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Room-temperature preparation of polymer-based covalent hybrids, which with multiple functional characteristics, is instrumental to overcome the performance shortcomings of single-polymer materials and broaden their applications thus. Herein, by introducing chitosan (CS) as a starting substrate into benzoxazine-isocyanide chemistry (BIC)/sol-gel reaction system, a novel polyamide (PA)/SiO2/CS covalent hybrid (PA-Si-CS) was successfully prepared in-situ at 30 °C. PA-Si-CS's chemical structure and elementary properties were characterized here. The introduction of CS combining with the presence of diverse N, O-containing segments (amide, phenol -OH, Si-OH, etc.) in PA-Si-CS provided its synergistic adsorption for Hg2+ and anionic dye Congo red (CR). The capture of PA-Si-CS for Hg2+ was rationally applied to the "enrichment"-type electrochemical probing of Hg2+. Relevant detection range, detection limit, interference, and probing mechanism were systematically analyzed. Compared with the experimental results of control electrodes, the electrode modified with PA-Si-CS (PA-Si-CS/GCE) showed a significantly enhanced electrochemical response to Hg2+, with a detection limit up to ~2.2 × 10-8 mol/L. In addition, PA-Si-CS also exhibited the specific adsorption for CR. Systematic analyses of dye adsorption selectivity, kinetics, isothermal models, thermodynamics, and adsorption mechanism told that PA-Si-CS can be used as an efficient CR adsorbent, with a maximum adsorption capacity of ~348 mg/g.

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Herein, ß-cyclodextrin-containing hybrid polymers (P1, P2 and P3) were prepared through crosslinking partially benzylated ß-cyclodextrin (PBCD) by octavinylsilsesquioxane (OVS). P1 stood out in screening studies and the residual hydroxyl groups of PBCD was sulfonate-functionalized. The obtained P1-SO3Na showed greatly enhanced adsorption towards cationic MPs and maintained the excellent adsorption performance towards neutral MPs. The rate constants (k2) of cationic MPs upon P1-SO3Na were 9.8-34.8 times larger than those upon P1. The equilibrium uptakes of the neutral and cationic MPs upon P1-SO3Na were above 94.5 %. Meanwhile, P1-SO3Na demonstrated appreciable adsorption capacities, excellent selectivity, effective adsorption of mixed MPs at environmental levels and good reusability. These results confirmed the great potential of P1-SO3Na as effective adsorbent to remove MPs from water.

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Herein, through knitting benzylated ß-cyclodextrin (BnCD) by dimethoxypillar[5]arene (P[5]), porous copolymers (P[5]-BnCDs) containing two kinds of macrocycles were synthesized with yields not <97 %. The molar ratio of P[5]/BnCD greatly influenced the P[5]-BnCDs' porosity and adsorption performance. When the molar ratio of P[5]/BnCD was 4/1, the P[5]-BnCD (4-1), demonstrated a surface area up to 515.95 m2/g and showed fast adsorption kinetic, high adsorption capacity and good reusability towards the model organic micropollutants (OMPs). The adsorption fitted well with the pseudo-second-order and the Langmuir models, while the thermodynamic studies revealed spontaneous physisorption process. The adsorption mechanism was dominant by host-guest and hydrophobic interactions and the adsorption at environmentally relevant concentrations experiments showed the practicality and superiority in extraction of the OMPs at µg/L level. This study paves a way for the development of versatile porous organic polymers with multiple macrocycles for efficient removal of OMPs from water.

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An effective method has been developed for the simultaneous determination of four bisphenols (bisphenol A, S, F and B) in various foodstuffs. The contaminants were extracted by QuEChERS-based strategy and subjected to ion-exchange solid-phase extraction for further clean-up. The critical variables were screened by Plackett-Burman design and then optimized by central composite design. Under the optimized conditions, satisfactory accuracy (recoveries 76%-116%) and precision (RSDs < 12%) were achieved. The established method was then used to assess the contamination status of 379 real samples. Bisphenol A was demonstrated to be the predominant bisphenol with highest incidence (79.7%) and average concentration (14.3 µg/kg). The positive rates (mean concentration) of bisphenol S, F and B were 37.7% (1.6 µg/kg), 26.9% (1.4 µg/kg) and 0.0% (not detected), respectively. Finally, the daily dietary intakes of ∑4bisphenolsfor adult residents were estimated (55.9-76.1 ng/kg bw/day) according to the contamination concentrations and the daily recommended intakes.

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A new cationic gemini surfactant-resorcinol/formaldehyde resin was designed and synthesized. Cationic gemini surfactant was introduced into the resorcinol/formaldehyde resin for the first time and led to the retention of negatively charged endocrine disrupting compounds (EDCs) through electrostatic interactions, hydrogen bonding and π-π interactions. The synthesized material showed good performance in the dispersive micro-solid phase extraction (D-µ-SPE) of EDCs such as alkylphenol and phenoxy acid herbicides from food packaging migrants. Extraction parameters such as pH, adsorbent dose, extraction time and salting out effect were optimized. The limits of detections were in the range of 0.5-0.8 ng/mL, and the recoveries were in the range of 90-100%. The developed method was applied to the analysis of EDCs from food contacting materials migrants with pentachlorophenol, 2,4-dichlorophenoxyacetic acid and bisphenol A detected in the concentration range of 0.2-1.2 mg/kg. It also showed great potential in the D-µ-SPE of other compounds with negative charge or high hydrophobicity.

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A novel liquid-phase microextraction based on the ferrofluid was successfully applied for the extraction and determination of four phenolic compounds (bisphenol-A, bisphenol-AF, tetrabromobisphenol-A and 4-tert-octylphenol) in milks and fruit juices. In this study, a range of alkyl (C4-C10) alcohols as the carrier liquid were used for the preparation of ferrofluids. The study showed that an appropriate chain length of alkyl alcohol may improve the extraction efficiency and maintain the integrity of ferrofluids during extraction, so 1-heptanol (C7) was selected as the optimal carrier liquid. Specifically, the effects of various parameters on the extraction of phenolic compounds were investigated and optimized. Under the optimized conditions, the limits of detection were between 0.35 and 0.66 µg L-1. The intra-day and inter-day precision (RSD %) for the analytes at 10 and 50 µg L-1 were in the range of 3.2-6.7 % and 2.9-7.1%, respectively.

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A specific, precise and accurate high performance liquid chromatographic (HPLC) analytical method with a fluorescence detector (FLD) was established for the simultaneous determination of nine bisphenols (BPs) in milk samples. Samples were extracted ultrasonically with acetonitrile and cleaned using the QuEChERS technique. Under the optimized conditions, good linearity was obtained for the nine BPs and the correlation coefficients (R2) ranged from 0.9942 to 0.9997. Recovery values for the nine bisphenols in spiked samples were 75.82-93.86% with intra-day and inter-day relative standard deviations (RSDs) from 2.6 to 11.1%. The limits of detection (LODs) and quantification (LOQs) were 1.0-3.1 µg/kg and 3.5-9.8 µg/kg, respectively. The results demonstrated clearly that the approach developed provides reliable, simple, rapid and environmentally-friendly quantification and identification of nine bisphenols in a fatty matrix and could be used for monitoring bisphenols in milk.

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Organic micropollutants in aquatic environment such as plasticizer, pesticide and pharmaceuticals, have posed a serious threat to human health and are emerging as a great challenge to humanity. Traditional water treatment techniques fail to achieve high removal efficiency for low concentration of organic micropollutants. Here we demonstrate a water-insoluble crosslinked ß-cyclodextrin (ß-CD) polymer able to remove a broad-spectrum of organic micropollutants from water by rapid adsorption. A family of ß-CD polymers (ß-CDPs) were synthesized by nucleophilic aromatic substitution of ß-CD hydroxyl groups and 4,4'-difluorodiphenylsulfone. The ß-CDPs were used to adsorb various organic micropollutants in water by static or dynamic adsorption process. It was found that more than 99% micropollutants in water were removed by flowing the feed water through the column of ß-CDPs. The results of static adsorption experiments indicated the adsorption process was fast and the adsorption capacity was very high (the maximal value was 113.0mg of bisphenol A per gram of ß-CDP). The adsorption process was fitted well with the quasi-second-order kinetics and the Langmuir isothermal adsorption model, suggesting that it is mainly a chemical adsorption of monolayer. The water-insoluble characteristic of the ß-CDPs is convenient for their separation from the treated solution after adsorption saturation for regeneration and reuse. The adsorption ability of ß-CDPs was kept nearly unchanged after five filtration-regeneration cycles.

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The Egusi Okra soup is a traditional African meal that is considered of high nutritional value and protective against weight loss. We introduce the concept of "kitchen toxicology" to analyse the recipe of the Egusi Okra soup and highlight possible mitigation measures for toxic and/or antinutritional effects in the wide spectrum of health and nutritional needs of HIV+/AIDS subjects. In particular, we focus on toxicants (environmental contaminants, process contaminants, substances leaching from food contact materials) dysregulating the immune status, as well as on interactions between nutrients, contaminants, and/or antinutrients which may lead to secondary/conditioned nutritional deficiencies or imbalances; in their turn, these can modulate the ability to cope with toxicants, and increase nutritional requirements. Recommendations are given for practices preserving the Egusi Okra soup from such risk factors, identifying points of particular attention during meal preparation, from purchase of raw ingredients through to food handling, cooking, storage, and consumption. The Egusi Okra soup is discussed in the context of a diet that is asked to mitigate complications (weight loss, opportunistic infections) and support antiretroviral therapy in African countries with high HIV/AIDS prevalence. The paper discusses how nutritional interventions benefit of the integration of kitchen toxicology practices in everyday life. Toxicological risk assessment is crucial to understand the history and status of the person exposed to or affected by infectious diseases.

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A magnesium-aluminum layered double hydroxides coated on magnetic nanoparticles (Fe3O4@MgAl-LDHs NPs) combined with the supramolecular solvents (SUPRASs) as the magnetic supramolecular fluids were successfully applied to the extraction and determination of four phenolic compounds (Bisphenol-A (BPA), bisphenol-AF (BPAF), tetrabromobisphenol-A (TBBPA) and 4-tert-octylphenol (4-TOP)). Magnetic supramolecular fluids (ferrofluids) composites were prepared through adding the mixture of n-octanol and tetrahydrofuran in distilled water as the supramolecular solvents into the solution containing magnetic Fe3O4@MgAl-LDHs NPs. Under the optimized conditions, the calibration curve was obtained in range of 5-1000µgL-1. The limits of detection (S/N=3) for BPA, BPAF, TBBPA and 4-TOP, were obtained for 0.54, 0.48, 0.37 and 0.63µgL-1, respectively. The intra-day and inter-day precision (RSDs %) for bisphenols (BPs) and 4-TOP at 100 and 300µgL-1 were in the range of 4.0-7.8. The enrichment factors were between 16 and 24.

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A multiresidue method for the determination of 17 emerging contaminants in vegetables was developed based on ultrasound-assisted matrix solid-phase dispersion (MSPD). The analysis was performed using isotope dilution gas chromatography tandem mass spectrometry. In the development of the MSPD procedure, different parameters such as sonication and the type of sorbent or extraction solvent were assayed. Manual and in situ derivatization was assayed and the chromatographic response was higher when the reaction takes place in the injection port. The limits of detection obtained for the studied compounds were in the range of 0.1-0.4ngg(-1) for the different vegetables analyzed. The developed method was applied to vegetables obtained from several local markets. At least one of the organophosphates was detected in the analyzed samples at levels ranging from 0.6 to 4.6ngg(-1) and bisphenol A was detected in all the samples at concentration up to 16ngg(-1).

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A new method for simultaneous determination of five bisphenols in canned energy drinks by UPLC with fluorescence detection, after clean up on molecularly imprinted polymers, is herein described. The method was validated at two concentration levels, calculating trueness, repeatability and within-laboratory reproducibility, specificity, linearity of detector response, the limits of quantifications and the limits of detection for each bisphenol. The method is specific, reliable and very sensitive, allowing for determination of bisphenol F diglycidyl ether (BFDGE), bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol A diglycidyl ether (BADGE) down to 0.50ng/mL; it was employed to determine contamination levels from these bisphenols in forty energy drinks of different brands, collected from the market in Naples. BPA was detected in 17 out of 40 samples (42.5%); in some energy drinks also BPF, BADGE and BFDGE were determined.

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Nanofibrous molecularly imprinted membranes (nano-MIMs) with multi-analyte selectivity were prepared by encapsulating two types of molecularly imprinted polymer nanoparticles (MIP-NPs) into electrospun polyvinyl alcohol nanofibers. The obtained nano-MIMs maintained high molecular selectivity offered by each of the MIP-NPs. Nano-MIM embedding BPA-imprinted nanoparticles and TBZ-imprinted nanoparticles together showed the highest binding selectivity for acid bisphenol A (BPA) and basic tebuconazole (TBZ). This nano-MIM was used as affinity material of membrane-based molecularly imprinted solid-phase extraction (m-MISPE) to extract trace BPA and TBZ in vegetables and juices simultaneously. The recoveries of BPA and TBZ from different samples were higher than 70.33% with RSDs lower than 9.57%. m-MISPE gave better HPLC separation efficiencies and higher recoveries than conventional SPE based on C18/SCX. Multi-analyte selective m-MISPE combined with HPLC realized selective and simultaneous determination of several trace analytes with opposite charges/polarities in different food samples.

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Among the numerous chemicals discharged into the surrounding environment, bisphenol A (BPA) and octylphenol (OP) have been shown to increase oxidative stress in body by disturbing the prooxidant/antioxidant balance of cells. Cinnamon aqueous extract (CAE) is a natural product rich in polyphenolic compounds that have antioxidant activity. This study was designed to investigate the protective efficacy of CAE against oxidative disorders induced by BPA and OP in male albino rats. Animals were divided into 6 groups (10 rats each) and treated orally, 3 times weekly for 50 days. Group 1: control vehicle (olive oil); group 2 (25 mg BPA/kg b.wt./day); group 3 (25 mg OP/kg b.wt./day); group 4 (200 mg CAE/kg b.wt./day); group 5 (CAE 2 h before BPA administration); and group 6 (CAE 2 h before OP administration). BPA- and OP-exposed groups showed insignificant elevation in the final body weight; weight gains and significant reduction only in the relative kidneys weight. Also, BPA and OP exposure resulted in significant increase in serum urea, creatinine and kidney, brain, testicular malondialdehyde (MDA) levels. Significant reduction in tissues reduced glutathione (GSH) contents; catalase (CAT) and superoxide dismutase (SOD) activities were also recorded in BPA and OP exposed animals compared to the control vehicle group. Pretreatment with CAE 2 h either before BPA or OP administration ameliorated the BPA- and OP-induced body weight; weight gains and relative organs weight changes and biochemical adverse effects. CAE pretreatment also protected against the recorded pathological changes in kidney, brain and testis. In conclusion, CAE could ameliorate the oxidative toxic effects of BPA and OP indicating its protective antioxidant effect.