Maturity impact on physicochemical composition and polyphenol properties of extra virgin olive oils obtained from Manzanilla, Arbequina, and Koroneiki varieties in Iran.

This study investigated the physicochemical properties and polyphenol composition of extra virgin olive oils (EVOOs) extracted from three olive cultivars. The investigated cultivars were Arbequina, Koroneiki, and Manzanilla, grown in Olive Research Station in Rudbar county, Gilan province, Iran, at three ripening stages. Several parameters were analyzed, including peroxide and acidity values, unsaponifiable matter, oxidative stability, total aliphatic alcohols, fatty acids (FAs), sterols, and triacylglycerol composition. The results showed that as maturity increased, parameters such as oil content, acidity value, and iodine value, rise, while parameters including peroxide value, oxidative stability, aliphatic alcohols, and unsaponifiable matter decreased (p < .05). The saponification value was slightly reduced in the developing ripening process (p > .05). The MUFA/PUFA ratio and total sterol content declined during the olive ripening stages (p < .05). The triterpenes decreased in Arbequina and Koroneiki cultivars but increased in Manzanilla cultivar during the maturity stages. According to the data, oleuropein decreased while oleuropein aglycone, oxidized aldehyde, and hydroxylic form of oleuropein increased for all EVOOs during maturation. Apigenin, quercetin, ligstroside aglycone, aldehyde and hydroxylic form, ferulic acid, caffeic acid, and catechin decreased during the ripening of fruits (p < .05). The main triglycerides were triolein (OOO), palmitodiolein (POO), dioleolinolein (OOL), and palmitooleolinolein (PLO) in all EVOOs. In addition, the olive cultivar and harvesting date influence the physicochemical properties and polyphenol composition of EVOOs extracted from olive varieties grown in one region. In conclusion, the results can present helpful information to determine the optimum maturity stage for the investigated olive cultivars.

An investigation on conjugated linoleic acid content, fatty acid composition, and physicochemical characteristics of Iranian Kurdish butter oil.

In this study, physicochemical and quality properties, fatty acid composition, and triglyceride composition of Iranian Kurdish butter oil (IKBO) obtained from yogurt drink (doogh) butter were investigated. Local doogh butter, prepared from cow's (CIKBO) and ewe's milk (EIKBO), was utilized as the raw material for this purpose. The free fatty acids (FFA) and peroxide values of IKBOs of the cow (CIKBO) and ewe (EIKBO) were obtained at 0.41 ± 0.01 and 0.39 ± 0.01 (g Oleic acid 100/g oil), and 1.32 ± 0.00 and 1.35 ± 0.00 (meq O2 kg/oil), respectively. The amounts of saturated fatty acids (SFAs): 70.27 ± 0.62 and 72.13 ± 0.84 (g/100 g), monounsaturated fatty acids (MUFAs): 19.37 ± 0.74 and 20.56 ± 0.97 (g/100 g), and polyunsaturated fatty acids (PUFAs): 1.22 ± 0.12 and 2.75 ± 0.38 (g/100 g) were obtained in CIKBO and EIKBO, respectively. The significant majority of the fatty acids (FAs) in the examined CIKBO and EIKBO were myristic (CIKBO: 13.76 ± 0.02 (g/100 g) and EIKBO: 14.83 ± 0.07 (g/100 g)), palmitic (CIKBO: 33.14 ± 0.28 (g 100/g) and EIKBO: 31.86 ± 0.02 (g/100 g)), stearic (CIKBO: 8.27 ± 0.06 (g/100 g) and EIKBO: 7.95 ± 0.06 (g/100 g)), capric (CIKBO: 4.83 ± 0.03 (g/100 g) and EIKBO: 6.75 ± 0.01 (g/100 g)), and oleic acids (CIKBO: 15.37 ± 0.12 (g/100 g) and EIKBO: 17.83 ± 0.02 (g/100 g)). The average of conjugated linoleic acid (CLA) content in EIKBO (2.20 ± 0.22 (g/100 g)) was higher than that in CIKBO (0.92 ± 0.25 (g/100 g)) (p < .05). Therefore, EKIBO is considered the superior natural supply of CLA.

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.

Magnetic Beads of Zero Valent Iron Doped Polyethersolfun Developed for Removal of Arsenic from Apatite-Soil Treated Water.

The drop immerses calcium chloride aqueous solution was utilized to prepare the zero valent iron-doped polyethersulfone beads (PES/ZVI) for the efficient removal of arsenic from apatite-soil treated waters. The proposed beads can assist in promoting uptake efficiency by hindering ZVI agglomeration due to a high porosity and different active sites. The PES/ZVI beads were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetism (VSM). The main objective of this study was to investigate the function of new PES/ZVI beads with an increased removal efficiency for the remediation of arsenic ions from the apatite-soil treated waters. A maximum adsorption removal of 82.39% was achieved when the experiment was performed with 80 mg of adsorbent for a contact time of 180 min. Based on the results, a removal efficiency >90% was obtained after 300 min of shaking time with an arsenic concentration of 20 mg·L-1. The experimental process was fitted with the Langmuir model due to the high R2 (0.99) value compared to the Freundlich model (0.91) with an adsorption capacity of 41.32 mg·g-1. The adsorption process speed was limited by pseudo-second-order (R2 = 0.999) and the adsorption mechanism nature was endothermic and physical.

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.

Synthesis of new Zn-decorated metal-organic frameworks for enhanced removal of carcinogenic textile dye: equilibrium and kinetic modeling studies.

This paper describes the synthesis and characterization of Zn2+ decorated (adipic and terephthalic acid as linkers) piperazine-based metal-organic framework (P-MOFs) and their extraction behavior toward the Chicago sky blue (CSB) dye. The formation of Zn2+-decorated P-MOFs was confirmed by FT-IR spectroscopy, energy-dispersive spectroscopy, X-ray diffraction, BET surface area analysis and TGA. Adsorption behavior of the synthesized P-MOFs was explored through solid-phase adsorption (batch method) prior to UV-Vis spectrophotometric determination. Adsorption parameters, including adsorbent dosage, pH of solution, dye concentration, and time, were optimized. Excellent percentage removal of 94% and 95% for AP-Zn-MOF and TP-Zn-MOF, respectively, was achieved at pH 7.5. Kinetics studies indicated that the synthesized adsorbents AP-Zn-MOF and TP-Zn-MOF followed the pseudo-second-order rate model with R2 value 0.9989. The Freundlich isotherm with high R2 value as compared to Langmuir isotherm indicated that CSB adsorption for the synthesized MOFs follows multilayer adsorption.

Papain grafted into the silica coated iron-based magnetic nanoparticles 'IONPs@SiO2-PPN' as a new delivery vehicle to the HeLa cells.

The present study aims at engineering, fabrication, characterization, and qualifications of papain (PPN) conjugated SiO2-coated iron oxide nanoparticles 'IONPs@SiO2-PPN'. Initially fabricated iron oxide nanoparticles (IONPs) were coated with silica (SiO2) using sol-gel method to hinder the aggregation and to enhance biocompatibility. Next, PPN was loaded as an anticancer agent into the silica coated IONPs (IONPs@SiO2) for the delivery of papain to the HeLa cancer cells. This fabricated silica-coated based magnetic nanoparticle is introduced as a new physiologically-compatible and stable drug delivery vehicle for delivering of PPN to the HeLa cancer cell line. The IONPs@SiO2-PPN were characterized using FT-IR, AAS, FESEM, XRD, DLS, and VSM equipment. Silica was amended on the surface of iron oxide nanoparticles (IONPs, γ-Fe2O3) to modify its biocompatibility and stability. The solvent evaporation method was used to activate PPN vectorization. The following tests were performed to highlight the compatibility of our proposed delivery vehicle: in vitro toxicity assay, in vivo acute systemic toxicity test, and the histology examination. The results demonstrated that IONPs@SiO2-PPN successfully reduced the IC50 values compared with the native PPN. Also, the structural alternations of HeLa cells exposed to IONPs@SiO2-PPN exhibited higher typical hallmarks of apoptosis compared to the cells treated with the native PPN. The in vivo acute toxicity test indicated no clinical signs of distress/discomfort or weight loss in Balb/C mice a week after the intravenous injection of IONPs@SiO2 (10 mg kg-1). Besides, the tissues architectures were not affected and the pathological inflammatory alternations detection failed. In conclusion, IONPs@SiO2-PPN can be chosen as a potent candidate for further medical applications in the future, for instance as a drug delivery vehicle or hyperthermia agent.

Adsorption and in vitro release study of curcumin form polyethyleneglycol functionalized multi walled carbon nanotube: kinetic and isotherm study.

Polyethylene glycol functionalized with oxygenated multi-walled carbon nanotubes (O-PEG-MWCNTs) as an efficient nanomaterial for the in vitro adsorption/release of curcumin (CUR) anticancer agent. The synthesized material was morphologically characterized using scanning electron microscopy, Fourier transform infrared spectroscopy and transmission electron microscopy. In addition, the CUR adsorption process was assessed with kinetic and isotherm models fitting well with pseudo-second order and Langmuir isotherms. The results showed that the proposed O-PEG-MWCNTs has a high adsorption capacity for CUR (2.0 × 103 mg/g) based on the Langmuir model. The in vitro release of CUR from O-PEG-MWCNTs was studied in simulating human body fluids with different pHs (ABS pH 5, intestinal fluid pH 6.6 and body fluid pH 7.4). Lastly, to confirm the success compliance of the O-PEG-MWCNT nanocomposite as a drug delivery system, the parameters affecting the CUR release such as temperature and PEG content were investigated. As a result, the proposed nanocomposite could be used as an efficient carrier for CUR delivery with an enhanced prolonged release property. Graphical Abstract ᅟ.

Electroless-coated magnetic three-dimensional graphene with silver nanoparticles used for the determination of pesticides in fruit samples.

A new type of adsorbent composed of magnetic three-dimensional graphene coated with silver nanoparticles was synthesized by an electroless technique and used in the magnetic solid-phase extraction of selected pesticides (fenitrothion, chlorpyrifos, and hexaconazole) before gas chromatography with a micro-electron capture detector. The adsorbent was characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometry, and field-emission scanning electron microscopy. The important extraction parameters such as pH, adsorbent dose, extraction time, and desorption conditions were investigated. Under the optimal conditions, the analytical figures of merit were obtained as: linear dynamic range of 0.1-5 ng/g with determination coefficients of 0.991-0.996; limit of detection of 0.07-0.13 ng/g; limit of quantification of 0.242-0.448 ng/g; and the intraday and interday relative standard deviations (C = 5 ng/g, n = 3) were 3.8-8.7 and 6.6-8.9%, respectively. The developed method was successfully applied for analysis of the selected pesticides in tomato and grape with extraction recoveries in the range of 72.8-109.6%.

Magnetic graphene coated inorganic-organic hybrid nanocomposite for enhanced preconcentration of selected pesticides in tomato and grape.

The new magnetic graphene based hybrid silica-N-[3-(trimethoxysilyl)propyl]ethylenediamine (MG@SiO2-TMSPED) nanocomposite was synthesized via sol-gel process, and used as an effective adsorbent in magnetic solid phase extraction (MSPE) of three selected pesticides followed by gas chromatography micro-electron capture detection (GC-µECD). The adsorbent was characterized using Fourier transform-infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDXS) techniques. The analytical validity of the developed method was evaluated under optimized conditions and the following figures of merit were obtained: linearity, 1-20µgkg-1 with good determination coefficients (R2=0.995-0.999); limits of detection (LODs), 0.23-0.30µgkg-1 (3×SD/m, n=3); and limits of quantitation (LOQ), 0.76-1.0µgkg-1 (10×SD/m, n=3). The precision (RSD%) of the proposed MSPE method was studied based on intra-day (3.43-8.83%, n=3) and inter-day (6.68-8.37%, n=12) precisions. Finally, the adsorbent was applied to determination of pesticides in tomato and grape samples and good recoveries were obtained in the range from 82 to 113% (RSDs 5.1-8.1%, n=3).

New magnetic graphene-based inorganic-organic sol-gel hybrid nanocomposite for simultaneous analysis of polar and non-polar organophosphorus pesticides from water samples using solid-phase extraction.

A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL-1 for phosphamidon and dimethoate, and 10-100 pg mL-1 for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL-1 for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL-1) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g-1) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.

Simultaneous preconcentration of polar and non-polar organophosphorus pesticides from water samples by using a new sorbent based on mesoporous silica.

A new mesoporous silica based on the sol-gel material cyanopropyltriethoxysilane (CNPrTEOS) was successfully synthesized by the hydrolysis and condensation of CNPrTEOS in the presence of ammonium solution as catalyst and methanol as solvent. It was used as a solid-phase extraction sorbent for the simultaneous extraction of three organophosphorus pesticides, namely, polar dicrotophos and non-polar diazinon and chlorpyrifos. Analysis was performed using high-performance liquid chromatography with UV detection. CNPrTEOS was characterized by FTIR spectroscopy, field-emission scanning electron microscopy and nitrogen gas adsorption. The surface area and average pore diameter of the optimum sol-gel CNPrTEOS are 379 m(2) /g and 4.7 nm (mesoporous), respectively. The proposed solid-phase extraction based on CNPrTEOS exhibited good linearity in the range of 0.8-100 µg/L, satisfactory precision (1.15-3.82%), high enrichment factor (800) and low limit of detection (0.072-0.091 µg/L). The limits of detection obtained using the proposed solid-phase extraction method are well below the maximum residue limit set by European Union and are also lower (13.6-48.5×) than that obtained by using a commercial CN-SPE cartridge (0.98-4.41 µg/L). The new mesoporous sol-gel CNPrTEOS showed promising alternative as SPE sorbent material for the simultaneous extraction of polar and non-polar organophosphorus pesticides.

Synthesis of Polyaniline-Coated Graphene Oxide@SrTiO3 Nanocube Nanocomposites for Enhanced Removal of Carcinogenic Dyes from Aqueous Solution.

The present investigation highlights the synthesis of polyaniline (PANI)-coated graphene oxide doped with SrTiO3 nanocube nanocomposites through facile in situ oxidative polymerization method for the efficient removal of carcinogenic dyes, namely, the cationic dye methylene blue (MB) and the anionic dye methyl orange (MO). The presence of oxygenated functional groups comprised of hydroxyl and epoxy groups in graphene oxide (GO) and nitrogen-containing functionalities such as imine groups and amine groups in polyaniline work synergistically to impart cationic and anionic nature to the synthesised nanocomposite, whereas SrTiO3 nanocubes act as spacers aiding in segregation of GO sheets, thereby increasing the effective surface area of nanocomposite. The synthesised nanocomposites were characterised by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The adsorption efficiencies of graphene oxide (GO), PANI homopolymer, and SrTiO3 nanocubes-doped nanocomposites were assessed by monitoring the adsorption of methylene blue and methyl orange dyes from aqueous solution. The adsorption efficiency of nanocomposites doped with SrTiO3 nanocubes were found to be of higher magnitude as compared with undoped nanocomposite. Moreover, the nanocomposite with 2 wt % SrTiO3 with respect to graphene oxide demonstrated excellent adsorption behaviour with 99% and 91% removal of MB and MO, respectively, in a very short duration of time.