Design and manufacture of new hybrid hydrogel and superabsorbent polymer for controlled release of fulvic acid based on grafted xanthan gum/gelatin using electron irradiation and its use in fodder corn cultivation.

A humic acid-gelatin (HA-Gel) hydrogel, a gallic acid-xanthan gum (GA-XG) hydrogel, a HA-Gel/GA-XG hydrogel, and superabsorbent polymer (SAP) of HA-Gel/GA-XG/polyacrylamide (PAM) hydrogel were synthesized using electron beam irradiation method. The capability of synthesized hydrogels in loading and controlled release of fulvic acid (FA) was studied. The chemical and physical structure of sorbents was confirmed by various analyses. The effect of irradiation dose on mechanical properties, gel percentage, swelling, and absorbency under load (AUL) of the sorbents was investigated. By changing the hydrogel structures into the SAP form, its swelling capacity was increased from 37 to 320 g/g. Both hybrid hydrogel and SAP were reusable for up to 7 cycles. The maximum fertilizer loading capacities for SAP and hybrid hydrogel were 402.1 and, 175.5 mg g-1, respectively. In comparison to hydrogels, the SAP showed a slower FA-release performance. Thus, in soil media, 86 % of FA was released in 15-20 days from the hybrid hydrogel while with the SAP, 81 % of FA was released in 30-35 days. The significant improvement in the growth of fodder corn treated with FA-loaded SAP in the greenhouse media in comparison to the control groups showed the effective performance of the designed SAP, favoring its practical applications.

Dispersive solid-phase extraction of buprenorphine from biological fluids using metal-organic frameworks and its determination by ultra-performance liquid chromatography.

In this work, various types of metal-organic frameworks were synthesized, and their affinities toward buprenorphine were evaluated using dispersive solid-phase extraction. The extracted buprenorphine was determined by ultra high performance liquid chromatography-ultraviolet detection system. The highest extraction recovery was observed by employing zeolitic imidazole framework-67. Then, a facile and fast extraction method was designed for the extraction and purification of the target drug. Optimization of the extraction method was carried out by the design of experiment approach. A linearity range of 1-1000 µg/L with the limit of detection of 0.15 µg/L and relative standard deviations (50 µg/L, n = 5) of 3.4% was obtained for standard sample analysis. Under optimized experimental and instrumental conditions, the relative recoveries were in the range of 95 to 111%. Eventually, zeolitic imidazole framework-67 was successfully employed for the extraction and determination of buprenorphine in the biological fluids with satisfactory results.

Design of a pseudo stir bar sorptive extraction using graphenized pencil lead as the base of the molecularly imprinted polymer for extraction of nabumetone.

Molecularly imprinted polymer (MIP) was synthesized through the coprecipitation method on the graphene oxide anchored pencil lead as a substrate for the first time and applied as an efficient sorbent for pseudo stir bar sorptive extraction of nabumetone. The extracted analyte was determined by a novel spectrophotometric method based on the aggregation of silicate sol-gel stabilized silver nanoparticles in the presence of the analyte. The synthesized polymer was characterized using Fourier transform infrared spectroscopy and field emission scanning electron microscopy. Optimization of important parameters affecting the extraction efficiency was done using central composite design whereas the spectrophotometric method was optimized via one at a time variable. Under the optimal conditions, the calibration curve exhibited linearity in the concentration range of 1.5-20.0 µg L-1. A limit of detection of 0.20 µg L-1, an enhancement factor of 393 and relative standard deviations (at 10 µg L-1, n = 6) of 4.6% and 8.1% for intra- and inter-day analysis were obtained. The developed procedure was successfully utilized for the quantification of traces of nabumetone in tap water and biological samples with the complex matrix including human urine and serum.

Doxycycline drug delivery using hydrogels of O-carboxymethyl chitosan conjugated with caffeic acid and its composite with polyacrylamide synthesized by electron beam irradiation.

Two hydrogels of O-carboxymethyl chitosan conjugated with caffeic acid and its composite with polyacrylamide were synthesized using electron beam irradiation. The synthesized hydrogels were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and mechanical properties studies. The hydrogels were loaded with doxycycline by swelling and its release was investigated in various media. The effect of the dose of electron beam irradiation and PAAm amount on the properties of hydrogels including swelling, drug loading, drug release, mechanical properties, and gel content were studied. The release of doxycycline form hydrogels in different media obeyed the mechanism of non-Fickian diffusion and best fitted to the Higuchi model and Korsmeyer-Peppas. In-vitro doxycycline release consideration indicated that the drug's release from composite hydrogel occurs with higher amounts than the other one. The cytotoxic study confirmed the non-toxicity of the prepared hydrogels dressing. Moreover, the growth inhibition of permissive bacteria against Staphylococcus aureus and Escherichia coli were observed for doxycycline-loaded hydrogels. So, the synthesized hydrogels are appropriate for practical application as a new antibacterial wound dressing.

Electron beam irradiation synthesis of porous and non-porous pectin based hydrogels for a tetracycline drug delivery system.

Electron beam irradiation was used for the synthesize of porous and non-porous pectin based hydrogels through conjugation of pectin with 5-hydroxytryptophan in the presence and absence of sodium dodecyl sulfate, respectively. The hydrogels were characterized by different methods. Tetracycline hydrochloride was loaded on the hydrogels by swelling equilibrium method and its release in different media was studied. The effect of SDS amount and electron beam irradiation dose on the swelling, drug loading, drug release, gel content, and mechanical properties were investigated. The release of drug form both hydrogels followed non-Fickian diffusion mechanism and was best fitted with the Korsmeyer-Peppas model. In vitro, drug release studies revealed that the release of drug from non-porous hydrogel is relatively slow while its release from porous hydrogel occurs with higher amounts and faster rate. Biocompatibility and cytotoxic analysis indicate that the prepared hydrogels dressing are non-thrombogenic, non-hemolytic and non-toxic. Furthermore, acceptable bacteria growth inhibition against Escherichia coli and Staphylococcus aureus were observed for both drug-loaded hydrogels. Thus, these hydrogels are suitable for the application of an antibacterial wound dressing.

A novel theranostic system of AS1411 aptamer-functionalized albumin nanoparticles loaded on iron oxide and gold nanoparticles for doxorubicin delivery.

Recently DNA aptamers have attracted remarkable attention as possible targeting ligands since selective targeting of cancer cells is a critical step in cancer diagnosis and therapy. Here, the development of AS1411 aptamer-functionalized albumin nanoparticles loaded on iron oxide and gold nanoparticles is reported for target delivery of the well-known anticancer drug of doxorubicin (Dox). Iron oxide nanoparticles (IONPs) and gold nanoparticles (GNPs) were prepared by ultrasound-assisted and controlled seeded growth synthetic methods, respectively. The nanocarrier was synthesized by a desolvation cross-linking method and characterized by dynamic light scattering, zeta potential measurement, thermogravimetric analysis, transmission electron microscopy, as well as vibrating sample magnetometer. The synthesized nanoparticles were found to be spherical with an average diameter of 120 nm and zeta potential of about -50.3 mV. The in-vitro anti-tumor effect of the designed delivery vehicle on MCF7 and SKBR3 human cancer cells was evaluated by MTT assay. The experimental results revealed that it could significantly inhibit the proliferation of cancerous cells. Moreover, GNPs and IONPs with the coating of albumin did not show any toxicity. AS1411 aptamer-functionalized nanoparticles improved cellular uptake and efficiency to MCF7 breast cancer cells as compared to non-targeting nanoparticles because of the high affinity of mentioned aptamer toward the overexpressed nucleolin on MCF7 cell surface.

Simultaneous Functionalization and Reduction of Magnetic Graphene Oxide by L-Histidine and its Application for Magnetic Separation/Preconcentration of Antioxidant Trace Elements.

In the present study, for the first time, the magnetic graphene oxide was simultaneously functionalized and reduced with the aim of imidazole-based L-histidine amino acid (rGO/Fe3O4-histidine). The prepared nanocomposite was characterized by field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy, and vibrating sample magnetometer. The synthesized rGO/Fe3O4-histidine nanosheets were implied for solid phase extraction of ultra-trace amounts of Zn2+, Cu2+, and Mn2+ from biological samples prior to ICP-OES determination. The calibration curves were linear in the concentration ranges of 0.4-182.0, 0.4-215.0, and 0.2-168.5 µg L-1 for Zn2+, Cu2+, and Mn2+, respectively. The limits of detection were 0.12, 0.10, and 0.04 µg L-1 for Zn2+, Cu2+, and Mn2+, respectively. The relative standard deviations (RSDs) at 50.0 µg L-1 for single-sorbent repeatability and sorbent-to-sorbent reproducibility were less than 6.7 and 9.2% (n = 5), respectively. The accuracy of the method was confirmed by the analysis of a serum quality control material (QCM, Seronorm™ Human Serum REF NO 203105) and hair certified reference material (CRM, Human Hair IAEA-086).

Synthesis of composite hydrogel of glutamic acid, gum tragacanth, and anionic polyacrylamide by electron beam irradiation for uranium (VI) removal from aqueous samples: Equilibrium, kinetics, and thermodynamic studies.

A bio-compatible hydrogel sorbent was prepared through chemical conjugation of glutamic acid (GA) with gum tragacanth (GT) followed by mixing with anionic polyacrylamide (PAAm) and irradiating by the electron beam. The prepared composite of the hydrogel of GA-GT/PAAm was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, point zero charge (PZC) analysis, thermogravimetric analysis (TGA), and X-ray diffraction-(XRD). The sorption capability of the hydrogel was investigated for the removal of U(VI) from aqueous samples. The sorption data were analyzed by Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models and the experimental results were in agreement with Langmuir isotherm. The sorption process was found to be endothermic and spontaneous. The maximum sorption capacity of the composite of GA-GT/PAAm hydrogel for U(VI) determined from Langmuir isotherm was 384.6 mg g-1. The experimental data were also analyzed by four different kinetic equations, and the results were fitted well with the pseudo-second-order model.

Temperature-controlled liquid-liquid microextraction combined with high-performance liquid chromatography for the simultaneous determination of diazinon and fenitrothion in water and fruit juice samples.

A simple, environmentally benign, and rapid method based on temperature-controlled liquid-liquid microextraction using a deep eutectic solvent was developed for the simultaneous extraction/preconcentration of diazinon and fenitrothion. The method involved the addition of deep eutectic solvent to the aqueous sample followed by heating the mixture in a 75°C water bath until the solvent was completely dissolved in the aqueous phase. Then, the resultant solution was cooled in an ice bath and a cloudy solution was formed. Afterward, the mixture was centrifuged and the enriched deep eutectic solvent phase was analyzed by high-performance liquid chromatography with ultraviolet detection for quantification of the analytes. The factors affecting the extraction efficiency were optimized. Under the optimized extraction conditions, the limits of detection for diazinon and fenitrothion were 0.3 and 0.15 µg/L, respectively. The calibration curves for diazinon and fenitrothion exhibited linearity in the concentration range of 1-100 and 0.5-100 µg/L, respectively. The relative standard deviations for five replicate measurements at 10.0 µg/L level of analytes were less than 2.8 and 4.5% for intra- and interday assays, respectively. The developed method was successfully applied to the determination of diazinon and fenitrothion in water and fruit juice samples.

A novel sensor for determination of naproxen based on change in localized surface plasmon peak of functionalized gold nanoparticles.

A highly selective and sensitive colorimetric sensor for the determination of naproxen (NAP) based on the aggregation of the thiolated ß-cyclodextrin (Tß-CD) functionalized gold nanoparticles (Tß-CD-Au NPs) in the presence of NAP and Zn2+is described. The hydrophobic end of NAP interacts with the immobilized Tß-CD on the Au NPs and forms the complex of Tß-CD:NAP while the Zn2+ ions form a 1:2 complex of (NAP)2Zn with the carboxyl groups of NAP resulting in the aggregation of functionalized gold nanoparticles. As a result of aggregation, the localized surface plasmon resonance (LSPR) band of functionalized gold nanoparticles around 520nm decreases and a new red shifted band at 650nm appears which increases gradually as the function of NAP concentration. The calibration graph derived from the intensity ratios of absorbance at 650nm to 520nm was linear in the concentration range of 4-180µgL-1of NAP. At the optimum conditions, the limit of detection (LOD) and quantification (LOQ) were found to be 0.6 and 2.1µgL-1, respectively and the relative standard deviation at 20µgL-1of NAP (n=5) was 2.5%. The selectivity and applicability of the method was verified through analyzes of the synthetic samples containing the major interference compounds reported in literature as well as tablets, wastewater and urine samples. The accuracy of the method was evaluated by recovery experiments and analysis of pharmaceutical tablets.

Application of Deep Eutectic Solvent Modified Cotton as a Sorbent for Online Solid-Phase Extraction and Determination of Trace Amounts of Copper and Nickel in Water and Biological Samples.

Deep eutectic solvent (DES) was used as the extractant to improve the extraction properties of cotton. DES of choline chloride-urea (ChCl-urea) was prepared and immobilized on the surface of cotton fibers. The resulting sorbent was packed on a microcolumn, and a flow injection flame atomic absorption spectrometry was designed for the online separation and determination of trace amounts of copper and nickel. Various parameters affecting the extraction recovery of analytes such as pH, sample volume, sample loading rate, nature, volume, concentration, and flow rate of eluent were investigated and optimized. Under the optimum conditions, the method showed good linearity in the concentration range of 0.25-50.0 and 4.0-125.0 µg L-1 with the coefficient of determination (r 2) of 0.9991 and 0.9990 for copper and nickel, respectively. The method was very sensitive with the detection limits (defined as 3Sb/m) of 0.05 and 0.60 µg L-1 for Cu and Ni, respectively. It was successfully applied for the determination of Cu and Ni in water and biological samples. The accuracy of the method was evaluated through the recovery experiments and independent analysis by electrothermal atomic absorption spectrometry.

Preconcentration of valsartan by dispersive liquid-liquid microextraction based on solidification of floating organic drop and its determination in urine sample: Central composite design.

In this work, a fast, easy, and efficient dispersive liquid-liquid microextraction method based on solidification of floating organic drop followed by high-performance liquid chromatography with UV detection was developed for the separation/preconcentration and determination of the drug valsartan. Experimental design was applied for the optimization of the effective variables (such as volume of extracting and dispersing solvents, ionic strength, and pH) on the extraction efficiency of valsartan from urine samples. The optimized values were 250.0 µL ethanol, 65.0 µL 1-dodecanol, 4.0% w/v NaCl, pH 3.8, 1.0 min extraction time, and 4.0 min centrifugation at 4000 rpm min(-1) . The linear response (r(2) = 0.997) was obtained in the range of 0.013-10.0 µg mL(-1) with a limit of detection of 4.0 ng mL(-1) and relative standard deviations of less than 5.0 % (n = 6).

Application of modified stir bar with nickel:zinc sulphide nanoparticles loaded on activated carbon as a sorbent for preconcentration of losartan and valsartan and their determination by high performance liquid chromatography.

In this study, the stir bar was coated for the first time with the ​nicel:zins sulphide nanoparticles (Ni:ZnS NPs) loaded on activated carbon (AC) (Ni:ZnS-AC) as well as 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) using sol gel technique and was used for stir bar sorptive extraction (SBSE) of losartan (LOS) and valsartan (VAL) as the model compounds. The extracted analytes were then quantified by high performance liquid chromatography (HPLC) equipped with an ultra violet detector. The best extraction performance for LOS and VAL was obtained through the optimization of the parameters affecting SBSE including pH of sample solution, ionic strength, extraction time, volume of desorption solvent, desorption time, and stirring speed. The fractional factorial design (FFD) was used to find the most important parameters, which were then optimized by the central composite design (CCD) and the desirability function (DF). Under the optimal experimental conditions, wide linear ranges of 0.4-50µgL(-1) and 0.5-50µgL(-1) and good RSDs (at level of 5µgL(-1) and n=6) of 4.4 and 4.9% were obtained for LOS and VAL, respectively. With the enrichment factors (EFs) of 188.6 and 184.8-fold, the limits of detection (LODs, S/N=3) of the developed method were found to be 0.12 and 0.15µgL(-1) for LOS and VAL, respectively. The developed method was successfully applied to the determination of LOS and VAL in urine and plasma matrices.

Development of a novel method for determination of mercury based on its inhibitory effect on horseradish peroxidase activity followed by monitoring the surface plasmon resonance peak of gold nanoparticles.

A highly sensitive and simple indirect spectrophotometric method has been developed for the determination of trace amounts of inorganic mercury (Hg(2+)) in aqueous media. The method is based on the inhibitory effect of Hg(2+) on the activity of horseradish peroxidase (HRP) in the oxidation of ascorbic acid by hydrogen peroxide followed by the reduction of Au(3+) to Au-NPs by unreacted ascorbic acid and the measurement of the absorbance of localized surface plasmon resonance (LSPR) peak of gold nanoparticles (at 530 nm) which is directly proportional to the concentration of Hg(2+). Under the optimum conditions, the calibration curve was linear in the concentration range of 1-220 ng mL(-1). Limits of detection (LOD) and quantification (LOQ) were 0.2 and 0.7 ng mL(-1), respectively and the relative standard deviation at 100 ng mL(-1) level of Hg(2+) was 2.6%. The method was successfully applied to the determination of mercury in different water samples.

Deep eutectic liquid organic salt as a new solvent for liquid-phase microextraction and its application in ligandless extraction and preconcentraion of lead and cadmium in edible oils.

Deep eutectic liquid organic salt was used as the solvent and a liquid phase microextraction (DES-LPME) combined with electrothermal atomic absorption spectrometry (ETAAS) was developed for separation, preconcentration and determination of lead and cadmium in edible oils. A 4:1 mixture of deep eutectic solvent and 2% nitric acid (200 µL) was added to an oil sample. The mixture was vortexed and transferred into a water bath at 50 °C and stirred for 5 minutes. After the extraction was completed, the phases were separated by centrifugation, and the enriched analytes in the deep eutectic solvent phase were determined by ETAAS. Under optimized extraction conditions and for an oil sample of 28 g, enhancement factors of 198 and 195 and limits of detection (defined as 3 Sb/m) of 8 and 0. 2 ng kg(-1) were achieved for lead and cadmium respectively. The method was successfully applied to the determination of lead and cadmium in various edible oils.

Solid phase microextraction of diclofenac using molecularly imprinted polymer sorbent in hollow fiber combined with fiber optic-linear array spectrophotometry.

A simple solid phase microextraction method based on molecularly imprinted polymer sorbent in the hollow fiber (MIP-HF-SPME) combined with fiber optic-linear array spectrophotometer has been applied for the extraction and determination of diclofenac in environmental and biological samples. The effects of different parameters such as pH, times of extraction, type and volume of the organic solvent, stirring rate and donor phase volume on the extraction efficiency of the diclofenac were investigated and optimized. Under the optimal conditions, the calibration graph was linear (r(2)=0.998) in the range of 3.0-85.0 µg L(-1) with a detection limit of 0.7 µg L(-1) for preconcentration of 25.0 mL of the sample and the relative standard deviation (n=6) less than 5%. This method was applied successfully for the extraction and determination of diclofenac in different matrices (water, urine and plasma) and accuracy was examined through the recovery experiments.

Combination of solid phase extraction and dispersive liquid-liquid microextraction for separation/preconcentration of ultra trace amounts of uranium prior to its fiber optic-linear array spectrophotometry determination.

A simple and sensitive method for the separation and preconcentration of the ultra trace amounts of uranium and its determination by spectrophotometry was developed. The method is based on the combination of solid phase extraction and dispersive liquid-liquid microextraction. Thus, by passing the sample through the basic alumina column, the uranyl ion and some cations are separated from the sample matrix. The retained uranyl ion along with the cations are eluted with 5 mL of nitric acid (2 mol L(-1)) and after neutralization of the eluent, the extracted uranyl ion is converted to its anionic benzoate complex and is separated from other cations by extraction of its ion pair with malachite green into small volume of chloroform using dispersive liquid-liquid microextraction. The amount of uranium is then determined by the absorption measurement of the extracted ion pair at 621 nm using flow injection spectrophotometry. Under the optimum conditions, with 500 mL of the sample, a preconcentration factor of 1980, a detection limit of 40 ng L(-1), and a relative standard deviation of 4.1% (n=6) at 400 ng L(-1) were obtained. The method was successfully applied to the determination of uranium in mineral water, river water, well water, spring water and sea water samples.

Suspended nanoparticles in surfactant media as a microextraction technique for simultaneous separation and preconcentration of cobalt, nickel and copper ions for electrothermal atomic absorption spectrometry determination.

The aim of this study was to describe a new method of microextraction based on the suspension of alumina nanoparticles in the surfactant media for simultaneous separation and preconcentration of the ultra-traces of cobalt, nickel and copper ions. In this technique, the alumina nanoparticles were suspended in the non-ionic surfactant solution of Triton X-114. The analytes in the sample solution were adsorbed onto the nanoparticles. After the phase separation based on the cloud point of the mixture at 40 °C, the nanoparticles settled down in the surfactant rich phase. Then 120 µL of nitric acid (3.0 mol L(-1)) was added to the surfactant rich phase which caused desorption of the analytes. Finally, the liquid phase was separated by centrifugation from the nanoparticles and was used for the quantification of the analytes by the electrothermal atomic absorption spectrometry (ETAAS). The parameters affecting the extraction and detection processes were optimized. Under the optimized experimental conditions (i.e. pH∼8, Triton X-114, 0.05% (v/v); temperature 40 °C), a sample volume of 25 mL resulted in the enhancement factors of 198, 205 and 206 and detection limits (defined as 3Sb/m) of 2.5, 2.8 and 2.6 ng L(-1) for Co(II), Ni(II) and Cu(II) respectively. The sorbent showed high capacity for these metal ions (30-40 mg g(-1) sorbent). The method was successfully applied to the determination of the analytes in natural water samples.

Spectrophotometric determination of iron species using a combination of artificial neural networks and dispersive liquid-liquid microextraction based on solidification of floating organic drop.

A dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) and artificial neural networks method was developed for the simultaneous separation/preconcentration and speciation of iron in water samples. In this method, an appropriate mixture of ethanol (as the disperser solvent) and 1-undecanol (as the extracting solvent) containing appropriate amount of 2-thenoyltrifluoroacetone (TTA) (as the complexing agent) was injected rapidly into the water sample containing iron (II) and iron (III) species. At this step, the iron species interacted with the TTA and extracted into the 1-undecanol. After the phase separation, the absorbance of the extracted irons was measured in the wavelength region of 450-600 nm. The artificial neural networks were then applied for simultaneous determination of individual iron species. Under optimum conditions, the calibration graphs were linear in the range of 95-1070 µg L(-1) and 31-350 µg L(-1) with detection limits of 25 and 8 µg L(-1) for iron (II) and iron (III), respectively. The relative standard deviations (R.S.D., n=6) were lower than 4.2%. The enhancement factor of 162 and 125 were obtained for Fe(3+) and Fe(2+) ions, respectively. The procedure was applied to power plant drum water and several potable water samples; and accuracy was assessed through the recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry.

QSAR models for CXCR2 receptor antagonists based on the genetic algorithm for data preprocessing prior to application of the PLS linear regression method and design of the new compounds using in silico virtual screening.

The CXCR2 receptors play a pivotal role in inflammatory disorders and CXCR2 receptor antagonists can in principle be used in the treatment of inflammatory and related diseases. In this study, quantitative relationships between the structures of 130 antagonists of the CXCR2 receptors and their activities were investigated by the partial least squares (PLS) method. The genetic algorithm (GA) has been proposed for improvement of the performance of the PLS modeling by choosing the most relevant descriptors. The results of the factor analysis show that eight latent variables are able to describe about 86.77% of the variance in the experimental activity of the molecules in the training set. Power prediction of the QSAR models developed with SMLR, PLS and GA-PLS methods were evaluated using cross-validation, and validation through an external prediction set. The results showed satisfactory goodness-of-fit, robustness and perfect external predictive performance. A comparison between the different developed methods indicates that GA-PLS can be chosen as supreme model due to its better prediction ability than the other two methods. The applicability domain was used to define the area of reliable predictions. Furthermore, the in silico screening technique was applied to the proposed QSAR model and the structure and potency of new compounds were predicted. The developed models were found to be useful for the estimation of pIC50 of CXCR2 receptors for which no experimental data is available.