mg/mL. The in situ colorimetric detection of H2O2 secreted by HepG2 cells further confirmed its promising biocompatibility, showing its great promises as label-free colorimetric probe in early cancer detection and pathological process monitoring.

Green preparation of carbon dots from Momordica charantia L. for rapid and effective sensing of p-aminoazobenzene in environmental samples.

p-Aminoazobenzene (pAAB) is a hazardous azo dye that causes considerable harm to human health and the environment. The development of novel and sensitive sensors for the rapid detection of pAAB is in high demand. In this study, a simple fluorescent sensor for pAAB detection is designed based on carbon dots (CDs) which are prepared using green carbon source of Momordica charantia L. via a facile hydrothermal approach. The fluorescence spectra of CDs exhibit considerable overlap with the absorption band of pAAB, and the fluorescence is specifically suppressed in the presence of pAAB ascribed to the inner filter effect. Good and wide linearity is observed in the pAAB concentration range of 0.01-12.5 µg mL-1 with a lower detection limit of 3.9 ng mL-1. The established method achieves good results with a rapid analysis of pAAB in different practical water and soil samples. The as-constructed fluorescent sensor provides a simple, rapid, economical and eco-friendly platform and possesses prospective applications for the effective, selective and sensitive detection of pAAB in the environmental field.

Chemical characteristics and source apportionment of PM2.5 in a petrochemical city: Implications for primary and secondary carbonaceous component.

To study the pollution features and underlying mechanism of PM2.5 in Luoyang, a typical developing urban site in the central plain of China, 303 PM2.5 samples were collected from April 16 to December 29, 2015 to analyze the elements, water soluble inorganic ions, organic carbon and elemental carbon. The annual mean concentration of PM2.5 was 142.3 µg/m3, and 75% of the daily PM2.5 concentrations exceeded the 75 µg/m3. The secondary inorganic ions, organic matter and mineral dust were the most abundant species, accounting for 39.6%, 19.2% and 9.3% of the total mass concentration, respectively. But the major chemical components showed clear seasonal dependence. SO42- was most abundant specie in spring and summer, which related to intensive photochemical reaction under high O3 concentration. In contrast, the secondary organic carbon and ammonium while primary organic carbon and ammonium significantly contributed to haze formation in autumn and winter, respectively. This indicated that the collaboration effect of secondary inorganic aerosols and carbonaceous matters result in heavy haze in autumn and winter. Six main sources were identified by positive matrix factorization model: industrial emission, combustion sources, traffic emission, mineral dust, oil combustion and secondary sulfate, with the annual contribution of 24%, 20%, 24%, 4%, 5% and 23%, respectively. The potential source contribution function analysis pointed that the contribution of the local and short-range regional transportation had significant impact. This result highlighted that local primary carbonaceous and precursor of secondary carbonaceous mitigation would be key to reduce PM2.5 and O3 during heavy haze episodes in winter and autumn.

One-step polymerization of hydrophilic ionic liquid imprinted polymer in water for selective separation and detection of levofloxacin from environmental matrices.

A novel green hydrophilic levofloxacin imprinted polymer was presented via one-step polymerization in water using ionic liquid 1,6-hexa-3,3'-bis-1-vinylimidazolium bromine with multiple hydrophilic groups and 2-hydroxyethyl methacrylate as a co-functional monomer. Adsorption experiment revealed that the ionic liquid significantly improved the water compatible of imprinted polymer, and the excellent recognition of molecularly imprinted polymer for levofloxacin in water corresponds to the synergetic effect of H-bonding and the electrostatic and π-π interactions between the levofloxacin and co-functional monomer. Furthermore, the adsorption process of the imprinted material towards levofloxacin fitted the Langmuir model, and the maximum binding amount of levofloxacin onto the imprinted and corresponding non-imprinted polymer were 16.45 and 6.82 mg/g at 25°C, respectively. After optimizing the parameters affecting solid phase extraction performance, an enrichment and determination system was achieved to separate and detect levofloxacin from water and sediment samples with recoveries that ranged from 83.67 to 101.33% and relative standard deviation of less than 5.59%.

Halogenated Organic Pollutant Residuals in Human Bared and Clothing-Covered Skin Areas: Source Differentiation and Comprehensive Health Risk Assessment.

To comprehensively clarify human exposure to halogenated flame retardants (HFRs) and polychlorinated biphenyls (PCBs) through dermal uptake and hand-to-mouth intake, skin wipe samples from four typical skin locations from 30 volunteers were collected. The total concentration of the target chemicals (24 HFRs and 16 PCBs) ranged from 203 to 4470 ng/m2. BDE-209 and DBDPE accounted for about 37 and 40% of ∑24HFRs, respectively, and PCB-41 and PCB-110 were the dominant PCB congeners, with proportion of 24 and 10%, respectively. Although exhibiting relatively lower concentrations of contaminants than bared skin locations, clothing-covered skin areas were also detected with considerable levels of HFRs and PCBs, indicating clothing to be a potentially significant exposure source. Significant differences in HFR and PCB levels and profiles were also observed between males and females, with more lower-volatility chemicals in male-bared skin locations and more higher-volatility compounds in clothing-covered skin locations of female participants. The mean estimated whole-body dermal absorption doses of ∑8HFRs and ∑16PCBs (2.9 × 10-4 and 6.7 × 10-6 mg/kg·d) were 1-2 orders of magnitude higher than ingestion doses via hand-to-mouth contact (6.6 × 10-7 and 3.1 × 10-7 mg/kg·d). The total noncarcinogenic health risk resulted from whole-body dermal absorption and oral ingestion to ∑7HFRs and ∑16PCBs were 5.2 and 0.35, respectively.

A new ionic liquid surface-imprinted polymer for selective solid-phase-extraction and determination of sulfonamides in environmental samples.

Toward improving the selective adsorption performance of molecularly imprinted polymers in strong polar solvents, in this work, a new ionic liquid functional monomer, 1-butyl-3-vinylimidazolium bromide, was used to synthesize sulfamethoxazole imprinted polymer in methanol. The resulting molecularly imprinted polymer was characterized by Fourier transform infrared spectra and scanning electron microscopy, and the rebinding mechanism of the molecularly imprinted polymer for sulfonamides was studied. A static equilibrium experiment revealed that the as-obtained molecularly imprinted polymer had higher molecular recognition for sulfonamides (e.g., sulfamethoxazole, sulfamonomethoxine, and sulfadiazine) in methanol; however, its adsorption of interferent (e.g., diphenylamine, metronidazole, 2,4-dichlorophenol, and m-dihydroxybenzene) was quite low. 1 H NMR spectroscopy indicated that the excellent recognition performance of the imprinted polymer was based primarily on hydrogen bond, electrostatic and π-π interactions. Furthermore, the molecularly imprinted polymer can be employed as a solid phase extraction sorbent to effectively extract sulfamethoxazole from a mixed solution. Combined with high-performance liquid chromatography analysis, a valid molecularly imprinted polymer-solid phase extraction protocol was established for extraction and detection of trace sulfamethoxazole in spiked soil and sediment samples, and with a recovery that ranged from 93-107%, and a relative standard deviation of lower than 9.7%.

A novel fluorescent aptasensor for sensitive and selective detection of environmental toxins fumonisin B1 based on enzyme-assisted dual recycling amplification and 2D δ-FeOOH-NH2 nanosheets.

Fumonisin (FB) is a pervasive hazardous substance in the environment, presenting significant threats to human health and ecological systems. Thus, the selective and sensitive detection of fumonisin B1 (FB1) is crucial due to its high toxicity and wide distribution in corn, oats, and related products. In this work, we developed a novel and versatile fluorescent aptasensor by combining enzyme-assisted dual recycling amplification with 2D δ-FeOOH-NH2 nanosheets for the determination of FB1. The established CRISPR/Cas12a system was activated by using activator DNA (aDNA), which was released via a T7 exonuclease-assisted recycling reaction. Additionally, the activated Cas12a protein was utilized for non-specifically cleavage of the FAM-labeled single-stranded DNA (ssDNA-FAM) anchored on δ-FeOOH-NH2 nanosheets. The pre-quenched fluorescence signal was restored due to the desorption of the cleaved ssDNA-FAM. Due to the utilization of this T7 exonuclease-Cas12a-δ-FeOOH-NH2 aptasensor for signal amplification, the detection range of FB1 was expanded from 1 pg/mL to 100 ng/mL, with a limit of detection (LOD) as low as 0.45 pg/mL. This study not only provides novel insights into the development of fluorescence biosensors based on 2D nanomaterials combined with CRISPR/Cas12a, but also exhibits remarkable applicability in detecting other significant targets.

Terpenes based hydrophobic deep eutectic solvents for dispersive liquid-liquid microextraction of aliphatic aldehydes in drinking water and alcoholic beverages.

Aliphatic aldehydes are a class of organic compounds containing aldehyde groups, which are widespread, and closely related to people's daily life and health. In this work, a series of terpenes based hydrophobic deep eutectic solvents were designed and synthesized using hexafluoroisopropanol as hydrogen bond donor and menthol/thymol as hydrogen bond acceptor. Then they are used as extraction solvent in dispersive liquid-liquid microextraction for extracting and determining seven aliphatic aldehydes from drinking water and alcoholic beverage combined with high performance liquid chromatography-ultraviolet. Due to the fact that these hydrophobic deep eutectic solvents are liquid at the room temperature, a density greater than that of water, a lower viscosity (≤26.10 mPa s, 25 °C), after extraction and centrifugation, the microvolume DES-rich phase in the bottom is convenient for collection and direct analysis without further dissolution or dilution with organic solvents. Some factors affecting the extraction recovery were optimized by one-variable-at-a-time and response surface methodology. Under the optimal conditions, the enrichment factors for the seven aliphatic aldehydes were 48-56. The method had good performance: linear ranges of 1.0-200, 0.5-200, 0.2-200, 0.4-400, 1.0-400, 0.4-400 and 0.4-400 µg L-1 for seven aliphatic aldehydes (r2 ≥ 0.9949), limits of detection of 0.1-0.5 µg L-1, intra-day and inter-day precisions <4.9%. The recoveries of seven aliphatic aldehydes ranged from 76.0 to 119.0%. The proposed dispersive liquid-liquid microextraction method is simple, rapid, highly efficient, and green, which effectively reduces the amount of toxic chemical reagents used and their impact on the environment. Rapid and efficient detection of aliphatic aldehydes helps ensure a healthy diet and has great application prospects in food safety analysis.

Acid induced dispersive liquid-liquid microextraction based on in situ formation of hydrophobic deep eutectic solvents for the extraction of bisphenol A and alkylphenols in water and beverage samples.

This study describes the development of an acid induced dispersive liquid-liquid microextraction method based on the in situ formation of hydrophobic deep eutectic solvents for the extraction of bisphenol A and alkylphenols from environmental water and beverage samples. Hydrochloric acid altered the hydrophilic-hydrophobic state of fatty acid salts to obtain hydrophobic fatty acids, which formed hydrophobic deep eutectic solvents with analytes in situ to extract the analytes. Under optimized conditions, the limits of detection and limits of quantitation were 0.03-0.1 µg L-1 and 0.12-0.3 µg L-1, the intraday and interday relative standard deviations were less than 3.9 %, and the enrichment factor was 29-32. The recoveries of bisphenol A and alkylphenols were 95.9-104.9 % and 86.9-105.0 %, respectively. The extraction process used only hydrochloric acid and fatty acid salts, and the extraction process required less than 1 min. This method has the advantages of simplicity, speed, low cost and environmental friendliness.

Carbonized polymer dots-based molecular imprinting: An adsorbent with enhanced selectivity for highly efficient recognition and removal of ceftiofur sodium from complex samples.

Highly selective removal of residual cephalosporin antibiotics from complex systems is crucial for human health and ecological environment protection. Herein, a newly molecularly imprinted polymer adsorbent (CPDs-NH2@MIP) with enhanced selectivity for ceftiofur sodium (CTFS) was developed by using the special carbonized polymer dots (CPDs-NH2) as functional monomer. The CPDs-NH2 has a nano-spherical structure and functionalized groups (CC, -NH2) via the incomplete carbonization polymerization of citric acid, acrylamide and ethylenediamine, which can accurately interact with CTFS by overcoming steric hindrance, resulting in more precisely imprinted sites and reducing non-imprinted regions in MIP. The presented CPDs-NH2@MIP exhibited excellent adsorption capacity for CTFS (68.62 mg g-1), achieving equilibrium within 10 min, and highly selectivity in mixed solution containing five coexisting substances, with an imprinted factor (5.61). Compared with commercial adsorbents and MIPs prepared with traditional chain functional monomers, the CPDs-NH2@MIP showed significant advantage in selective recognition and separation of target. Analysis of microstructure and mechanism proved that usage of the spherical functional monomer generated precise imprinting sites and dense structure in CPDs-NH2@MIP, which effectively enhanced the selectivity in complex system combined with hydrogen bonding interaction. The idea of designing and using spherical functional monomer will promote the practicality of molecularly imprinted polymer adsorbents.

Fast and eco-friendly synthesis of carbon dots from pinecone for highly effective detection of 2,4,6-trinitrophenol in environmental samples.

2,4,6-Trinitrophenol (TNP) has high explosive risks and biological toxicity, and there has been considerable concern over the determination of TNP. In the present work, fluorescent carbon dots (CDs) stemmed from a green carbon source of pinecone by the facile hydrothermal approach. A novel environment- friendly fluorescent probe was developed to efficiently detect TNP by using the obtained CDs with remarkable fluorescence stability. The fluorescent CDs exhibited obvious excitation dependence with the highest peaks for excitation and emission occurring at 321 and 411 nm, respectively. The fluorescence intensity is significantly reduced by TNP owing to the inner filter effect with the CDs. The probe exhibited good linearity with TNP concentrations in the range of 0.025-20 µg mL-1, and the limit of detection was as low as 8.5 ng mL-1. Additionally, the probe proved successful in sensing TNP quantitatively in actual environmental samples with satisfied recoveries of 95.6-99.6%. The developed fluorescent probe offered an environment-friendly, efficient, rapid, and reliable platform for detecting trace TNP in the environmental field.HighlightsNovel carbon dots were synthesised from green precursors of pineal powder.The highly effective quenching process was put down to the inner filter effect.The as-constructed fluorescent probe was successfully utilised for sensing 2,4,6-trinitrophenol in environmental samples.The proposed method was simple, rapid, efficient, economical, and eco-friendly.

A novel carbonized polymer dots-based molecularly imprinted polymer with superior affinity and selectivity for oxytetracycline removal.

Molecularly imprinted polymers (MIPs) synthesized from chain functional monomers are restricted by spatial extension and exhibit relatively poor affinity and selectivity; this results in unsatisfactory applications in complex media. In this study, we prepared unique spherical carbonized polymer dots (CPDs-OH) via the incomplete carbonization of 1-allyl-3-vinylimidazolium bromide and ethylene glycol, and used it as a functional monomer to prepare a newly imprinted polymer (CPDs-OH@MIP) in aqueous media. As a result, the CPDs-OH@MIP exhibited effective recognition of oxytetracycline with an impressive imprinting factor of 6.17, surpassing MIPs prepared with chain functional monomers (1-3). Furthermore, CPDs-OH@MIP exhibited excellent adsorption for oxytetracycline (278.52 mg g-1) and achieved equilibrium in 30 min, with stronger resistance to coexisting cations, anions, and humic acid. Compared to other MIPs and adsorbents, the recognition performance of CPDs-OH@MIP improved 2-4 times; this polymer could remove >92.1% of oxytetracycline in real water samples with at least 10 cycle times. CPDs-OH@MIP prepared using the special spherical monomer forms a denser structure with fewer nonimprinted regions and precisely imprinted sites, remarkably improving the affinity and selectivity of MIPs combined via hydrogen bonds and electrostatic and π-π interactions. Our proposed strategy provides an effective basis for breakthroughs in the practical application of MIPs.

Magnetotactic Bacteria AMB-1 with Active Deep Tumor Penetrability for NIR-II Photothermal Tumor Therapy.

The complex tumor structure and microenvironment such as abnormal tumor vasculature, dense tumor matrix, and elevated interstitial fluid pressure greatly hinder the penetration and retention of therapeutic agents in solid tumors. The development of an advanced method for robust penetration and retention of therapeutic agents in tumors is of great significance for efficient tumor treatments. In this work, we demonstrated that magnetotactic bacteria AMB-1 with hypoxic metabolism characteristics can actively penetrate the tumor to selectively colonize deep hypoxic regions, which emerge as a promising intelligent drug carrier. Furthermore, AMB-1 presents intrinsic second near-infrared (NIR-II) photothermal performance that can efficiently convert a 1064 nm laser into heat for tumor thermal ablation. We believe that our investigations not only develop a novel bacteria-based photothermal agent but also provide useful insights for the development of advanced tumor microbial therapies.

Constructing an eco-friendly and ratiometric fluorescent sensor for highly efficient detection of mercury ion in environmental samples.

Mercury ion (Hg2+) is a highly toxic and ubiquitous pollutant, whose effective detection has aroused widespread concern. A novel ratiometric fluorescent sensor has been designed to rapidly and efficiently detect Hg2+ based on blue/red carbon dots (CDs) with environmental friendliness. This sensor was well characterized via TEM, FTIR, XPS, UV-vis, and zeta potential analysis and displayed excellent fluorescence properties and stability. The fluorescence of blue CDs at 447 nm was significantly quenched with the addition of Hg2+ resulted from the static quenching, whereas that of red CDs at 650 nm remained invariable. A sensitive method for Hg2+ determination was constructed in the range of 0.05-7.0 nmol mL-1 with optimal conditions, and the detection limit was down to 0.028 nmol mL-1. Meanwhile, compared to other 17 metal ions, the ratiometric fluorescent sensor exhibited high selectivity for Hg2+. Furthermore, satisfied recoveries had also been obtained for measuring trace Hg2+ in practical environmental samples. This developed ratiometric fluorescent sensor provided a reliable, environmental-friendly, rapid, and efficient platform for the detection of Hg2+ in environmental applications.

[Effects of pH, Calcium, and Phosphate on the Solubility of Arsenic in Paddy Soil Based on Surface Complexation Modeling].

This study aimed to obtain a better understanding on the environmental behavior of As in paddy soil and to reveal the influence mechanisms of different environmental factors on the availability of As in the soil solution. The effects of pH, calcium, and phosphate on the solubility and speciation distribution of As in the paddy soil collected from Zhuzhou of Hunan province were studied by combining the adsorption experiments with the NOM-CD model. The results showed that the minimum concentration of soluble As in the soil was at approximately a pH of 6.0, which was mainly affected by both electrical interactions and site competition between Ca2+, PO43-, As(Ⅲ), and As(Ⅴ). The adsorption of As onto soil particles could be increased by an increase in Ca2+ in the soil system, leading to the decrease in soluble As concentration. This effect became significant at a higher pH, because adsorbed Ca2+ increased the positive charge on (hydr)oxide surfaces. With phosphate addition, the reduction in As(Ⅴ) in the soil was inhibited at pH<5.5, whereas it was promoted at pH>5.5. Moreover, the concentration of soluble As(Ⅲ) and As(Ⅴ) in the soil solution was dramatically increased with the addition of phosphate owing to the competitive adsorption between As and phosphate. At a lower background of Ca2+, there was a higher fraction of As(Ⅲ) in the soil either with or without phosphate addition. This phenomenon might be caused by the higher bioavailability of phosphorus in soil at a lower concentration of Ca2+, which favors the dissimilatory reduction of As or iron (hydr)oxides. The results indicated that the NOM-CD model could predict the influence of pH, calcium, and phosphate on the solubility and speciation distribution of As in paddy soil and reveal its main mechanisms. Therefore, the NOM-CD model would provide the quantitative and scientific method for evaluating the risk of As in soils or other solid-water systems.

Switchable ROS Scavenger/Generator for MRI-Guided Anti-Inflammation and Anti-Tumor Therapy with Enhanced Therapeutic Efficacy and Reduced Side Effects.

Photosensitizer in photodynamic therapy (PDT)  accumulates in both tumor and adjacent normal tissue due to low selective biodistribution, results in undesirable side effect with limited clinic application. Herein, an intelligent nanoplatform is reported that selectively acts as reactive oxygen species (ROS) scavenger in normal tissue but as ROS generator in tumor microenvironment (TME) to differentially control ROS level in tumor and surrounding normal tissue during PDT. By down-regulating the produced ROS with dampened cytokine wave in normal tissue after PDT, the nanoplatform reduces the inflammatory response of normal tissue in PDT, minimizing the side effect and tumor metastasis in PDT. Alternatively, the nanoplatform switches from ROS scavenger to generator through the glutathione (GSH) responsive degradation in TME, which effectively improves the PDT efficacy with reduced GSH level and amplified oxidative stress in tumor. Simultaneously, the released Mn ions provide real-time and in situ signal change of magnetic resonance imaging (MRI) to monitor the reversal process of catalysis activity and achieve accurate tumor diagnosis. This TME-responsive ROS scavenger/generator with activable MRI contrast may provide a new dimension for design of next-generation PDT agents with precise diagnosis, high therapeutic efficacy, and low side effect.

One-step derivatization and temperature-controlled vortex-assisted liquid-liquid microextraction based on the solidification of floating deep eutectic solvents coupled to UV-Vis spectrophotometry for the rapid determination of total iron in water and food samples.

In our work, hydrophobic thymol-based deep eutectic solvents (DESs) with strong reducibility, a lower density than water, and a slightly higher melting point than room temperature were synthesized. Based on these solid DESs, one-step derivatization and temperature-controlled vortex-assisted liquid-liquid microextraction based on the solidification of a floating DES (TC-VA-LLME-SFDES) via UV-Vis spectrophotometry for the rapid determination of total iron was developed. The derivatization and TC-VA-LLME were carried out simultaneously by the addition of DES as both the reducing agent and extraction solvent. After optimization, the calibration curve (5-250 µg L-1, R2 = 0.9982), limit of detection (1.5 µg L-1), limit of quantitation (5.0 µg L-1), precision (≤4.0%) and enrichment factor (92) was obtained. This method was applied for the determination of total iron in water and food samples with satisfactory recoveries (85.4-106.2%). One-step derivatization and TC-VA-LLME only required 2 min. Furthermore, this method opened up the application of solid DESs in liquid-liquid microextraction.

Fast and efficient "on-off-on" fluorescent sensor from N-doped carbon dots for detection of mercury and iodine ions in environmental water.

A kind of nitrogen doped carbon dots (N-CDs) was facilely fabricated from polyethyleneimine and anhydrous citric acid, and which was adopted to develop a neoteric "on-off" and "off-on" fluorescent sensor for rapidly and efficiently sensing Hg2+ and I-. The fluorescence of N-CDs was notably quenched (off) in the existence of Hg2+ derived from strong interaction and the electron transfer between N-CDs and Hg2+, while the quenched fluorescence of the N-CDs and Hg2+ system was strikingly regained by addition of I- (on) resulted from the separation of N-CDs and Hg2+ due to the higher binding preference between Hg2+ and I-. Under optimal conditions, the linear detection ranges were 0.01-20 µM for Hg2+ and 0.025-7 µM for I-, respectively. Meanwhile, the detection limits could be down to 3.3 nM for Hg2+ and 8.5 nM for I-, respectively. Satisfied recoveries had also been gained for measuring Hg2+ and I- in practical water samples. The constructed "on-off-on" fluorescent sensor provided a simple, rapid, robust and reliable platform for detecting Hg2+ and I- in environmental applications.

Surface imprinted polymer on a metal-organic framework for rapid and highly selective adsorption of sulfamethoxazole in environmental samples.

The demand for the removal of pollutants in aqueous solution has triggered extensive studies to optimize the performance of adsorbents, but the adsorption rate and selectivity of adsorbents have been overlooked. Hierarchically ordered porous vinyl-functionalized UIO-66 was used as supporter to prepare a surface molecular imprinted polymer (MIP-IL@UIO-66). The UIO-66 with large specific surface area significantly increased the number of active site of polymer, and so the MIP-IL@UIO-66 can achieve the rapid and highly selective adsorption of sulfamethoxazole (SMZ) in water. The structure and morphology of MIP-IL@UIO-66 was examined using scanning electron microscopy, Fourier transform infrared spectroscopy, nitrogen adsorption-desorption isotherms, thermogravimetry, X-ray photoelectron spectroscopy, and X-ray powder diffraction. Results indicate that the presented MIP-IL@UIO-66 has an ultrafast equilibrium rate (equilibrium time, 10 min), large adsorption capability (maximum capacity, 284.66 mg g-1), excellent adsorption selectivity (selectivity coefficient, 11.36), and good reusability (number of cycles, 5 times) via equilibrium adsorption experiments. Subsequently, as a novel solid phase extraction (SPE) adsorbent, the adsorption performance of SMZ onto MIP-IL@UIO-66 was better than that of a commercial SPE adsorbent. A MISPE column combined with high-performance liquid chromatography (HPLC) was presented to detect SMZ in water, soil, egg, and pork samples with recoveries of 91-106%. Hydrogen bonds, electrostatic and π-π interactions, and molecular memory were attributed to recognizing the SMZ of MIP-IL@UIO-66.

Air-assisted liquid-liquid microextraction based on the solidification of floating deep eutectic solvents for the simultaneous determination of bisphenols and polycyclic aromatic hydrocarbons in tea infusions via HPLC.

Deep eutectic solvents (DESs) are a new class of green "designer solvent"; its physicochemical properties can be easily tuned by adjusting DES' constituents, chemical ratio and water content. In this study, three hydrophobic DESs with low viscosity, low density, and melting points close to room temperature were designed and synthesized. Based on these DESs, an air-assisted liquid-liquid microextraction technique was developed based on the solidification of floating DESs for the simultaneous determination of bisphenols and polycyclic aromatic hydrocarbons (PAHs) via HPLC. The microextraction parameters were optimized via the Plackett-Burman design and response surface methodologies. The method shows satisfactory linearity (R2 ≥ 0.9928), a low limit of detection (0.16-0.75 µg L-1) and satisfactory precision (≤2.3%), and was successfully applied for the simultaneous determination of bisphenols and PAHs from tea infusions with satisfactory recoveries (82.0-116.6%). This method is simple, rapid, economical, environmentally compatible, dispersive solvent-frees and centrifugation-free, and has promising applications in food safety.