Laser irradiation for controlling size of TiO2-Zeolite nanocomposite in removal of 2,4-dichlorophenoxyacetic acid herbicide.

This study focused on the synthesis of TiO2-Zeolite nanocomposite through a sol-gel approach. The decrease in the size of the nanocomposite is considered a primary parameter to improve photocatalytic activity. In this regard, fabricated samples were exposed to laser irradiation (532 nm) for four different time intervals in order to investigate the size variation of the nanocomposite. FTIR, UV-Vis, XRD, DLS, SEM and EDX analyses were applied to characterize and determine the size of the products. An optimized nanocomposite sample, in term of the particle size, was used for photodegradation of 2,4-D herbicide from aqueous solution. Photodegradation was carried out under UV irradiation (12 W) and Xe lamp irradiation (200 W). The obtained results showed that laser irradiation time has a substantial effect on controlling the size of the nanocomposite. Results from the photocatalyst study indicated that the elimination of 2,4-D under the Xe lamp irradiation was higher compared with the UV irradiation. Also, the final synthesized nanocomposite exhibited higher catalytic activity for photodegradation of 2,4-D compared with pure Zeolite and pure anatase TiO2 samples. The reusability of TiO2-Zeolite nanocomposite was studied in four successive cycles to evaluate the removal of 2,4-D under UV irradiation.

Magnetic nanoparticles modified with organic dendrimers containing methyl methacrylate and ethylene diamine for the microextraction of rosuvastatin.

Magnetic nanoparticles (MNPs) modified with organic dendrimers are shown to be a viable sorbent of the microextraction of the drug rosuvastatin (RST; also known as Crestor). The MNPs were prepared from iron(II) chloride and iron(III) chloride and then coated with silicon dioxide. The coated MNPs produced by this method have diameters ranging from 10 to 60 nm according to scanning electron microscopy. The MNPs were further modified with organic dendrimers containing methyl methacrylate and ethylene diamine. The resulting MNPs were characterized by SEM, Fourier transform infra-red and thermal gravimetry analysis. Then, the efficacy of the modified MNPs with respect to the extraction of RST was studied. The adsorption of RST by MNPs can be best described by a Langmuir isotherm. Following elution with buffer, RST was quantified by HPLC. The method was applied to the determination of RST in (spiked) human blood plasma, urine, and in tablets. RST extraction efficiencies are 54.5% in plasma, 86.6% from the drug matrix, and 94.3% in urine. The highest adsorption capacity of the RST by the MNPs adsorbent was 61 mg⋅g-1. Graphical abstract Co-precipitation was used to synthesize magnetic nanoparticles (MNPs). They were coated with a layer of SiO2 and then branched by organic dendrimers containing methyl methacrylate (MMA) and ethylene diamine (EDA). Rosuvastatin (RST) drug was trapped between dendrimer branches, therefore adsorption capacity of the drug was strongly increased.

Study on non-linear equilibrium, kinetics and thermodynamic of deltamethrin removal in aqueous solution using modified magnetic iron oxide nanoparticles.

The purpose of modification of magnetic iron oxide nanoparticles is an eco-friendly, emerging and economical method for removing deltamethrin in the aqueous solution and wastewater effluents when compared with other adsorbent methods. Modified magnetic iron oxide nanoparticles were synthesized by co-precipitation and then coupled with 3-hydroxytyraminium chloride. The nano-sorbent was characterized by thermogravimetric analysis, elemental analysis, transmission electron microscopy, scanning electron microscope, Fourier transform infrared spectroscopy, zero point charge and surface area determination. Batch studies were conducted and adsorption equilibrium, kinetic and thermodynamic non-linear models were carried out. The resulting equilibrium data were tested with Langmuir and Freundlich non-linear isotherm models, and the results showed that the Langmuir isotherm fitted the data well. Kinetic studies were done with different initial deltamethrin concentrations, adsorbent dosage and temperature, and the data were assimilated with pseudo-first order, pseudo-second order and intra-particle diffusion kinetic equations, and it was found that the studied nano-sorbent processes followed the pseudo-second order kinetic equation. Thermodynamic analysis was also carried out to estimate the changes in free energy (ΔG0), enthalpy (ΔH0), and entropy (ΔS0). The thermodynamic parameters revealed that the adsorption of deltamethrin into the nano-sorbent was spontaneous, feasible and showed an endothermic process.

Preparation of functionalized graphene oxide and its application as a nanoadsorbent for Hg(2+) removal from aqueous solution.

A poly(allyl acetoacetate)-grafted graphene oxide (GO-GAA) was successfully synthesized using Hummer's method by divinyl sulfone modification and allyl acetoacetate polymerizaton. This novel functionalized graphene oxide was characterized thoroughly by FTIR, XRD, FE-SEM, TEM, and TG-DT analyses. GO-GAA was then employed as an adsorbent for Hg(2+) removal from aqueous solutions. It exhibited higher adsorption capacity with regard to the pristine graphene oxide because of its effective functionalities, especially the dicarbonyl groups which are significant chelating agents. The effects of pH, temperature, and contact time on Hg(2+) adsorption were also investigated. The optimum Hg(2+) adsorption was obtained at pH 4 and T = 20-30 °C. The adsorption isotherm and kinetics were found to follow the Langmuir and pseudo-second-order models, respectively, with a correlation coefficient of 0.99 for both. The calculated maximum adsorption capacity of the adsorbent was 282.7 mg Hg(2+) per unit mass of GO-GAA, which is much more than 56 mg/g of that obtained for GO. The results showed that adsorption reaches up to 95 % of its maximum in less than 2 min. The synthesized GO-GAA as a novel and efficient adsorbent has been regenerated by HNO3 and reused. It retained its performance for Hg(2+) removal for several times and a less than 5 % decrease in removal efficiency was observed after four cycles of adsorption-desorption.

Selective Solid-Phase Extraction of Zinc(II) from Environmental Water Samples Using Ion Imprinted Activated Carbon.

A simple ion imprinted amino-functionalized sorbent was synthesized by coupling activated carbon with iminodiacetic acid, a functional compound for metal chelating, through cyanoric chloride spacer. The resulting sorbent has been characterized using FTIR spectroscopy, elemental analysis, and thermogravimetric analysis and evaluated for the preconcentration and determination of trace Zn(II) in environmental water samples. The optimum pH value for sorption of the metal ion was 6-7.5. The sorption capacity of the functionalized sorbent was 66.6 mg/g. The chelating sorbent can be reused for 10 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 100% was obtained for the metal ion with 0.5 M nitric acid as the eluent. Compared with nonimprinted polymer particles, the prepared Zn-imprinted sorbent showed high adsorption capacity, significant selectivity, and good site accessibility for Zn(II). Scatchard analysis revealed that the homogeneous binding sites were formed in the polymer. The equilibrium sorption data of Zn(II) by modified resin were analyzed by Langmuir, Freundlich, Temkin, and Redlich-Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.139, 12.82, and 2.34, respectively, at 25°C.

Selective extraction of clonazepam from human plasma and urine samples by molecularly imprinted polymeric beads.

A molecularly imprinted polymer (MIP) based on free-radical polymerization was prepared with 1-(N,N-biscarboxymethyl)amino-3-allylglycerol and N,N-dimethylacrylamide as functional monomers, N,N-methylene diacrylamide as the cross-linker, copper ion-clonazepam as the template and 2,2-azobis(2-methylbutyronitrile) as the initiator. The imprinted polymer was characterized by Fourier transform infrared spectroscopy, elemental analysis, thermo-gravimetric analysis, and SEM. The MIP of agglomerated microparticles with multipores was used for SPE. The imprinted polymer sorbent was selective for clonazepam. The optimum pH and sorption capacity were 5 and 0.18 mg/g at 20C, respectively. The profile of the drug uptake by the sorbent reflects good accessibility of the active sites in the imprinted polymer sorbent. The MIP-SPE was the most feasible technique for the extraction of clonazepam with a high recovery from human plasma and urine samples.

Hollow-fiber-supported liquid membrane microextraction of amlodipine and atorvastatin.

A simple, environmentally friendly, and efficient method, based on hollow-fiber-supported liquid membrane microextraction, followed by high-performance liquid chromatography has been developed for the extraction and determination of amlodipine (AML) and atorvastatin (ATO) in water and urine samples. The AML in two-phase hollow-fiber liquid microextraction is extracted from 24.0 mL of the aqueous sample into an organic phase with microliter volume located inside the pores and lumen of a polypropylene hollow fiber as acceptor phase, but the ATO in three-phase hollow-fiber liquid microextraction is extracted from aqueous donor phase to organic phase and then back-extracted to the aqueous acceptor phase, which can be directly injected into the high-performance liquid chromatograph for analysis. The preconcentration factors in a range of 34-135 were obtained under the optimum conditions. The calibration curves were linear (R(2) ≥ 0.990) in the concentration range of 2.0-200 µg/L for AML and 5.0-200 µg/L for ATO. The limits of detection for AML and ATO were 0.5 and 2.0 µg/L, respectively. Tap water and human urine samples were successfully analyzed for the existence of AML and ATO using the proposed methods.

Preparation of responsive nano-adsorbent to near-infrared laser based on tungsten disulfide for bicalutamide extraction in human biological fluids.

Bicalutamide (BLT), a non-steroidal anti-androgen, is widely used in patients with advanced prostate cancer. This study aimed to synthesize a smart modified nano-adsorbent (SMNA) based on tungsten disulfide (WS2) for solid-phase extraction of BLT from human plasma and urine samples. Briefly, we increased drug loading capacity of SMNA through the polymer grafting onto the WS2 nano-sheets. Specifically, poly (N-vinylcaprolactam) as a thermo-sensitive polymer was incorporated into the synthesized polymer networks. SMNA was characterized via TGA, XRD, FE-SEM and FT-IR techniques. The influential variables including pH (6), adsorption temperature (30°C), and contact time (10 min) were carefully optimized. After drug loading process, SMNA was exposed to 808 nm near-infrared light, the shrinkage of the thermo-sensitive polymer took place quickly and the loaded BLT released in a short time of laser irradiation. In the end, the extracted BLT was analyzed with RP-HPLC-UV system (at 270 nm wavelength). The proposed method provided favorable linearity in the range of 0.1-15 µg/mL (R2 ≥ 0.9998), the LOD and LOQ values were obtained 0.01 µg/mL and 0.04 µg/mL, respectively. The mean results of drug recovery (at the three different concentrations) of the spiked BLT in human plasma (92.08%) and urine (94.17%) were satisfactory.

pH-responsive glycodendrimer as a new active targeting agent for doxorubicin delivery.

The present study synthesized a new kind of pH-responsive active targeting glycodendrimer (ATGD) for doxorubicin delivery to cancerous cells. First, the glycodendrimer was synthesized based on the cultivation of chitosan dendrons on amine-functionalized, silica-grafted cellulose nanocrystals. Afterward, glycodendrimer was conjugated with folic acid to provide a folate receptor-targeting agent. The response surface method was employed to obtain the optimum conditions for the preparation of doxorubicin-loaded ATGD. The effect of doxorubicin/ATGD ratio, temperature, and pH on doxorubicin loading capacity was evaluated, and high loading capacity was achieved under optimized conditions. After determining doxorubicin release pattern at acidic and physiological pH, ATGD cytotoxicity was surveyed by MTT assay. Based on the results, the loading behavior of doxorubicin onto ATGD was in good agreement with monolayer-physisorption, and drug release was Fickian diffusion-controlled. ATGD could release the doxorubicin much more at acidic pH than physiological pH, corresponding to pH-responsive release behavior. Results of MTT assay confirmed the cytotoxicity of doxorubicin-loaded ATGD in cancer cells, while ATGD (without drug) was biocompatible with no tangible toxicity. These results suggested that ATGD has the potential for the treatment of cancer.

Design of 3-aminophenol-grafted polymer-modified zinc sulphide nanoparticles as drug delivery system.

Zinc sulphide (ZnS) nanoparticles were synthesized by the coprecipitation method. The ZnS nanoparticle surface was polymerized with allyl glycidyl ether (AGE), and 3-aminophenol was then deposited as a ligand on nanosorbent. The modified nanosorbent was investigated with Fourier transform infrared spectroscopy and thermogravimetric analysis. The particle size of the modified nanosorbent was studied with scanning electron microscopy. Some characteristic factors of the adsorption process such as pH and time were investigated for famotidine using the modified nanosorbent. The equilibrium adsorption study of famotidine by 3-aminophenol-grafted AGE/ZnS was analysed by adsorption isotherms of the Langmuir, Freundlich, and Temkin models. The famotidine-releasing process was investigated in simulated biological fluids (intestinal fluid at pH of 7.4 and gastric fluid at pH of 1.2) and demonstrated 65% and 73% famotidine release during periods of 30 h (pH = 7.4) and 60 min (pH = 1.2), respectively. These results reveal the optimal performance of 3-aminophenol-grafted AGE/ZnS for sustained drug delivery.

Analysis and health risk assessment of phthalate esters (PAEs) in indoor dust of preschool and elementary school centers in city of Tehran, Iran.

Individuals spend a lot of time indoors; thus they are generally exposed to phthalates used in consumer products. Therefore, those exposed to phthalates as indoor contaminants are at high risks. The present study was conducted to evaluate the carcinogenic and non-carcinogenic hazard of phthalate esters (PAEs), like dimethyl phthalate, diethyl phthalate, di(nbutyl) phthalate, butyl benzyl phthalate, dioctyl phthalate, and di(2-ethylhexyl) phthalate in the dust obtained from 21 schools in Tehran, in 2019. A total of 63 indoor dust specimens were obtained by a vacuum cleaner. After transferring dust samples to the laboratory, 100 mg of each sample was centrifuged and mixed with 20 ml acetone and kept through a night and ultrasonicated within 30 min. Eventually, PAEs' contents were measured via gas chromatography-mass spectrometry. Based on the findings, median concentrations of DMP, DEP, DnBP, BBP, DEHP, and DnOP were 0.90, 0.10, 6.0, 0.20, 118.30, and 4.10 mg kg-1 respectively. Moreover, the overall average daily exposure doses (ADD) of phthalate esters via dust ingestion, skin contact, and inhalation were 1.56E-03, 1.70E-06, and 1.56E-07 mg kg-1 day-1, respectively, and the lifetime average daily exposure doses (LADD) were 1.83E-04, 2.34E-08, and 2.46E-08 mg kg-1 day-1, respectively; thus ingestion of dust particles was found to be the main pathway of exposure to phthalate for non-carcinogenic and carcinogenic risks. Although based on the results, the studied samples were below the US Environmental Protection Agency threshold of 1.00E-06, due to the disadvantages of phthalates in human safety, these kinds of investigations are helpful in understanding the main ways of exposure to PAEs and providing a science-based framework for the future attempts for mitigating the PAEs indoor emissions.

New anion-exchange solid-phase extraction support used for preconcentration and determination of lead in water samples by flame atomic absorption spectrometry.

A new chelating resin was prepared by coupling Amberlite XAD-2 with Brilliant Green through an azo spacer. The resulting resin has been characterized by FTIR spectrometry, elemental analysis, and thermogravimetric analysis and studied for the preconcentration and determination of trace Pb(II) ions from solution samples. The anionic complex of Pb(II) and iodide was retained on the resin by the formation of an ion associate with Brilliant Green on Amberlite XAD-2 in weak acidic medium. The optimum pH value for sorption of the metal ion was 5.5. The sorption capacity of the functionalized resin is 53.8 mg/g. The chelating resin can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 103% was obtained for the metal ion with 0.1 M EDTA as the eluting agent. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The resin was subjected to evaluation through batch binding and column chromatography of Pb(II). The equilibrium adsorption data of Pb(II) on modified resin were analyzed by Langmuir, Freundlich, and Temkin models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined to be 0.192, 13.189, and 3.418 at pH 5.5 and 25 degrees C. The method was applied for lead ion determination in tap water samples.

Synthesis of chitosan-grafted-poly(N-vinylcaprolactam) coated on the thiolated gold nanoparticles surface for controlled release of cisplatin.

The gold nanoparticles surface was modified by thioglycolic acid ligand and their surface was coated by the chitosan-grafted-poly(N-vinylcaprolactam) (chitosan-g-PNVCL) copolymer. The cisplatin anticancer drug was loaded into the synthesized nanocarriers and its performance was investigated for the treatment of MCF-7 breast cancer cells in vitro. The synthesized nanoparticles were characterized using FTIR, DLS, TEM, SEM, EDX and TGA analysis. The lower critical solution temperature (LCST) of PNVCL/chitosan and PNVCL/chitosan coated gold nanoparticles were found to be 38 and 39 °C, respectively. The cisplatin loading efficiency, cisplatin release from nanoparticles at different temperatures and pH values as well as the pharmacokinetic studies were examined. The maximum cisplatin release from nanoparticles was achieved at T > LCST (42 °C) and pH of 5. The Korsemeyer-Peppas model was best described the cisplatin release from nanoparticles. The maximum MCF cell death was found to be 92% using cisplatin loaded-gold/TGA/chitosan-g-PNVCL nanoparticles under an induction heating system.

Application of polyamide thin-film composite layered on polysulfone-GO/TiO2 mixed matrix membranes for removal of nitrotoluene derivatives from petrochemical wastewaters.

Release of harmful organic intermediates or byproducts during the manufacture of petrochemical compounds is a serious problem in petrochemical plants. In this work, polysulfone membranes blended with GO/TiO2 nanocomposite were synthesized by phase inversion method and coated with a polyamide layer formed by interfacial polymerization to prepare a thin-film composite (TFC) sample. Analysis and characterization of the sample were carried out by XRD, FE-SEM, BET, FTIR/ATR, AFM, TGA, and zeta potential. Results indicated that incorporation of GO/TiO2 into the membrane structure enhanced porosity, surface roughness, and macrovoid formation along the cross-section of the sublayer and permeability of the membrane. The TFC membranes were applied to remove mononitrotoluene (MNT) and dinitrotoluene (DNT) as the basic intermediates of toluene diisocyanate (TDI). The membranes demonstrated high efficiency (> 90%) for the removal of MNT and DNT according to the charge exclusion mechanism and Donnan effect. Application of the TFC membrane for treatment of wastewater in the TDI plant showed that the removal of pollutants is variable in the range of 45-65% and 53-69% for the membrane with the highest flux and highest rejection in different transmembrane pressure, respectively.

Synthesis, characterization, and application of m-phenylendiamine-modified Amberlite XAD-4 resin for preconcentration and determination of metal ions in water samples.

A new chelating resin is prepared by coupling Amberlite XAD-4 (Serva, Heidelberg, New York) with m-phenylendiamine through an azo spacer, characterized (by elemental analysis, infrared, and thermogravimetric analysis) and studied for preconcentrating nickel(II), cobalt(II), zinc(II), copper(II), and chromium(III) using flame atomic absorption spectrometry for metal monitoring. The optimum pH values for sorption of the above-mentioned metal ions were 8.5, 8.5, 6.5, 6.5, and 5.5, respectively. The resin was subjected to evaluation through batch binding and column chromatography of the mentioned metal ions. Quantitative desorption occurred instantaneously with 0.5 M HNO3. Various flowrates of sorption and desorption of nickel(II) have been studied. The sorption capacity was found to be 3.89, 3.27, 2.96, and 3.44 mmol/g of resin for cobalt, copper, zinc, and nickel, respectively. The chelating resin can be reused for 10 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of >98% was obtained for all the metal ions, with 0.5 M HNO3 as the eluting agent. The method was applied for determination of metal ions from an industrial wastewater sample.

Synthesis and characterization of magnetized-PEGylated dendrimer anchored to thermosensitive polymer for letrozole drug delivery.

Letrozole as a target loaded drug on siliceous magnetized Fe3O4 nanoparticles grafted with high-branched dendrimers. Grafted polymer coating contained N-vinyl caprolactam as a stimulus-responsive polymer which functionalized with five generations of dendrimers containing oxime functional group. The precursors underwent PEGylating polymerization to form PEGylated dendrimer coating on the particle surface as the final carrier. The final product has the average size of ˜79 nm. The final product characterized by FT-IR, TGA, VSM, SEM-EDAX to investigate carrier features further. Some characteristic parameters in adsorption process like pH, time, the temperature investigated for letrozole using the final carrier. The physical and chemical properties of the final polymerized generations were also studied. Letrozole releasing process examined in the simulated intestinal fluid (pH = 7.4) revealed 95% of letrozole released during 25 h which also considered by Korsmeyer-Peppas equation to verify Fickian diffusion mechanism.

Synthesis of high generation thermo-sensitive dendrimers for extraction of rivaroxaban from human fluid and pharmaceutic samples.

In this present study, poly (N-isopropylacrylamide) as a thermo-sensitive agent was grafted onto magnetic nanoparticles, then ethylenediamine and methylmethacrylate were used to synthesize the first generation of poly amidoamine (PAMAM) dendrimers successively and the process continued alternatively until the ten generations of dendrimers. The synthesized nanocomposite was investigated using Fourier transform infrared spectrometry, thermalgravimetry analysis, X-ray diffractometry, elemental analysis and vibrating-sample magnetometer. The particle size and morphology were characterized using dynamic light scattering, field emission scanning electron microscopy and transmission electron microscopy. Batch experiments were conducted to investigate the parameters affecting adsorption and desorption of rivaroxaban by synthesized nanocomposite. The maximum sorption of rivaroxaban by the synthesized nanocomposite was obtained at pH of 8. The resulting grafted magnetic nanoparticle dendrimers were applied for extraction of rivaroxaban from biologic human liquids and medicinal samples. The specifications of rivaroxaban sorbed by a magnetic nanoparticle dendrimer showed good accessibility and high capacity of the active sites within the dendrimers. Urine and drug matrix extraction recoveries of more than 92.5 and 99.8 were obtained, respectively.

Preconcentration and Determination of Mefenamic Acid in Pharmaceutical and Biological Fluid Samples by Polymer-grafted Silica Gel Solid-phase Extraction Following High Performance Liquid Chromatography.

Mefenamic acid is a nonsteroidal anti-inflammatory drug (NSAID) that has analgesic, anti-infammatory and antipyretic actions. It is used to relieve mild to moderate pains. Solid-phase extraction of mefenamic acid by a polymer grafted to silica gel is reported. Poly allyl glycidyl ether/iminodiacetic acid-co-N, N-dimethylacrylamide was synthesized and grafted to silica gel and was used as an adsorbent for extraction of trace mefenamic acid in pharmaceutical and biological samples. Different factors affecting the extraction method were investigated and optimum conditions were obtained. The optimum pH value for sorption of mefenamic acid was 4.0. The sorption capacity of grafted adsorbent was 7.0 mg/g. The best eluent solvent was found to be trifluoroacetic acid-acetic acid in methanol with a recovery of 99.6%. The equilibrium adsorption data of mefenamic acid by grafted silica gel was analyzed by Langmuir model. The conformation of obtained data to Langmuir isotherm model reveals the homogeneous binding sites of grafted silica gel surface. Kinetic study of the mefenamic acid sorption by grafted silica gel indicates the good accessibility of the active sites in the grafted polymer. The sorption rate of the investigated mefenamic acid on the grafted silica gel was less than 5 min. This novel synthesized adsorbent can be successfully applied for the extraction of trace mefenamic acid in human plasma, urine and pharmaceutical samples.

Synthesis and characterization of poly[N-isopropylacrylamide-co-1-(N,N-bis-carboxymethyl)amino-3-allylglycerol] grafted to magnetic nano-particles for the extraction and determination of fluvoxamine in biological and pharmaceutical samples.

In this research, a novel method is reported for the surface grafting of N-isopropylacrylamide as a thermosensitive agent and 1-(N,N-bis-carboxymethyl)amino-3-allylglycerol with an affinity toward fluvoxamine onto magnetic nano-particles modified by 3-mercaptopropyltrimethoxysilane. The grafted nano-particles were characterized by Fourier transform infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The surface morphology was studied with scanning electron microscopy and transmission electron microscopy. The resulting grafted nano-particles were used in solid phase extraction and determining of trace fluvoxamine in biological human fluids and pharmaceutical samples. The profile of the fluvoxamine uptake by the modified magnetic nano-particles indicated good accessibility of the active sites in the grafted copolymer. It was found that the adsorption behavior could be fitted by the Freundlich adsorption isotherm model. It was observed that a maximum amount of fluvoxamine was released at a temperature above the lower critical solution temperature of the polymer.