Photodecoration of tungsten oxide nanoparticles onto eggshell as an ultra-fast adsorbent for removal of MB dye pollutant.

Nowadays, the use of natural wastes and adsorbents along with their modification by simple and new methods based on metal oxides to remove dye pollutants has been the focus of many researchers. In this study, for the first time, simple and low-cost modification of eggshell (EGS) with tungsten oxide (WO3) based on the photochemical modification method as a green, ultra-fast, cost-effective, and biodegradable adsorbent is reported to remove of methylene blue (MB) dye pollutant. The EGS modified by WO3 was investigated by EDX, EDX mapping, XRD, FE-SEM, and UV-Vis Diffuse Reflectance (DRS) analyses. The obtained results show that the modified EGS by WO3 has more than ten times (78.5%) the ability to remove MB dye pollutant within 3 min compared to bare EGS (11%). Various parameters including dye pollutant pH, dye concentration, adsorbent dosage, and reusability of the WO3/EGS adsorbent for removal of MB dye pollutant were investigated and the result show that the adsorbent capacity of WO3/EGS is 1.64 mg g-1. EGS adsorbent The synthesis of WO3/EGS adsorbent with a novel photochemical method as a fast and very cheap adsorbent with excellent efficiency can be a promising alternative adsorbent for various purposes in removing dye pollutants from water environments.

Decolorization, COD and turbidity removal of the raw vinasse effluent by a one-step electro-oxidation process on a Pb/PbO2 anode.

In this research, and for the first time, the application of anode Pb/PbO2 (prepared from combined thermal oxidation and electrochemical oxidation method) and steel cathode in a flow sample electrochemical treatment process of vinasse and in the wastewater of alcohol factories, has been investigated. The combination of electrodes of Pb/PbO2 as an anode, steel, and/or graphite as a cathode was used in the proposed electrochemical treatment setup. The efficiency of the proposed electrochemical treatment was determined by the removal percentage of chemical oxygen demand (COD), turbidity and color of vinasse samples. The response surface method (RSM) by Minitab 18 was used to determine the effect of the studied factors as well as to detect the relationship between variables. The results showed that under optimum conditions (Pb/PbO2 electrode as the anode and steel electrode as the cathode, a voltage of 30 V, pH 6.5, and reaction time of 45 min), the percentage reduction values of COD, turbidity and color were 97.7, 77.3 and 92.7%, respectively.

Simple and complex coacervation methods for the nanoencapsulation of Rosa damascena mill L. anthocyanin in zein/potato starch: A new approach to enhance antioxidant and thermal properties.

The structure and antioxidant properties of zein and potato starches as well as the stability of anthocyanins strongly depend on the pH. However, due to the stability of anthocyanins in at acidic medium, their encapsulation has been limited to low pHs. In the present work, an encapsulation of anthocyanins extracted from Rosa damascena mill L. (as a model) into zein, starch, and their binary mixtures by simple and complex coacervation methods over a wide range of pH (especially higher pHs), and different encapsulating agent doses and different initial volumes of anthocyanin were studied in order to obtain new conditions for the preservation of anthocyanins and to improve the antioxidant activities of zein and potato starches. High levels of antioxidant activity and encapsulation efficiency for zein/starch/anthocyanin nanocapsules and maximum antioxidant activity for zein/starch nanocapsules (without anthocyanin) were obtained at pHs 8 and 2, respectively. Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray powder diffraction, and thermal gravimetric analysis techniques were used to analyze simple and complex coacervates biopolymer interactions, morphology, and thermal stability. The size of zein nanocapsules (283-366 nm) decreased in the range of 50-175 nm after the encapsulation of anthocyanin (pH 8), which makes them suitable for drug delivery processes. The prepared nanocapsules showed a high scavenging ability.

Introducing potato starch-ecofriendly silver nanoparticles as a novel binary system for nanoencapsulation of riboflavin.

Riboflavin (Rf), an externally supplied nutrient, is highly photosensitive, and should be protected from sunlight once used in food and pharmaceutical manufacturing. The applications of encapsulated Rf have recently developed due to their therapeutic properties. In this study, the use of green silver nanoparticles (AgNPs) synthesized by Rosa damascena mill L. extract to control the encapsulation efficiency of Rf in potato starch was demonstrated for the first time. Starch/Rf, Starch/AgNPs/Rf and Starch/AgNPs nanocapsules were characterized by Fourier-transform infrared, field emission scanning electron microscopy, differential scanning calorimetry, and brunauer-Emmett-Teller techniques. The obtained results showed that the presence of AgNPs reduces Rf nanocapsules size (from 340 to 327 nm), increases the encapsulation efficiency (21.14 ± 0.62 to 92.52 ± 1.32 %) and improves the thermal stability, antibacterial and antioxidant activities. Moreover, UV-vis spectroscopy demonstrated the stronger association of AgNPs/Rf and AgNPs/Rf/Starch nanocapsules with BSA under physiological conditions.

Rapid detection of apple juice concentrate adulteration with date concentrate, fructose and glucose syrup using HPLC-RID incorporated with chemometric tools.

The present study investigates the substitute of apple juice concentrate with some cheap sweeteners including glucose syrup, fructose syrup, and date concentrate, as the most common adulterants. For this purpose, pure and authenticated apple juice concentrate was individually adulterated with 10% to 50% of glucose syrup, fructose syrup, and date concentrate. High-performance liquid chromatography coupled with a refractive index detector (HPLC-RID) was applied to determine the carbohydrates profile of samples. The results of HPLC-RID were subjected to multivariate statistical analysis, namely principal component analysis (PCA) and linear discriminant analysis (LDA). The results showed that the glucose/fructose ratio and maltose content were the best indicators to detect adulteration of apple juice concentrate. A set of glucose, sorbitol, sucrose, maltose, and glucose/fructose ratio was used as a discriminating factor. Using this approach, adulteration of apple juice concentrate with cheaper sweeteners was detected at a limit of 10%, depending on the adulterant.

Highly-sensitive and fast detection of human telomeric G-Quadruplex DNA based on a hemin-conjugated fluorescent metal-organic framework platform.

The formation of G-quadruplex (G4) structures in Human telomeric DNA (H-Telo) has been demonstrated to inhibit the activity of telomerase enzyme that is associated with the proliferation of many cancer cells. Accordingly, G-quadruplex structures have become one of the well-established targets in anticancer therapeutic strategies. And, the development of simple and selective detection platforms for G4 structures has become a significant focus of research in recent years. In this study, a simple "off-on" fluorometric method was developed for the selective detection of picomolar quantities of H-Telo G4 DNA based on a fluorescent cerium-based metal organic framework (Ce-MOF) conjugated with hemin to form the sensing probe, Hemin@Ce-MOF. The solvothermal synthesis of the Ce-MOF took advantage of 5-aminoisophtlalic acid (5AIPA) as the organic bridging ligand, (Ce2(5AIPA)3(DMF)2). Characterization of Ce-MOF and Hemin@Ce-MOF was performed by XRD, XPS, TEM, SEM, BET and FTIR techniques. The detection and quantification of the H-Telo was carried out through the adsorption/incorporation of hemin molecules on the pores and surface of Ce-MOF resulting in the fluorescent quenching of the system followed by the restoration of the fluorescence upon addition of H-Telo probably due to a competition between H-Telo and Ce-MOF to bind to hemin. The impact of the key variables including MOF quantity, hemin concentration and detection time was investigated and optimized. Under the optimized conditions, the developed probe provides a limit of detection (LOD) of 665 pM, linear dynamic range (LDR) of 1.6-39.7 nM and excellent selectivity towards H-Telo. Taken together, these results present a simple, novel and superior platform for the selective detection of H-Telo G4 DNA.

Application of diatomite for sorption of Pb, Cu, Cd and Zn from aqueous solutions: kinetic, thermodynamic studies and application of response surface methodology (RSM).

Contamination of water and soil with toxic metals is a serious environmental issue. To study the Pb, Cu, Cd, and Zn sorption behavior by diatomite, batch experiments were carried out with increasing levels of initial concentration (0-200 mg/L) under different contact times (0-360 min) and temperatures (283, 293, 303, and 313 K). The effects of concentration (0-200 mg/L), pH (3-6), and ionic strength (0.01-0.06 mol/L) on the sorption were modeled using response surface methodology (RSM). Results showed that adsorption data were well-fitted by the Langmuir equation. The sorption of metals intensified by increasing initial concentration and pH but ionic strength had inverse effect. High value for R2 (0.99) and adjusted R2 (0.99) showed that the removal of ions can be described by response surface method. One-way ANOVA showed (p-value < 0.0001) that quadratic model is the best model for determining the interaction of variables. The values of the sorption energy parameter from Dubinin-Radushkevich model (E < 8 kJ K-1  mol-1 ) and negative values of ∆G showed that the sorption of the metals was physical and spontaneous. The positive values of enthalpy (ΔH) indicated that the sorption reaction of metals was endothermic at 283-313 K. PRACTITIONER POINTS: Applications of diatomite increased the sorption of Pb, Cd, Zn, and Cu from aqueous solutions. Diatomite, as low-cost adsorbent, had significant potential to sorption of ions. The sorption of heavy metals by adsorbent intensified by increasing initial concentration and pH but ionic strength had inverse effect. High value for R2 (0.99) and adj-R2 (0.99) showed that removal of metals can be described by response surface method (RSM) and the initial concentration of metal was the most significant factor.

Colorimetric speciation analysis of chromium using 2-thiobarbituric acid capped silver nanoparticles.

In the present work, 2-thiobarbituric acid (TBA)-capped silver nanoparticles (AgNPs) have been introduced as a novel nanoprobe in the construction of a sensitive and selective colorimetric sensor for Cr(iii) and Cr(vi) ions. Cr(iii) can be linked to TBA on the AgNP surface via -N or -OH groups and form a bridge between two or more AgNPs causing their aggregation. This phenomenon leads to a dramatic color change in TBA-AgNPs from yellow to pinkish red. UV-Vis spectrophotometry, FT-IR and transmission electron microscopy (TEM) were utilized for quantitative analyses, characterization of modified AgNPs and determination of the interaction mechanism of TBA-AgNPs - Cr(iii). The color change depended on the concentration of Cr(iii) and the ratio of UV-Vis absorption intensity at 520 nm to that at 418 nm (A520/A418) was linearly proportional to the concentration of Cr(iii) from 0.012 to 3.25 mg L-1 (LOD = 8.4 µg L-1). To eliminate or reduce the interference of other cations in Cr(iii) determination, EDTA was used as a masking agent at pH 6.5. Moreover, the developed method was used for the determination of Cr(vi) in the presence of ascorbic acid (AA) (as a reducing agent) in the concentration range of 0.20 to 1.40 mg L-1. The proposed probe was successfully applied for the determination of Cr(iii) and Cr(vi) in cement factory wastewater.

Monolithic mixed matrix membrane based on polyethersulfone/functionalized MWCNTs nanocomposite as an SPME fiber: Application to extract chlorophenols from human urine and serum samples followed by GC-ECD.

A monolithic mixed matrix membrane of functionalized multi-walled carbon nanotubes-polyethersulfone (MWCNT/PES) was prepared in a non-covalent approach and employed as an SPME fiber for extraction of chlorophenols (CPs). The proposed extraction method was followed by GC-ECD to determine the analytes. The influencing factors on the extraction efficiency such as pH, ionic strength, extraction and desorption temperature and time were studied. Under the selected conditions, calibration curves were linear over a wide concentration range from 0.005 to 1000 µgL-1 (r2 > 0.9961) for target analytes. In addition, the limits of detection (LOD) of the method were obtained in the range of 0.3-30 ng L-1. The relative standard deviation (RSD) for single fiber repeatability (n = 5) is from 1.4 to 4.6%. Fiber-to-fiber repeatability (n = 3) was also evaluated and the RSD is in the range of 1.3-6.3%. Applications of proposed fiber for extraction of CPs from the headspace of urine and serum samples were successfully investigated. The relative recovery in the biological samples spiked with different levels of CPs were in the range of 91.6-102.5%.

Silver nanoparticles-tragacanth gel as a green membrane for effective extraction and determination of capecitabine.

A novel eco-friendly and effective electromembrane extraction method combining high-performance liquid chromatography with UV detection was developed for the enrichment and determination of capecitabine. Tragacanth-silver nanoparticles conjugated gel was prepared by dissolving the tragacanth powder in synthesized silver nanoparticles solution and was used as a green membrane in electromembrane extraction. The porosity and presence of silver nanoparticles in the gel were characterized by field emission scanning electron microscopy. This new electromembrane extraction approach uses neither organic solvent nor carrier agents to extract the target analyte. The best electromembrane extraction efficiency was obtained by using 4.0 mm membrane gel thickness containing 2.5% w/v of tragacanth gum, donor phase pH = 5.0, acceptor phase pH = 3.0, applied voltage 50 V, extraction time 20 min, and agitation rate 500 rpm. During method validation under the optimized conditions, good linearity dynamic range between 1 and 500 ng/mL with the coefficient of determination (R2 ) = 0.998 was obtained. Limit of detection and Limit of quantitation were estimated to be 0.84 and 1.0 ng/mL, respectively. Finally, the applicability of this method in real samples was confirmed by an acceptable performance in extraction and determination of capecitabine in human plasma samples.

Screen printed carbon electrode modified with a copper@porous silicon nanocomposite for voltammetric sensing of clonazepam.

The work describes an electrochemical sensor for the determination of the tranquilizer clonazepam (CZP) in serum and pharmaceutical preparations. A screen printed carbon electrode (SPCE) was modified with copper nanoparticles anchored on porous silicon (PSi). The surface of the SPCEs modified with the Cu/PSi nanostructure was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoemission spectroscopy, energy dispersive X-ray spectroscopy and field-emission scanning electron microscopy. Cyclic and differential pulse voltammetric methods were used for the electrochemical studies and electrochemical detection, respectively. Several parameters controlling the performance of the modified SPCE were optimized. The peak current values (at a potential of -0.52 V) were used to construct calibration plots. Under the optimum conditions, the calibration plot is linear in the 0.05-7.6 µM CZP concentration range, and the detection limit is 15 nM. The sensor is reproducible, repeatable, highly selective and sensitive. It was successfully applied to the determination of CPZ in spiked serum and in drugs. Graphical abstract Scheme of electrochemical reduction of clonazepam on the designed copper@porous silicon modified screen printed carbon electrode (CuNPs/PSi/SPCE). This electrode was employed for the determination of clonazepam in tablets and human blood plasma using differential pulse voltammetry.

Fe3 O4 @GO on silica sand as an efficient and economical adsorbent; Typical application for removal of phenol and 2,4-dichlorophenol from water samples.

In this research, the layer-by-layer coating of silica sand surface with monolayer of graphene oxide (GO) immobilized on magnetite nanoparticles (Fe3 O4 MNPs) sublayer was investigated as a novel, low-cost, effective, and green nanocomposite material for adsorption of phenol and 2,4-dichloro-phenol (DCP). Several characterization techniques such as FTIR spectroscopy, X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM) were used to confirm the successful synthesis of Fe3 O4 MNPs@GO on silica. The efficiency of Fe3 O4 MNPs@GO-coated silica (SiO2 ) for the removal of the target phenolic compounds from water samples was evaluated. The maximum removal of phenol (52%) and DCP (73%) was observed using 1.0 g adsorbent, initial concentration of 12.5 mg/dm3 (for phenol) and 15 mg/dm3 (for DCP), sample volume of 10 ml (for phenol) and 15 ml (for DCP), contact time of 20 min (for phenol) and 10 min (for DCP), and pH = 5. The adsorption isotherm models of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich as well as kinetic and intraparticle diffusion models were also examined. Eventually, SiO2 /Fe3 O4 MNPs@GO was regenerated five times for removal of examined contaminants and their removal efficiency from the water inlet of a water treatment plant was assessed. PRACTITIONER POINTS: Immobilizing monolayer of GO nanosheets on silica sands surface for the first time has been achieved. GO monolayer anchors on silica sands through Fe3 O4 nanoparticles as sublayer without using very expensive tris(hydroxymethyl) aminomethane agent. Modified silica sands are introduced as a novel and economic pollutants adsorbent, which can be used in filter sands of water treatment industry. The SiO2 /Fe3 O4 MNPs@GO significantly reduces the amount of phenol and 2,4-dichloro-phenol (DCP) as model organic pollutants from water samples.

Extraction and Trace Analysis of Trihalomethanes in Water Samples Using Zein@Fe3O4 Nanocomposite.

This study presents a simple dispersive solid phase extraction (DSPE) technique combined with headspace thermal desorption (HSTD) for extraction and determination of the most significant trihalomethanes (THMs), bromodichloromethane, bromoform, chloroform and dibromochloromethane, in water samples by using Zein@Fe3O4 nanocomposite coupled with gas chromatography/micro electron capture detection (GC-MECD). Various parameters affecting the DSPE-HSTD performance were investigated and optimized. The obtained results revealed that under optimum conditions, LOD and LOQ values were in the range of 0.1-0.36, 0.3-1.08 µg L-1, respectively. The intra-day and inter-day precisions of the method at a concentration of 10 µg L-1 for each analyte (n = 5) were obtained in the range of 5.69-6.70% and 6.12-7.34%, respectively. Finally, the proposed method was successfully applied for extraction and determination of four THMs in drinking water samples.

Rapid ionic liquid-supported nano-hybrid composite reinforced hollow-fiber electromembrane extraction followed by field-amplified sample injection-capillary electrophoresis: An effective approach for extraction and quantification of Imatinib mesylate in human plasma.

The focus of this study is development of a new, convenient, rapid and sensitive electromembrane extraction approach (based on an ionic liquid-supported MWCNTs/ZnO reinforced hollow fiber, for the first time) as an off-line sample clean-up/preconcentration method coupled with capillary electrophoresis (CE-UV) using field-amplified sample injection (FASI) for quantification of Imatinib mesylate in human plasma. The nano-hybrid sorbent, coated by 1-octyl-3-methylimidazolium bromide ionic liquid ([OMIm]Br) in this research, was prepared by a feasible basic catalyzed sol-gel method. Then, it was immobilized (supported by capillary forces and sonication) in pores of a segment of a polypropylene hollow fiber membrane as the extraction unit after dispersing in 2-nitrophenyl octyl ether (NPOE) solvent and subsequently served as the supported liquid membrane (SLM) composition. Significant variables affecting the proposed method were evaluated and optimized to achieve the maximum extraction performance. Optimal conditions were obtained by NPOE with 4mgmL-1 nano-sorbent as the SLM composition, 105V as the driving force, pH 2 and 1.8 of the donor and acceptor phases, respectively, an extraction time of 15min and an agitation rate of 800rpm. The developed method was validated according to FDA guidelines. Regarding the validation results, the method is proved to be linear (R2=0.998) over concentrations ranging from 25 to 1500ngmL-1 (LOD=6.24ngmL-1). The mean RSD values for intra- and inter-day precision studies were 6.83 and 7.71%, respectively and the mean recoveries ranged between 98 and 106%. Finally, the validated method was successfully applied for sensitive, selective and rapid determination of Imatinib in patient's plasma samples.

Fluorescent Carbon Dot as Nanosensor for Sensitive and Selective Detection of Cefixime Based on Inner Filter Effect.

Here a simple and sensitive fluorescent assay for detecting Cefixime based on inner filter effect (IFE) has been proven, which is conceptually different from the previously reported CEF fluorescent assays. In this sensing platform, fluorescent carbon dots (CDs) were prepared by one-pot synthesis and was directly used as fluorophore in IFE. The method is based on the complexation reaction between cefixime and palladium ion in the presence of acidic buffer solution (pH 4). The Pd(II)-CEFcomplex was capable of functioning as a powerful absorber in IFE to influence the excitation of fluorophore (CDs). Production Pd(II)-CEFcomplex induced the absorption band transition from 310 to 400 nm, which resulted in the complementary overlap with the excitation spectra of CDs. Due to the competitive absorption, the excitation of CDs was significantly weakened, resulting in the quenching of CDs. The present IFE-based sensing strategy showed a good linear relationship from 0.2 × 10-6 M to 8 × 10-6 M (R2 = 0.987) and provided an exciting detection limit of 0.5 × 10-7 (3δ/slope). The proposed method has been successfully applied for the determination of cefixime in raw milk and human urine samples.

Application of zein-modified magnetite nanoparticles in dispersive magnetic micro-solid-phase extraction of synthetic food dyes in foodstuffs.

A simple method for the simultaneous and trace analysis of four synthetic food azo dyes including carmoisine, ponceau 4R, sunset yellow, and allura red from some foodstuff samples was developed by combining dispersive µ-solid-phase extraction and high-performance liquid chromatography with diode array detection. Zein-modified magnetic Fe3 O4 nanoparticles were prepared and used for µ-solid-phase extraction of trace amounts of mentioned food dyes. The prepared modified magnetic nanoparticles were characterized by scanning electron microscopy and FTIR spectroscopy. The factors affecting the extraction of the target analytes such as pH, amount of sorbent, extraction time, type and volume of the desorption eluent, and desorption time were investigated. Under the optimized conditions, the method provided good repeatability with relative standard deviations lower than 5.8% (n = 9). Limit of detection values ranged between 0.3 and 0.9 ng/mL with relatively high enrichment factors (224-441). Comparing the obtained results indicated that Fe3 O4 nanoparticles modified by zein biopolymer show better analytical application than bare magnetic nanoparticles. The proposed method was also applied for the determination of target synthetic food dyes in foodstuff samples such as carbonated beverage, snack, and candy samples.

Capillary electrophoresis with online stacking in combination with AgNPs@MCM-41 reinforced hollow fiber solid-liquid phase microextraction for quantitative analysis of Capecitabine and its main metabolite 5-Fluorouracil in plasma samples isolated from cancer patients.

The purpose of this study is the development and validation of a simple, novel, selective and fast off-line microextraction technique combining capillary electrophoresis with in-column field-amplified sample injection (FASI) for the simultaneous determination of capecitabine (CAP) and its active metabolite, 5-Fluorouracil (5-FU), in human plasma. At the moment, there is a lack of using cost-effective CE tool combined with novel miniaturized sample clean-up techniques for analysis of these important anti-cancer agents in plasma samples. This paper intends to fill this gap and describe a simple off-line sample pretreatment by means of AgNPs@MCM-41 reinforced hollow fiber Solid/Liquid phase microextraction (AgNPs@MCM41-HF-SLPME) with subsequent quantitation by FASI-CE. The separation of analytes was performed using a BGE containing 60mM phosphate-Tris buffer (pH 7) with 10% methanol as an organic modifier. Before sample loading, a short water plug (50mbar, 3s) was injected to permit FASI for stacking. Various parameters affecting the off-line microextraction efficiency as well as FASI were optimized. Migration time was found to be 6.6 (±0.1)min for 5-FU and 7.4 (±0.2)min for CAP. The linearity, precision, accuracy, recovery, selectivity, specificity, stability as well as the robustness of the method was evaluated from spiked plasma samples during the course of validation. The results revealed that the presented technique demonstrates acceptable accuracy and precision, miniaturized sample preparation and a reduced need for complicated equipment along with an acceptable analysis time. The validated method was successfully applied to determine CAP and 5-FU in patient's plasma samples.