Ultrasonic-induced grafted lanthanum sulfide decorated multi-walled carbon nanotube onto bacterial cellulose applied for adsorption of pesticides in environmental waters.

A new biosorbent was fabricated by modification of bacterial cellulose biopolymer grafted with lanthanum sulfide decorated carboxylated multiwall carbon nanotube (La2S3@MWCNT@BC). The sorbent was employed in a green alternative dispersive-solid phase extraction of a variety of 14 pesticides in environmental water samples. The analyses were performed using GC-µECD. The properties and structure of La2S3@MWCNT@BC nanocomposite were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and adsorption-desorption isotherms. The composition of the sorbent was also investigated to evaluate the adsorptive properties of its constituents. The impact of various parameters influencing extraction efficacies such as sorbent dose, adsorption time, sample pH, ionic strength, and desorption conditions was investigated. The method was validated by specificity, matrix effect % (-0.4 to -7.4), enrichment factor (4-10), limits of quantification (0.007-0.31 µg L-1), matrix-matched calibration linearity (0.01-200 µg L-1), determination coefficients (r2=0.9921-0.9998), and precision. The optimized method was applied for the analysis of multiclass pesticides in seven environmental and drinking waters and the recoveries were obtained in the 81-108 % range with RSDs of 2.5-4.7 %. This paper is the first report on the synthesis and use of La2S3@MWCNT@BC nanocomposite to extract pesticides from different water samples. The greenness of the procedure was evaluated by the AGREE protocols.

Bacterial cellulose-supported dual-layered nanofibrous adsorbent for thin-film micro-solid-phase extraction of antibiotics in municipal wastewaters.

In this study, bacterial cellulose was coated with composite nanofibers of polyvinyl alcohol doped with beta cyclodextrin and alginate (PVA-SA-ßCD), constructed using the electrospinning technique. This novel material served as an effective adsorbent for thin-film micro-solid-phase extraction (TF-µSPE) of antibiotics from water samples, followed by HPLC-UV analysis. The adsorbent was subjected to a comprehensive characterization using ATR-FTIR, FE-SEM, and BET techniques. These analyses provided valuable insights into its physicochemical structure and properties. Several key parameters that affect the performance of the TF-µSPE method were investigated including electrospinning factors (voltage, flow rate, needle tip-collector distance, and electrospinning time), desorption solvent type and volume, adsorbent dose, adsorption and desorption times, pH value, and salt percentage. Under the optimized conditions, the limits of detections and quantifications for target antibiotics were obtained in the ranges of 0.02-0.03 and 0.07-0.1 µg L⁻1, respectively. The linear range was 0.07-1000 µg L⁻1 with satisfactory determination coefficients (r2) of 0.9944-0.9984. The intra-day and inter-day precisions were obtained as 1.1-1.7 % and 2.2-3.5 %, respectively. The developed method was successfully applied to determine antibiotics in municipal wastewater samples, yielding recoveries within the range of 70-100 % (RSD%<3.7). The green features of the method were also assessed based on AGREE tool. This is the first report on the fabrication of a double-layered nanofibrous adsorbent and its application for the adsorption of antibiotics in wastewater. This robust approach combines efficiency with analytical accuracy, making it a valuable tool for antibiotic analysis in environmental samples.

An alginate-based eutectogel impregnated with polyvinylpyrrolidone/benzoic acid deep eutectic solvent and magnetic carboxylated multiwalled carbon nanotubes: Evaluated as sorbent in green microextraction of pesticides.

This article presents the synthesis and application of a novel magnetic eutectogel constituting a polymeric deep eutectic solvent (PDES), carboxylated multiwall carbon nanotube (MWCNT-COOH), and super-dispersible/super-paramagnetic polyvinylpyrrolidone coated-Fe3O4 nanocrystals incorporated in alginate gel. Different methods were used for the characterization of novel polymeric based DES gel including FT-NMR, ATR-FTIR, and SEM were used. The novel DES eutectogel was used for the extraction of pesticides from honey. The modified eutectogel with PDES, MWCNT, and PDES-MWCNT showed 1.8-, 1.4-, and 2.5-fold enhancement in the sorption efficiency under green magnetic micro-solid-phase extraction (MSPE) method before GC-MS analysis. Important factors including the acidity of the samples, adsorption and desorption conditions, and the ionic strength of the preparation solution were investigated. The matrix effect, specificity, the quantification limits (0.023-1.023 µg kg-1), linear dynamic range (0.023-500 µg kg-1 with R2 of 0.9845-0.9986), relative standard deviations (<8.4%), were evaluated. In addition, the method was used to analyze 12 pesticides in four samples of honey. In the spiked concentration range of 0.1 to 10 µg kg-, the obtained recoveries were between 73.2 and 110.8% (RSD% = 8.1%, n = 3).

Synthesis of a magnetic micro-eutectogel based on a deep eutectic solvent gel immobilized in calcium alginate: Application for green analysis of melamine in milk and dairy products.

A new three-component magnetic eutectogel composed of a crosslinked copolymeric deep eutectic solvent (DES) and polyvinylpyrrolidone-coated Fe3O4 nano-powder impregnated in calcium alginate gel was synthesized and applied as a sorbent material in a green alternative micro solid-phase extraction of melamine in milk and dairy products. The analyses were performed using the HPLC-UV technique. The copolymeric DES was prepared through thermally-induced free-radical polymerization of [2-hydroxyethyl methacrylate]:[thymol] DES (1:1 mol ratio) as functional monomer, azobisisobutyronitrile (as initiator), and ethylene glycol dimethacrylate (as crosslinker). The sorbent was characterized using ATR-FTIR, 1H & 13C FT-NMR, SEM, VSM, and BET techniques. The stability of the eutectogel in water and its effect on the pH of the aqueous solution was studied. A one-at-a-time approach was applied to optimize the impact of significant factors influencing sample preparation efficiency (sorbent mass, desorption conditions, adsorption time, pH, and ionic strength). The method validation was performed by evaluating matrix-matched calibration linearity (2-300 µg kg-1, r2 = 0.9902), precision, system suitability, specificity, enrichment factor, and matrix effect. The obtained limit of quantification (0.38 µg kg-1) was lower than the established maximum level for melamine by Food and Drug Administration (FDA) (0.25 mg kg-1), Food and Agriculture Organization (FAO) (0.5 & 2.5 mg kg-1), and The European Union (EU) (2.5 mg kg-1) in milk and dairy products. The optimized procedure was applied for the analysis of melamine in bovine milk, yogurt, cream, cheese, and ice cream. The obtained normalized recoveries of 77.4-105.3% (RSD% <7.0%) were acceptable regarding the practical default range set by the European Commission (70-120%, RSD≤20%). The sustainability and green aspects of the procedure were evaluated by the Analytical Greenness Metric Approach (0.6/1.0) and the Analytical Eco-Scale tool (73/100). This paper presents the first-time synthesis and application of this micro-eutectogel for the analysis of melamine in milk and milk-based dairy products.

Isolation of organophosphate pesticides from water using gold nanoparticles doped magnetic three-dimensional graphene oxide.

Pesticides are a large group of pristine organic contaminants, which are widely discharged into environmental water due to agricultural activities. Hence, extraction, determination, and removal of pesticides from water resources are necessary for human health. In this study, novel adsorbent was developed based on three-dimensional magnetic graphene coated with gold nanoparticles (3D-MG@AuNPs) for extraction of chlorpyrifos, dicrotophos, fenitrothion, and piperophos as four specific organophosphorus pesticides (OPPs) from wastewater and tap water samples. The proposed nanocomposite was characterized; FTIR and EDX are performed for the expected functional groups and elemental analysis, SEM showed the unique and spherical AuNPs are well dispersed over graphene sheets. In this investigation, the important parameters that have effect on the extraction efficiency, including the desorbing solvent, desorbing solvent volume, vortex time, the extraction time, adsorbent dosage, pH of sample solutions, and salt effect were evaluated. In conclusion, the measured amounts of the chosen OPPs were determined using the gas chromatography microelectron capture (µECD-GC) method. Limits of quantification (S/N ratio of 10) and detection (S/N ratio of 3) were attained at concentrations of 0.26-0.43 µg.L-1 and 0.08-0.14 µg.L-1, respectively. According to the results of the investigations, the synthesized 3D-MG@AuNPs did not require any complicated sample preparation methods; therefore, it is a very good choice for solid magnetic phase extraction studies.

Removal of lead ions from wastewater using magnesium sulfide nanoparticles caged alginate microbeads.

In this study, an adsorbent made of alginate (Alg) caged magnesium sulfide nanoparticles (MgS) microbeads were used to treat lead ions (Pb2+ ions). The MgS nanoparticles were synthesized at low temperatures, and Alg@MgS hydrogel microbeads were made by the ion exchange process of the composite materials. The newly fabricated Alg@MgS was characterized by XRD, SEM, and FT-IR. The adsorption conditions were optimized for the maximum removal of Pb2+ ions by adjusting several physicochemical parameters, including pH, initial concentration of lead ions, Alg/MgS dosage, reaction temperature, equilibration time, and the presence of co-ions. This is accomplished by removing the maximum amount of Pb2+ ions. Moreover, the adsorbent utilized more than six times with a substantial amount (not less than 60%) of Pb2+ ions was eliminated. Considering the ability of sodium alginate (SA) for excellent metal chelation and controlled nanosized pore structure, the adsorption equilibrium of Alg@MgS can be reached in 60 min, and the highest adsorption capacity for Pb2+ was 84.7 mg/g. The sorption mechanism was explored by employing several isotherms. It was found that the Freundlich model fits the adsorption process quite accurately. The pseudo-second-order model adequately described the adsorption kinetics.

Sulfide-Doped Magnetic Carbon Nanotubes Developed as Adsorbent for Uptake of Tetracycline and Cefixime from Wastewater.

In this study, a magnetic solid-phase extraction method was developed based on multi-wall carbon nanotubes decorated by magnetic nanoparticles (Fe3O4) and cadmium sulfide nanoparticles (Fe3O4@MWCNT-CdS) for trace extraction of cefixime and tetracycline antibiotics from urine and drug company wastewater. The adsorbent features were characterized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscope (FESEM), and energy dispersive X-ray analysis (EDX). Various effective parameters on the sorption and desorption cycle, such as sorption time, the mass of adsorbent, pH, salt addition, and material ratio, were investigated and optimized. The data were evaluated using isotherm models, and experimental data were well-fitted to both Langmuir (R2 = 0.975) and Freundlich (R2 = 0.985) models. Moreover, kinetic of reaction was agreement with pseudo-second-order (R2 = 0.999) as compared pseudo-first-order (R2 = 0.760). The maximum adsorption capacity for tetracycline and cefixime was achieved at 116.27 and 105.26 mg·g-1, respectively. Hence, the prepared adsorbent can be used as an alternative material for enhanced determination of pharmaceutical substances in biological fluids.

Superhydrophobic Nanosilica Decorated Electrospun Polyethylene Terephthalate Nanofibers for Headspace Solid Phase Microextraction of 16 Organochlorine Pesticides in Environmental Water Samples.

A new solid phase micro extraction (SPME) fiber coating composed of electrospun polyethylene terephthalate (PET) nanofibrous mat doped with superhydrophobic nanosilica (SiO2) was coated on a stainless-steel wire without the need of a binder. The coating was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectrometer (FTIR) techniques and it was used in headspace-SPME of 16 organochlorine pesticides in water samples prior to gass chromatography micro electron capture detector (GC-µECD) analysis. The effects of main factors such as adsorption composition, electrospinning flow rate, salt concentration, extraction temperature, extraction time, and desorption conditions were investigated. Under the optimum conditions, the linear dynamic range (8−1000 ng L−1, R2 > 0.9907), limits of detection (3−80 ng L−1), limits of quantification (8−200 ng L−1), intra-day and inter-day precisions (at 400 and 1000 ng L−1, 1.7−13.8%), and fiber-to-fiber reproducibility (2.4−13.4%) were evaluated. The analysis of spiked tap, sewage, industrial, and mineral water samples for the determination of the analytes resulted in satisfactory relative recoveries (78−120%).

Headspace Extraction of Chlorobenzenes from Water Using Electrospun Nanofibers Fabricated with Calix[4]arene-Doped Polyurethane-Polysulfone.

Chlorobenzenes (CBs) are persistent and potentially have a carcinogenic effect on mammals. Thus, the determination of CBs is essential for human health. Hence, in this study, novel polyurethane−polysulfone/calix[4]arene (PU-PSU/calix[4]arene) nanofibers were synthesized using an electrospinning approach over in-situ coating on a stainless-steel wire. The nanosorbent was comprehensively characterized using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) techniques. The SEM analysis depicted the nanofiber's unique morphology and size distribution in the range of 50−200 nm. To determine the levels of 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,3,4-tetrachlorobenzene in water samples, freshly prepared nanosorbent was employed using headspace-solid phase microextraction (HS-SPME) in combination with gas chromatography micro electron capture detector (GC-µECD). Other calixarenes, such as sulfonated calix[4]arene, p-tert-calixarene, and calix[6]arene were also examined, and among the fabricated sorbents, the PU−PSU/calix[4]arene showed the highest efficiency. The key variables of the procedure, including ionic strength, extraction temperature, extraction duration, and desorption conditions were examined. Under optimal conditions, the LOD (0.1−1.0 pg mL−1), the LDR (0.4−1000 pg mL−1), and the R2 > 0.990 were determined. Additionally, the repeatability from fiber to fiber and the intra-day and inter-day reproducibility were determined to be 1.4−6.0, 4.7−10.1, and 0.9−9.7%, respectively. The nanofiber adsorption capacity was found to be 670−720 pg/g for CBs at an initial concentration of 400 pg mL−1. A satisfactory recovery of 80−106% was attained when the suggested method's application for detecting chlorobenzenes (CBs) in tap water, river water, sewage water, and industrial water was assessed.

Green vortex-assisted emulsification microextraction using a ternary deep eutectic solvent for extraction of tetracyclines in infant formulas.

A novel green alternative vortex-assisted emulsification liquid-liquid microextraction based on a new hydrophobic deep eutectic solvent (DES) was developed to extract tetracyclines in infant formulas. Five new ternary DESs were synthesized and tested in this regard. Among them [thymol]:[ethylene glycol]:[benzyl alcohol] (2:2:1) DES demonstrated the highest extraction efficiency. The analyzes were performed by HPLC. The DES was characterized by attenuated total reflectance-FTIR, nuclear magnetic resonance spectroscopy, and octanol-water partition coefficient. The effect of type, mole ratio, and volume of DES, dispersing agent, pH, and ionic strength was studied. The limits of quantification and linear range were 3-9.32 and 3-500 µg kg-1, respectively. The method was applied to detect tetracyclines in infant formulas, and the recoveries were obtained as 68.9-102.0 % with relative standard deviations < 9 %. The procedure greenness was assessed using the Analytical Eco-Scale. This paper represents the first application of a novel ternary DES to analyze tetracyclines in infant formulas.

A green alternative QuEChERS developed based on green deep eutectic solvents coupled with gas chromatography-mass spectrometry for the analysis of pesticides in tea samples.

A novel green modified QuEChERS based on green deep eutectic solvents (DES) followed by GC-MS was developed to analyze pesticides in tea samples. Among different tested DESs for the extraction of analytes, ChCl:PEG (1:4) DES showed the highest efficiency. Three-dimensional magnetic graphene was functionalized by ChCl:urea (1:2) natural DES, characterized and used as sorbent in the in-syringe dispersive micro-SPE to cleanup tea extract. Under optimized conditions, linear range was 0.70-500 µg kg-1. The limits of quantification (0.70-1.90 µg kg-1) were lower than the maximum residue levels established by the European Union for pesticides in tea (0.015-0.1 mg kg-1). The method was applied to detect pesticides in green and black teas, and the recoveries were 70.2-105.2%. This work represents the first application of ChCl:PEG DES and 3DGA-Fe3O4/ChCl:urea in extraction of pesticides and tea sample cleanup, respectively. The greenness of procedure was evaluated by Analytical Eco-Scale and Complementary Green Analytical Procedure Index.

Development of a green miniaturized quick, easy, cheap, effective, rugged, and safe approach in tandem with temperature-assisted solidification of floating menthol droplet for analysis of multiclass pesticide residues in milk.

A new green miniaturized quick, easy, cheap, effective, rugged, and safe approach was developed and used for the extraction of multiclass 16 pesticides in milk before gas chromatography analysis. The miniaturization of method reduced the consumption of chemical reagents and samples. Magnetic three-dimensional graphene was used as sorbent in the clean-up step. Choline chloride:lactic acid (1:2) natural deep eutectic solvent was used as desorption solvent. Temperature-assisted solidification of floating menthol drop was executed for preconcentration of analytes. The method parameters including sorbent, desorption solvent, sorption and desorption times, menthol amount, pH, and ionic strength were optimized. The limit of quantification and linear range were 0.03-0.38 and 0.03-250 µg/kg, respectively. The accuracy was assessed by recovery evaluation at the spike levels of 50 and 100 µg/kg, in the range of 61-119%, with relative standard deviations within 2.1-18.2%. The method was applied to the analysis of pasteurized low and high-fat bovine milk, and various pesticide residues were detected in the concentrations range of 1.24-4.68 µg/kg. Finally, the greenness of the procedure was evaluated using the Analytical Eco-Scale. This work represents the first application of hybrid miniaturized extraction/preconcentration using a natural deep eutectic solvent and menthol to analyze pesticides.

Natural thymol-based ternary deep eutectic solvents: Application in air-bubble assisted-dispersive liquid-liquid microextraction for the analysis of tetracyclines in water.

Four new thymol-based ternary deep eutectic solvents were prepared and evaluated as the extractive phase in air-bubbles assisted dispersive liquid-liquid microextraction for extraction of tetracycline, doxycycline, and oxytetracycline from the water before high-performance liquid chromatography. The maximum extraction efficiencies were obtained using 400 µL of [choline chloride]:[thymol]:[nonanoic acid] in the molar ratio of 1:2:2 at pH = 5. The solvent was characterized by FTIR and NMR spectroscopy. The hydrophobicity of the deep eutectic solvent and its effect on the pH of water samples after mixing was also studied. Besides, the extraction efficiency of the ternary deep eutectic solvent was compared with that of two binary thymol-based deep eutectic solvents, including [choline chloride]:[thymol] and [thymol]:[nonanoic acid] at the same conditions. Under optimal conditions, limits of detection and quantification were 1.2-8.0 and 3.8-26.6 µg/L, respectively. The linear ranges were 18.2-500 µg/L for oxytetracycline, 26.6-500 µg/L for tetracycline, and 3.8-500 µg/L for doxycycline with the determination coefficients > 0.9912. Intra- and inter-day relative standard deviations were 1.2-3.8 and 7.7-11.2%, respectively. The developed method was applied to the analysis of tetracyclines in unspiked and spiked environmental water samples, and the obtained recoveries were 74.5-95.4% with relative standard deviations of 1.2-4.0%.

Deep eutectic solvent-based clean-up/vortex-assisted emulsification liquid-liquid microextraction: Application for multi-residue analysis of 16 pesticides in olive oils.

A new hydrophobic deep eutectic solvent (DES) composed of thymol and vanillin (1:1) was prepared and used as the extraction solvent in vortex-assisted emulsification liquid-liquid microextraction of 16 pesticides in olive oil before GC-µECD analysis. Due to the complexity of oil samples, a DES-based liquid-liquid solvent system (n-hexane/acetonitrile/DES) was developed to achieve an effective clean-up. Among the four examined hydrophilic DESs, [choline chloride]:[urea] led to improved sensitivity, and clean chromatograms with low noise and drift from the sample matrix. Besides, the effect of the significant factors such as extraction solvent volume, pH, ionic strength, and vortex time was investigated. At the optimized conditions, the validation parameters such as linear range 0.04-250 µg kg-1, the limits of detection of 0.01-0.08 µg kg-1, intra-day, and inter-day relative standard deviations (RSDs) < 6.8 and < 9.7%, were obtained. This method was followed by GC-µECD and applied to determine pesticides in five olive oil samples. The relative recoveries were in the range of 63.1-119.4%.

Levofloxacin nanoemulsion gel has a powerful healing effect on infected wound in streptozotocin-induced diabetic rats.

The aim of this study was to develop a novel oil-in-water (o/w) nanoemulsion gel containing levofloxacin for enhanced topical efficacy. Average particle size of sesame oil nanoemulsion without (SONE) and containing levofloxacin (SONEL) was found as 25.2 and 26.3 nm, respectively. Results from scratch test showed that SONEL had better proliferation effect in comparison with negative control. Treated animals with SONEL showed significant reduction in period of epithelialization, wound contraction, and number of inflammatory cells among all groups. Also, SONEL-treated group had the greatest collagen synthesis. Immunohistochemical analysis showed high intensity of CD31 and TGF-ß at wound site of treatment groups with SONEL on day 12 post-treatment (P < 0.05). Skin irritation test demonstrated safety of SONEL gel for skin topical application. In conclusion, our studies suggest that SONEL could be an effective formulation for treatment of diabetic wound infection by controlling infection and improving the healing process. Graphical Abstract .

Electrochemically controlled solid phase microextraction based on a conductive polyaniline-graphene oxide nanocomposite for extraction of tetracyclines in milk and water.

BACKGROUND: Tetracycline antibiotics are employed for human and animal health and for speeding up growth rates. However, their presence in food products and environmental waters has been a concern for some years. Therefore, a variety of sample preparation methods have been developed for the analysis of tetracycline residues in these matrices. RESULTS: An electrochemically controlled solid phase microextraction based on a modified copper electrode with polyaniline/graphene oxide (PANI/GO) conductive nanocomposite was developed for the extraction of oxytetracycline, tetracycline and doxycycline before high-performance liquid chromatography-UV analysis. PANI/GO was synthesized by in situ chemical oxidative polymerization, characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy, and bound on the electrode using high purity conductive double-sided adhesive carbon glue. The significant factors affecting the performance of microextraction were investigated and optimized. Under the optimized conditions [sample, 15 mL; sorbent, 10 mg; pH, 3.0; electroextraction voltage, -0.9 V; electroextraction time, 20 min; eluent (MeOH/NH3 ), 500 µL; and desorption time, 5 min], the limits of detection for target analytes were in the ranges 0.32-1.01 and 2.42-7.59 µg L-1 in water and milk samples, respectively. The linear ranges were 1.06-750 µg L-1 for water and 8.05-750 µg L-1 for milk samples. The intra-day and inter-day precisions were 2.32-3.80 and 3.29-4.25, respectively. The method was applied to the determination of analytes in milk and water samples with different fat contents, and the recoveries were obtained in the range 71-104%. CONCLUSION: The developed electro-microextraction method provides a facile, rapid, cost-effective, sensitive and efficient promising procedure for the extraction of antibiotics in complex matrices. © 2020 Society of Chemical Industry.

Monitoring of priority pollutants chlorophenols in water and milk by headspace solid-phase microextraction based on electrospun polycaprolactam nanofibers decorated with cadmium oxide-carbon nanotubes.

Priority pollutants chlorophenols are broadly used chemicals that are persistent in the environment and causing serious human health hazards. The current study introduces a novel adsorbent for the extraction of chlorophenols from river water, surface water, and milk by headspace solid-phase microextraction coupled with gas chromatography. The adsorbent composite was prepared by blending polycaprolactam (nylon-6) mat and newly synthesized carbon nanotubes decorated with cadmium oxide nanoparticles followed by electrospinning technique to produce based nanofiber. The proposed nanofiber was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction techniques. The main parameters that affect extraction efficiency, including ionic strength, extraction time, desorption time, and extraction temperature, were investigated and optimized. The linear range was 0.05-5 ng/mL; the limits of detection (signal/noise=3) were 0.02-0.04 ng/mL. The relative recoveries for real samples (river water, surface water, and milk) were in the range of 84-114%.

Nanosorbent-based solid phase microextraction techniques for the monitoring of emerging organic contaminants in water and wastewater samples.

This review (including 127 refs) summarizes applications of nanosorbent-based solid phase microextraction (SPME) for the cleanup, extraction, and quantification of Emerging Organic Contaminants (EOCs). SPME is the most widely used technique for the analysis of EOCs from water samples. The selection of sorbent material plays a key role in SPME applications. Here, we have collected information about recent developments in the application of nanosorbents in the SPME technique used for the extraction of EOCs from water and wastewater samples. In this review, the preparation, properties, advantages, and limitations of nanosorbents used in SPME applications are evaluated and discussed. Besides, the applications of these nanosorbents in SPME-based extraction techniques and their analytical characteristics for the determination of EOCs are reviewed. Graphical abstract.

Nano-Size Biomass Derived from Pomegranate Peel for Enhanced Removal of Cefixime Antibiotic from Aqueous Media: Kinetic, Equilibrium and Thermodynamic Study.

Nano-sized activated carbon was prepared from pomegranate peel (PG-AC) via NaOH chemical activation and was fully characterized using BET, FT-IR, FE-SEM, EDX, and XRD. The newly synthesized PG-AC was used for cefixime removal from the aqueous phase. The effective parameters on the adsorption process, including solution pH (2-11), salt effect (0-10%), adsorbent dosage (5-50 mg), contact time (5-300 min), and temperature (25-55 °C) were examined. The experimental adsorption equilibrium was in close agreement with the type IV isotherm model set by the International Union of Pure and Applied Chemistry (IUPAC). The adsorption process was evaluated with isotherm, kinetic, and thermodynamic models and it is were well fitted to the Freundlich isotherm (R2 = 0.992) and pseudo-second-order model (R2 = 0.999). The Langmuir isotherm provided a maximum adsorption capacity of 181.81 mg g-1 for cefixime uptake onto PG-AC after 60 min at pH 4. Hence, the isotherm, kinetic and thermodynamic models were indicated for the multilayer sorption followed by the exothermic physical adsorption mechanism.

Magnetic amino-functionalized hollow silica-titania microsphere as an efficient sorbent for extraction of pesticides in green and roasted coffee beans.

This study describes the synthesis and application of a magnetic amino-functionalized hollow silica-titania microsphere as a new sorbent for magnetic dispersive micro-solid phase extraction of selected pesticides in coffee bean samples. The sorbent was fully characterized by Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, transition electron microscopy, energy-dispersive X-ray spectroscopy, and vibrating sample magnetometry techniques. Significant extraction parameters affecting the proposed method, such as extraction time, sorbent amount, sample solution pH, salt amount, and desorption conditions (desorption solvent and time) were investigated and optimized. All the figures of merits were validated in coffee bean samples under the matrix-matched calibration method. Linear dynamic ranges were 5-250 µg/kg with the determination coefficients (R2 ) > 0.9980. The limits of detection for the pesticides of chlorpyrifos, malathion, hexaconazole, and atrazine were 1.42, 1.43, 1.35, and 1.33 µg/kg, respectively. Finally, the method was successfully applied for the determination of the pesticides in green and roasted coffee bean samples, and the obtained recoveries were in the range of 74-113% for spiked samples. The prepared sorbent could be used for the magnetic dispersive micro-solid phase extraction of pesticides in the plant-derived food matrix.