Square-wave adsorptive stripping voltammetric approaches at two in situ modified electrodes as first analytical methods for the quantitative determination of a new anticancer drug candidate

The two adsorptive stripping voltammetric approaches for detection and quantitative determination of diethyl (2E)-2-{(2E)-[1-(4-methylphenyl)imidazolidin-2-ylidene]hydrazinylidene}butanedioate (DIB)—a novel molecule of medical importance—using two sensitive sensors based on modified glassy carbon electrodes as reusable sensors, were developed for the first time. The proposed electrochemical methods are based on adsorptive/reductive behaviour of DIB at two modified carbonic electrodes: a bismuth film-modified glassy carbon electrode (BiF/GCE) and a lead film-modified glassy carbon electrode (PbF/GCE). The electron gain mechanism for the electrochemical reduction of DIB on both developed sensors was proposed for the first time. To achieve the highest sensitivity in adsorptive stripping determinations, various experimental variables (e.g. the composition and pH of the supporting electrolytes, deposition conditions of bismuth and lead films, concentrations of plating solutions, accumulation times and potentials of DIB, etc.) were extensively examined. The comparison of validation parameters obtained during the determination of DIB at two sensors was presented. The excellent linear correlation was found between the monitored adsorptive stripping voltammetric peak current and the DIB concentration in the range of 15–600 μg L⁻¹ at an accumulation time of 30 s (with LOD = 4.2 μg L⁻¹ and LOQ = 14.0 μg L⁻¹) using the BiF/GCE as a sensor. Furthermore, the excellent linear relationship was confirmed between the monitored adsorptive stripping voltammetric peak current and the DIB concentration in the range of 9–900 μg L⁻¹ at an accumulation time of 10 s (with better LOD = 1.5 μg L⁻¹ and LOQ = 5.0 μg L⁻¹), employing the PbF/GCE as a sensor. The two optimized adsorptive stripping voltammetric approaches—as facile, sensitive, reliable and inexpensive—were successfully used as first methods for the quantitative analysis of a novel anticancer agent (DIB) in its pure pharmaceutically acceptable form. However, the practical applicability of square-wave adsorptive stripping voltammetric determination of the electroactive DIB molecule at a PbF/GCE, as the modified electrode of higher sensitivity, was presented after its successful solid phase extraction from a real serum sample.

     

A novel silica supported chitosan/glutaraldehyde as an efficient sorbent in solid phase extraction coupling with HPLC for the determination of Penicillin G from water and wastewater samples

In this study, silica@chitosan-glutaraldehyde (Si@Cs-G) was synthesized as a novel adsorbent for extraction of Penicillin G (PG) from the synthetic and real samples followed by HPLC determination. The synthesized adsorbents were characterized by the scanning electron microscopy (SEM), X-ray diffraction (XRD), fourier transform infrared (FTIR), dynamic light scattering (DLS), transmission electron microscopy (TEM) and nitrogen adsorption–desorption techniques. The factors influencing the extraction efficiency including pH, sorbent dose, extraction time, extraction solvent type and its volume were investigated and optimized.Under the optimal conditions (sorbent dosage: 25 mg, desorption solvent (acetonitrile) with volume of 0.75 mL; pH: 6 and extraction time: 50 min), the Si@Cs-G demonstrated high efficiency and linearity (R² > 0.999) with the concentration of penicillin G ranging from 1 to 300 μg L⁻¹. Extraction recovery in synthetic samples was 98.977%, with LOD = 0.493 μg L⁻¹, LOQ = 1.638 μg L⁻¹ and RSD < 1.953%. The method was successfully applied for determination of PG in real water samples (tap, river, lake and well water) and wastewater samples (SH and SHB hospital effluent). The obtained relative recoveries were in the range of 91.31% -123.27% with RSD less than 6.34% for all the real samples. The dominant mechanism in the PG adsorption process was involved in the π-π interaction, hydrogen bonding, and electrostatic interaction.     

Electrophoretic deposition of polyaniline nanofibers on a stainless steel wire as an adsorbent for determination of tamoxifen by SPME/GC–FID in urine samples

Polyaniline nanofiber films were fabricated on the surface of stainless steel wire via a controllable and simple electrophoretic deposition route from a nonaqueous colloidal suspension consisting of polyaniline nanofibers. The prepared coating material was then characterized by field emission scanning electron microscopy equipped with energy dispersive spectroscopy and elemental mapping analysis. The fabricated polyaniline film-coated stainless steel wire was then utilized as an effective and novel sorbent phase for solid-phase microextraction of tamoxifen for subsequent gas chromatography/flame ionization detection of this anticancer drug. Parameters consisting of the temperature, extraction time, salt concentration, agitation speed, pH, temperature and time of desorption were studied and optimized using a one-at-a-time strategy. Under the optimum conditions, detection limit (S/N = 3), the limit of quantification (10/3 limit of detection), linear dynamic range, repeatability and reproducibility values of 0.51 μg L⁻¹, 1.7 μg L⁻¹, 2–1,130 μg L⁻¹, 5.7% and 8.6% were attained, respectively. The prepared fiber can preserve 90% of its efficacy after 20 consecutive cycles, demonstrating the suitable thermal stability and cyclability of the proposed solid-phase microextraction coating material for the determination of tamoxifen by gas chromatography/flame ionization detection. The route was effectively utilized to determine tamoxifen in urine samples, with relative recoveries ranging from 89 to 106%.     

Carrier-mediated hollow fiber liquid-phase microextraction for preconcentration followed by spectrophotometric determination of amoxicillin

Preconcentration followed by ultraviolet spectrophotometric determination of amoxicillin (Amox) in pharmaceuticals and water samples by using a three-phase hollow fiber microextraction technique based on carrier-mediated transport has been presented. Amox was extracted from an aqueous solution (source phase) at pH 9.0 into 1-octanol containing 5% (w/v) Aliquat-336 impregnated in the pores of a hollow fiber. It was then back-extracted into NaCl solution (pH = 4.0) which was already positioned as the receiving phase inside the lumen of the hollow fiber. The extraction took place due to the concentration gradient of the counterion between the source and the receiving phases. Under the optimized conditions, an enrichment factor of 240 and a limit of detection of 0.2 μmol L⁻¹ were obtained. The calibration curve was linear (R² = 0.9967) in the concentration range of 0.5–10.0 µmol L⁻¹ Amox. The interday relative standard deviation (n = 9) and the intraday relative standard deviation (n = 3) for 1.0 × 10⁻⁶ mol L⁻¹ Amox solution were 7.3 and 6.4%, respectively.

     

Newly selective electrochemical sensors for trace-level determination of Al(III) ions in drainage water,spiked tap water and pharmaceutical preparation samples

In this work, two newly sensitive and selective Al(III)-modified carbon paste electrodes (MCPEs) were developed based on diphenylcarbazone (DPC) modifier mixed with tricresyl phosphate plasticizer and either graphite powder (electrode I) or graphite powder mixed with graphene (electrode II). The potentiometric performance characteristics of the two electrodes were scrutinized and discussed. The proposed sensors showed a high electrochemical response in the linear concentration range of 1.0 × 10⁻⁶ to 1.0 × 10⁻² mol L⁻¹ with a good Nernstian slopes of 20.12 ± 0.30 mV decade⁻¹ and 20.63 ± 0.66 mV decade⁻¹ and limits of detection of 9.0 × 10⁻⁷ and 8.5 × 10⁻⁷ mol L⁻¹ for electrode (I) and electrode (II), respectively. Both electrodes showed a fast response time and reasonable thermal stability. The potentiometric response of the DPC-based electrodes was independent on the pH of the tested solutions in ranges of 2.5–5 and 2.5–5.5 for electrode (I) and electrode (II), respectively. The two electrodes can be also used in partially non-aqueous medium containing up to 20% (v/v) acetone or methanol with no significant changes in the working concentration ranges or the slopes. The proposed electrodes showed fairly good discriminating ability toward Al(III) ions in comparison with many other metal ions. The electrodes were applied successfully for Al(III) ions determination in drainage water, spiked tap water and pharmaceutical preparation samples. Furthermore, the electrode surfaces were characterized using energy-dispersive X-ray (EDX) and scanning electron microscopic (SEM) as surface characterization techniques and Fourier Transform Infrared (FT-IR) technique to confirm the interaction between Al(III) and DPC.

     

Synthesis of a novel electrode material containing phytic acid-polyaniline nanofibers for simultaneous determination of cadmium and lead ions

The development of nanostructured conducting polymers based materials for electrochemical applications has attracted intense attention due to their environmental stability, unique reversible redox properties, abundant electron active sites, rapid electron transfer and tunable conductivity. Here, a phytic acid doped polyaniline nanofibers based nanocomposite was synthesized using a simple and green method, the properties of the resulting nanomaterial was characterized by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A glassy carbon electrode modified by the nanocomposite was evaluated as a new platform for the simultaneous detection of trace amounts of Cd²⁺ and Pb²⁺ using differential pulse anodic stripping voltammetry (DPASV). The synergistic contribution from PANI nanofibers and phytic acid enhances the accumulation efficiency and the charge transfer rate of metal ions during the DPASV analysis. Under the optimal conditions, good linear relationships were obtained for Cd²⁺ in a range of 0.05–60 μg L⁻¹, with the detection limit (S/N = 3) of 0.02 μg L⁻¹, and for Pb²⁺ in a range of 0.1–60 μg L⁻¹, with the detection limit (S/N = 3) of 0.05 μg L⁻¹. The new electrode was successfully applied to real water samples for simultaneous detection of Cd²⁺ and Pb²⁺ with good recovery rates. Therefore, the new electrode material may be a capable candidate for the detection of trace levels of heavy metal ions.     

Poly(cyclotriphosphazene-co-phloroglucinol)PCPP as a solid phase extractant for preconcentrative separation of uranium(VI) from aqueous solution

Poly(cyclotriphosphazene-co-phloroglucinol) (PCPP) microspheres, a new solid phase extraction for extracting uranium(VI), synthesized via one-pot precipitation copolymerization. The PCPP microspheres were characterized by FT-IR, SEM/EDS, zeta potential and N₂ adsorption/desorption isotherms. Through the extraction experiment to evaluate the extraction behavior of the PCPP microspheres for uranium(VI). The extractant can achieve the optimal effect under the conditions of contact time with 60 min, pH = 3.5, initial concentration 100 mg L⁻¹ and extractant dosage 0.70 g L⁻¹. The extraction behavior obeyed with the pseudo second-order model and Langmuir isotherm model.

     

Application of response surface methodology to optimize pipette tip micro-solid phase extraction of dyes from seawater by molecularly imprinted polymer and their determination by HPLC

In this paper, a novel pipette tip micro-solid phase extraction based on molecularly imprinted polymer as a selective sorbent was developed and applied for extraction, pre-concentration and high-performance liquid chromatographic determination of trace amounts of malachite green (MG), rhodamine B (RB), methyl orange (MO) and acid red 18 (AR) dyes in seawater samples. Different parameters affecting the extraction efficiency such as type and volume of eluent solvent, sample volume, number of cycles of extraction and desorption, amount of sorbent and pH of the sample solution were evaluated using one-variable-at-a-time and response surface methodology. In order to optimize dyes extraction, seven factors in three levels were used for Box–Behnken experimental design. Under optimum extraction condition, pH of sample solution was 3.1 for MG, 3.0 for RB, 7.1 for MO and 6.1 for AR; volume of eluent solvent (HCl, 0.5 mol L⁻¹) was 200 µL; volume of the sample solution was 10 mL (for MG) and 4 mL (for RB, MO and AR); the concentration of triton X-114 was 0.085 (MG), 0.10 (RB), 0.08 (MO) and 0.075 (AR) % v/v; the number of extraction cycles was 10 (MG), 6 (RB), 5 (MO) and 7 (AR); the number of elution cycles was 10, 6, 5 and 9, respectively, for MG, RB, MO and AR; NaCl concentration was 0.4 mol L⁻¹; and amount of MIP was 2.0 mg for all dyes. The linear range of calibration curves was 0.5–250.0 µg L⁻¹ for malachite green and methyl orange and 0.5–150.0 µg L⁻¹ for both rhodamine B and acid red 18. The detection limits calculated to be 0.083, 0.10, 0.12 and 0.17 µg L⁻¹ for MG, RB, MO and AR, respectively. The developed protocol was successfully used for determination of dyes in seawater of Chabahar Bay. The mean recoveries were ranged between 76.1 and 97.3% by mean relative standard deviations of 1.2–7.1%.

     

Fully automated method based on on-line molecularly imprinted polymer solid-phase extraction for determination of lovastatin in dietary supplements containing red yeast rice

A fully automated method for the determination of lovastatin in dietary supplements containing red yeast rice has been developed. It uses a sequential injection analysis system combined with solid-phase extraction applying highly selective molecularly imprinted polymer sorbent. A miniaturized column for on-line extraction was prepared by packing 4.5 mg of the sorbent in a 5.0 × 2.5-mm-i.d. cartridge, which was used in the flow manifold. Sequential injection analysis manifold enabled all steps of lovastatin extraction and continuous spectrophotometric detection at 240 nm. A limit of detection of 60 μg g⁻¹, a limit of quantitation of 200 μg g⁻¹, and a linear calibration range of 200–2000 μg g⁻¹ were achieved. Intra-day and inter-day precision values (RSD) were ≤ 6.7% and ≤ 4.9%, respectively, and method recovery values of spiked red yeast rice extracts at 200, 1000, and 2000 μg g⁻¹ concentration levels were 82.9, 95.2, and 87.7%. Our method was used for determination of lovastatin lactone in four dietary supplements containing red yeast rice as a natural source of lovastatin, also known as monacolin K. The extracted samples were subsequently analyzed by the reference UHPLC-MS/MS method. Statistical comparison of results (F test, t test, α = 0.05) obtained by both methods did not reveal significant difference. A substantial advantage of the new automated approach is high sample throughput thanks to the analysis time of 7.5 min, miniaturization via down-scaling the extraction column, and smaller sample and solvent consumption, as well as reduced generation of waste.

ᅟ

     

Modified QuEChERS method for phenolic compounds determination in mustard greens (Brassica juncea) using UHPLC-MS/MS

A modified QuEChERS method (Quick, Easy, Cheap, Effective, Rugged, and Safe) for the determination of fifteen phenolic compounds in mustard greens (Brassica juncea) using ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) analysis was developed. The QuEChERS partitioning step and dispersive solid phase extraction (d-SPE) clean-up sorbents were investigated, aimed at phenolic compound extraction and pigment removal, respectively. QuEChERS acetate version combined with 25 mg of diatomaceous earth (DE) and 5.0 mg of graphitized carbon black (GCB) provided the best conditions for sample preparation of the target compounds. Under the optimized conditions, all phenolic compounds showed good linearity (r ≥ 0.99) over the concentration range of 0.1 to 8000 μg kg⁻¹, and the quantification limits were in the range of 0.06–230 μg kg⁻¹. The spectrophotometric analysis showed that the clean-up step promoted a significant removal of chlorophyll, which is the major pigment present in the sample. Furthermore, antioxidant activity analysis was also carried out after the clean-up step and, together with chromatographic data, showed that no significant retention of the phenolic compounds occurs in the clean-up step. Two mustard greens varieties – Southern Giant Curled (SGC) and Florida Broadleaf (FB) - were analyzed with the proposed method. Seven phenolic compounds (4-hydroxybenzoic, p-coumaric, ferulic and sinapic acids, naringenin, apigenin and kaempferol) were found in both varieties, the greatest abundance being for sinapic acid (1261.5 ± 23 μg kg⁻¹ in SGC and 1235.5 ± 26 μg kg⁻¹ in FB) and ferulic acid (2861 ± 24 μg kg⁻¹ in SGC and 3204.5 ± 45 μg kg⁻¹ in FB).     

Enrichment of pyrethroid residues in environmental waters using a multiwalled carbon nanotubes cartridge,and analysis in combination with high performance liquid chromatography

A sensitive method was developed using new carbon nanomaterial, multiwalled carbon nanotubes, as solid phase extraction adsorbents followed by high performance liquid chromatography with UV detection for determination of six pyrethroid pesticides at trace level in environmental water samples. Parameters influencing the extraction efficiency were investigated in detail. Under the optimal conditions, detection limits of 0.7–5.0 ng L⁻¹ were obtained for six pyrethroid pesticides, the linear ranges were between 0.1 and 40 μg L⁻¹ and the precisions were in the range of 2.0–5.8%. The method has been applied to determine the six target compounds in tap water, well water, river water and reservoir water. Good recoveries were obtained for all target analytes and these results indicated that the method developed can be used in the determination of such compounds at trace levels in environmental water samples.

     

Development of magnetic dispersive microsolid-phase extraction using lanthanum phosphate nanoparticles doped on magnetic graphene oxide as a highly selective adsorbent for pesticide residues analysis in water and fruit samples

Magnetic graphene oxide/lanthanum phosphate nanocomposite (MGO@LaP) was synthesized and used as an efficient adsorbent for magnetic dispersive microsolid-phase extraction (MD-µ-SPE) of pesticides before gas chromatography–electron capture detector (GC–ECD) analysis. The adsorbent was thoroughly characterized with scanning electron microscopy, vibrating sample magnetometer, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy. Optimized extraction conditions were investigated concerning extraction time, adsorbent amount, sample pH, and salt amount as well as desorption conditions (type and volume of desorption solvent and desorption time). Under the optimal conditions, the method demonstrated good linearity (3–1500 µg L^?1) with satisfactory determination coefficients of >?0.997 and low detection limits for both chlorpyrifos (0.67 µg L^?1) and hexaconazole (0.89 µg L^?1). Finally, the method showed high analyte relative recoveries in the range of 78–120% for the determination of the selected pesticides in water and fruit juice samples.

     

Simultaneous extraction and determination of albendazole and triclabendazole by a novel syringe to syringe dispersive liquid phase microextraction-solidified floating organic drop combined with high performance liquid chromatography

A syringe to syringe dispersive liquid phase microextraction-solidified floating organic drop was introduced and used for the simultaneous extraction of trace amounts of albendazole and triclabendazole from different matrices. The extracted analytes were determined by high performance liquid chromatography along with fluorescence detection. The analytical parameters affecting the microextraction efficiency including the nature and volume of the extraction solvent, sample volume, sample pH, ionic strength and the cycles of extraction were optimized. The calibration curves were linear in the range of 0.1–30.0 μg L⁻¹ and 0.2–30.0 μg L⁻¹ with determination coefficients of 0.9999 and 0.9998 for albendazole and triclabendazole respectively. The detection limits defined as three folds of the signal to noise ratio were found to be 0.02 μg L⁻¹ for albendazole and 0.06 μg L⁻¹ for triclabendazole. The inter-day and intra-day precision (RSD%) for both analytes at three concentration levels (0.5, 2.0 and 10.0 μg L⁻¹) were in the range of 6.3–10.1% and 5.0–7.5% respectively. The developed method was successfully applied to determine albendazole and triclabendazole in water, cow milk, honey, and urine samples.     

Development of a novel mixed hemimicelles dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene for the separation and preconcentration of fluoxetine in different matrices before its determination by fiber optic linear array spectrophotometry and mode-mismatched thermal lens spectroscopy

This study aims at developing a novel, sensitive, fast, simple and convenient method for separation and preconcentration of trace amounts of fluoxetine before its spectrophotometric determination. The method is based on combination of magnetic mixed hemimicelles solid phase extraction and dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene as a sorbent. The magnetic graphene was synthesized by a simple coprecipitation method and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The retained analyte was eluted using a 100 μL mixture of methanol/acetic acid (9:1) and converted into fluoxetine-β-cyclodextrin inclusion complex. The analyte was then quantified by fiber optic linear array spectrophotometry as well as mode-mismatched thermal lens spectroscopy (TLS). The factors affecting the separation, preconcentration and determination of fluoxetine were investigated and optimized. With a 50 mL sample and under optimized conditions using the spectrophotometry technique, the method exhibited a linear dynamic range of 0.4–60.0 μg L⁻¹, a detection limit of 0.21 μg L⁻¹, an enrichment factor of 167, and a relative standard deviation of 2.1% and 3.8% (n = 6) at 60 μg L⁻¹ level of fluoxetine for intra- and inter-day analyses, respectively. However, with thermal lens spectrometry and a sample volume of 10 mL, the method exhibited a linear dynamic range of 0.05–300 μg L⁻¹, a detection limit of 0.016 μg L⁻¹ and a relative standard deviation of 3.8% and 5.6% (n = 6) at 60 μg L⁻¹ level of fluoxetine for intra- and inter-day analyses, respectively. The method was successfully applied to determine fluoxetine in pharmaceutical formulation, human urine and environmental water samples.     

Magnetic field assisted μ-solid phase extraction of anti-inflammatory and loop diuretic drugs by modified polybutylene terephthalate nanofibers

A magnetic nanocomposite consisting of nanoparticles–polybutylene terephthalate (MNPs–PBT) was electrospun and used as an extracting medium for an on-line μ-solid phase extraction (μ–SPE)–high performance liquid chromatography (HPLC) set–up with an ultraviolet (UV) detection system. Due to the magnetic property of the prepared nanofibers, the whole extraction procedure was implemented under an external magnetic field to enhance the extraction efficiencies. The developed method along with the synthesized nanocomposite were found to be appropriate for the determination of trace levels of selected drugs including furosemide, naproxen, diclofenac and clobetasol propionate in the urine sample. The prepared MNPs-PBT electrospun nanocomposite was characterized using the scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and Fourier transform infrared (FT–IR) spectroscopy. The prepared magnetic fibers showed high porosity, which was another driving force for the extraction efficiency enhancement. Major parameters affecting the extraction efficiency of the selected drugs were optimized. The limits of detections (LOD) of the studied drugs were in the range of 0.4–1.6 μg L⁻¹ and the limits of quantification (LOQ) were 1–4 μg L⁻¹ under the optimized conditions. Relative standard deviation (RSD%) for three replicates at three concentration levels of 6, 100 and 400 μg L⁻¹ were 5.9–8.0% while acceptable linear range with two orders of magnitude was obtained (R² = 0.99). The method was validated by the determination of the selected drugs in urine samples and the results indicated that this method has sufficient potential for enrichment and determination of the desired drugs in the urine sample. The relative recovery values were found to be in the range of 78–91%. Implementing the developed on–line μ–SPE method under the external magnetic field induction, led to higher extraction efficiencies for the selected drugs with various diamagnetic properties.     

Simultaneous determination of dimethoate and its metabolite omethoate in curry leaf using LC-MS/MS and risk assessment

This study presents the method development, validation, and simultaneous determination of dimethoate and its metabolite omethoate in curry leaf. Samples were extracted following modified quick, easy, cheap, effective, rugged, and safe extraction protocol and analyzed using liquid chromatography-tandem mass spectrometry. The limit of quantification in the matrix was 0.005 μg g⁻¹ for dimethoate and omethoate. Extraction using acetonitrile recorded the average recoveries in the range of 82.25 to 112.97% for dimethoate and 85.57 to 107.22% for omethoate at 0.005, 0.025 and 0.050 μg g⁻¹ fortification levels and relative standard deviation less than 5%. Similarly, the relative standard deviation values for intraday (Repeatability) and interday (Reproducibility) tests were less than 15%. Dissipation kinetics of dimethoate 30% emulsifiable concentrate at 200 and 400 g a.i h⁻¹ recorded initial deposits of 5.20 and 10.05 μg g⁻¹ and 0.33 and 0.48 μg g⁻¹ for dimethoate and omethoate, respectively, and half-life of 3.07 and 3.34 days. The estimated hazard index value found more than one at a day after dimethoate application. It is not safe for consumer health to use curry leaves in the initial days after application.     

Polyaniline-silica doped with oxalic acid as a novel extractor phase in thin film solid-phase microextraction for determination of hormones in urine

In this study, different polyanilines were synthesized and evaluated for the determination of three hormones, including 17-β-estradiol, 17-α-ethinylestradiol, and estrone, in urine using a novel methodology based on thin film solid-phase microextraction technique, employing the sampling well plate system. The extractor phases, designated as polyaniline doped with hydrochloric acid, polyaniline doped with oxalic acid, polyaniline-silica doped with hydrochloric acid, and polyaniline-silica doped with oxalic acid, were characterized by electrical conductivity measurements, scanning electron microscopy, and Fourier transform infrared spectroscopy. The optimized extraction conditions were composed of 1.5 mL of urine and pH adjusted to 10, with no need to dilute sample and the desorption step, 300 μL of acetonitrile was used. The calibration curves were performed in the sample matrix, with detection and quantification limits ranged from 0.30 to 3.03 μg L⁻¹ and from 1.0 to 10.0 μg L⁻¹, respectively, with r ≥ 0.9969. The relative recoveries ranged from 71% to 115%, and intraday precision showed values ≤12% and interday ≤20%. The applicability of the method was successfully evaluated, and six urine samples from female volunteers were analyzed. The analytes were not detected or were below the limits of quantification in these samples.     

Separation of strontium and yttrium in nitric acid solutions using zirconium titanium phosphate and Dowex exchangers

Sulfonated ion irradiated (H⁺ and He²⁺) PEEK films were synthesized with a range of cross-linking density and a variety of sulfonation degrees. Batch adsorption experiments were carried out at an initial pH of 6.0 ± 0.2, initial concentrations of Pb²⁺ and ¹³⁷Cs ions of 10.0 mg L⁻¹ and 5500 Bq L⁻¹, respectively. The maximum adsorption capacity was 60 mg g⁻¹ for Pb²⁺, and the distribution coefficient reached 6200 cm³ g⁻¹ for ¹³⁷Cs. The results indicated that sulfonation could be used to recycle low cross-linked PEEK and prepare efficient adsorbents to remove toxic Pb²⁺ and ¹³⁷Cs from polluted aqueous solutions.

     

Extraction of thorium using primary amine N1923 levextrel resin by a micro-column

The extraction behavior of thorium from Baotou iron ore with primary amine N1923 levextrel resins by a micro-column was investigated under the decompression technology. Thorium was adsorbed on the micro-column conditioned by 3 mol L⁻¹ HCl solution before use. The washing liquor of 0.5 mol L⁻¹ H₂SO₄–0.1 mol L⁻¹ H₃PO₄ solution was used to wash impurity elements and the solution of 3 mol L⁻¹ HCl was used as the eluent for thorium. The method was applied to analyze thorium in the Baotou iron ore sample. The relative standard deviations of thorium in R-715 standard sample, Baotou main ore standard sample and Baotou west ore were of 0.49%, 1.63%, 1.16%, respectively. The accuracy of the method was satisfactory.

     

Kinetic study on preparation of substoichiometric tungsten oxide WO2.72 via hydrogen reduction process

Controlling the conditions of the oxygen partial pressure and temperature to prepare the WO_2.72 (W₁₈O₄₉) via reduction was possible through thermodynamic consideration. WO_2.72 was synthesized via heating to 1073 K in 5% H₂–95% Ar mixture gas flow from ammonium tungstate which was prepared by hydrothermal process. With the reducing prolonging time, the products were changed from WO_2.72 to WO₂ and then metal W. Thermogravimetric (TG) analysis showed ammonium tungstate decomposed completely to WO₃ at 773 K. Isothermal reductions using TG analysis were carried out at 905 K, 925 K, 945 K and 973 K in 5% H₂–95% Ar mixture gas flow, respectively. The whole reduction from WO₃ to WO_2.72 divided into three parts: initial nucleation and growth stage, final interfacial reaction stage and intermediate stage, was controlled jointly by both mechanisms. Fitting results showed that the initial stage obey the one-dimensional Avrami–Erofeev equation, the apparent activation energy was 132.7 ± 1.1 kJ mol⁻¹ and the pre-exponent factor was 4.82 × 10⁵ min⁻¹; the final stage expressed by 2-dimensional interfacial reaction, the apparent activation energy was 144.0 ± 2.1 kJ mol⁻¹ and the pre-exponent factor was 3.20 × 10⁵ min⁻¹.