Flame atomic absorption spectrometric (FAAS) determination of copper,iron and zinc in food samples after solid-phase extraction on Schiff base-modified duolite XAD 761

The present study involves the development of solid-phase extraction (SPE) procedure for the preconcentration of trace amounts of copper (Cu^2 +), iron (Fe^3 +) and zinc (Zn^2 +) ions on duolite XAD 761 modified by bis(2-hydroxyacetophenone)-2,2-dimethyl-1,3-propanediimine(BHAPDMPDI). The complexation between the metal ions and the proposed ligand was investigated potentiometrically. The metal ions retained on the sorbent were quantitatively determined via complexation with BHAPDMPDI. The complexed metal ions were efficiently eluted using 6 mL of 4 mol L^? 1 nitric acid in acetone. The influences of the analytical parameters, including pH, amounts of the ligand and the solid phase, eluent conditions and sample volume, on the recoveries of the metal ions were optimized. Using the optimized parameters, the linear response of the SPE method for Cu^2 +, Zn^2 + and Fe^3 + ions were in the ranges of 0.01–0.34, 0.01–0.28 and 0.02–0.31 μg mL^? 1, respectively, and the detection limits for Cu^2 +, Zn^2 + and Fe^3 + ions were 1.8, 1.6 and 2.4 μg mL^? 1, respectively. The proposed method exhibits a preconcentration factor of 208 for all of the ions studied and an enhancement factor for Cu^2 +, Fe^3 + and Zn^2 + ions of 34, 28 and 38, respectively. The presented results demonstrate the successful application of the proposed method for the determination of these metal ions in some real samples with high recoveries (> 95%) and reasonable relative standard deviation (RDS < 5%).     

Fabrication of a selective mercury sensor based on the adsorption of cold vapor of mercury on carbon nanotubes: Determination of mercury in industrial wastewater

A new sensor for the determination of mercury at μg ml^?1 levels is proposed based on the adsorption of mercury vapor on single-walled carbon nanotubes (SWCNTs). The changes in the impedance of SWCNTs were monitored upon adsorption of mercury vapor. The adsorption behaviour of mercury on SWCNTs was compared with that on multi-walled carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs). Cold vapor of mercury was generated at 65 °C using Sn(II) solution as a reducing agent. The limit of detection was 0.64 μg ml^?1 for Hg(II) species. The calibration curve for Hg(II) was linear from 1.0 to 30.0 μg ml^?1. The relative standard deviation (RSD) of eight replicate analyses of 15 μg ml^?1 of Hg(II) was 2.7%. The results showed no interfering effects from many foreign species and hydride forming elements. The system was successfully applied to the determination of the mercury content of different types of wastewater samples.     

Preparation of zeolite-A/chitosan hybrid composites and their bioactivities and antimicrobial activities

Zeolite-A/chitosan hybrid composites with zeolite contents of 20–55 wt.% were prepared by in situ transformation of silica/chitosan mixtures in a sodium aluminate alkaline solution through impregnation–gelation–hydrothermal synthesis. The products were characterized by X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mercury penetration porosimetry. Their in vitro bioactivities were examined using as-synthesized and Ca^2 +-exchanged hybrid composites in simulated body fluid (SBF) for hydroxyapatite (HAP) growth. Their antimicrobial activities for Escherichia coli (E. coli) in trypticase soy broth (TSB) were evaluated using Ag⁺-exchanged hybrid composites. The zeolite-A/chitosan hybrid composites could be prepared as various shapes, including cylinders, plates and thin films. They possessed macropores with pore sizes ranging from 100 to 300 μm and showed compressive mechanical strength as high as 3.2 MPa when the zeolite content was 35 wt.%. Fast growth on the Ca^2 +-exchanged hybrid composites was observed with the highest weight gain of 51.4% in 30 days. The 35 wt.% Ag⁺-exchanged hybrid composite showed the highest antimicrobial activity, which could reduce the 9 × 10⁶ CFU mL^? 1 E. coli concentration to zero within 4 h of incubation time with the Ag⁺-exchanged hybrid composite amount of 0.4 g L^? 1. The bioactivity and antimicrobial activity could be combined by ion-exchanging the composites first with Ca^2 + and then with Ag⁺. These zeolite-A/chitosan hybrid composites have potential applications on tissue engineering and antimicrobial food packaging.     

Modification of algae with zinc,copper and silver ions for usage as natural composite for antibacterial applications

Nanometer sized metal particles are used in many applications as antimicrobial materials. However in public discussion nanoparticular materials are a matter of concern due to potential health risks. Hence there is a certain demand for alternative antimicrobial acting materials. For this, the aim of this work is to realize an antimicrobial active material based on the release of metal ions from a natural depot. By this, the use of elemental metal particles or metal oxide particles in nanometer or micrometer scale is avoided. As natural depot four different algae materials (gained from Ascophyllum nodosum, Fucus vesicolosus, Spirulina platensis and Nannochloropsis) are used and loaded by bioabsorption with metal ions Ag⁺, Cu^2 + and Zn^2 +. The amount of metal bound by biosorption differs strongly in the range of 0.8 to 5.4 mg/g and depends on type of investigated algae material and type of metal ion. For most samples a smaller release of biosorbed Ag⁺ and Cu^2 + is observed compared to a strong release of Zn^2 +. The antibacterial activity of the prepared composites is investigated with Escherichia coli. Algae material without biosorbed metal has only a small effect on E. coli. Also by modification of algae with Zn^2 + only a small antibacterial property can be observed. Only with biosorption of Ag⁺, the algae materials gain a strong bactericidal effect, even in case of a small amount of released silver ions. These silver modified algae materials can be used as highly effective bactericidal composites which may be used in future applications for the production of antimicrobial textiles, papers or polymer materials.     

Synthesis and electrochemical properties of Ag0.333V2O5–V2O5 core–shell nanobelts for rechargeable lithium batteries

Ag_0.333V₂O₅–V₂O₅ core–shell nanobelts have been synthesized by a facile homogeneous reaction between peroxovanadic acid and AgNO₃ under hydrothermal conditions. The formation of Ag_0.333V₂O₅–V₂O₅ core–shell nanobelts is time dependent: Ag_0.333V₂O₅ nanobelts are formed firstly, and then V₂O₅ grows on the Ag_0.333V₂O₅ surfaces. The core–shell nanobelts exhibit stable lithium-ion intercalation/deintercalation reversibility and deliver specific discharge capacities of around 276.4 mAhg^?1 after 50 cycles at a rate of 0.25 Ag^?1. The value is lowered to 228 mAhg^?1 at 0.5 Ag^?1, and 147.2 mAhg^?1 at 0.75 Ag^?1. The good electrochemical properties of Ag_0.333V₂O₅–V₂O₅ core–shell nanobelts make them a promising candidate as a cathode material for rechargeable lithium batteries.     

4-Aminophenyl boronic acid modified gold platforms for influenza diagnosis

As a potential pandemic threat to human health, there has been an urgent need for rapid, sensitive, simpler and less expensive detection method for the highly pathogenic influenza A virus. For this purpose, Quartz Crystal Microbalance (QCM) and Surface Plasmon Resonance (SPR) sensors have been developed for the recognition of hemagglutinin (HA) which is a major protein of influenza A virus. 4-Aminophenyl boronic acid (4-APBA) has been synthesized and used as a new ligand for binding of sialic acid (SA) via boronic acid–sugar interaction. SA has an important role in binding of HA. QCM and SPR sensor surfaces have been modified with thiol groups and then 4-APBA and SA have been immobilized on sensor surfaces, respectively. Sensor surfaces have been screened with AFM and used for the determination of HA from aqueous solution. The selective recognition of the QCM and SPR sensors toward Concanavalin A has been reported in this work. Also, the binding capacity and detection limits of QCM and SPR sensors have been calculated and detection limits were found to be 4.7 × 10^? 2 μM, (0.26 μg ml^? 1) and 1.28 × 10^? 1 μM, (0.72 μg ml^? 1) in the 95% confidence interval, respectively.     

Voltammetric sensor based on carbon paste electrode modified with molecular imprinted polymer for determination of sulfadiazine in milk and human serum

A new sensitive voltammetric sensor for determination of sulfadiazine is described. The developed sensor is based on carbon paste electrode modified with sulfadiazine imprinted polymer (MIP) as a recognition element. For comparison, a non-imprinted polymer (NIP) modified carbon paste electrode was prepared. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods were performed to study the binding event and electrochemical behavior of sulfadiazine at the modified carbon paste electrodes. The determination of sulfadiazine after its extraction onto the electrode surface was carried out by DPV at 0.92 V vs. Ag/AgCl owing to oxidation of sulfadiazine. Under the optimized operational conditions, the peak current obtained at the MIP modified carbon paste electrode was proportional to the sulfadiazine concentration within the range of 2.0 × 10^? 7–1.0 × 10^? 4 mol L^? 1 with a detection limit and sensitivity of 1.4 × 10^? 7 mol L^? 1 and 4.2 × 10⁵ μA L mol^? 1, respectively. The reproducibility of the developed sensor in terms of relative standard deviation was 2.6%. The sensor was successfully applied for determination of sulfadiazine in spiked cow milk and human serum samples with recovery values in the range of 96.7–100.9%.     

Selective recognition of Pr3 + based on fluorescence enhancement sensor

(E)-2-(1-(4-hydroxy-2-oxo-2H-chromen-3-yl)ethylidene)hydrazinecarbothioamide (L) has been used to detect trace amounts of praseodymium ion in acetonitrile–water solution (MeCN/H₂O) by fluorescence spectroscopy. The fluorescent probe undergoes fluorescent emission intensity enhancement upon binding to Pr^3 + ions in MeCN/H₂O (9/1:v/v) solution. The fluorescence enhancement of L is attributed to a 1:1 complex formation between L and Pr^3 +, which has been utilized as the basis for selective detection of Pr^3 +. The sensor can be applied to the quantification of praseodymium ion with a linear range of 1.6 × 10^? 7 to 1.0 × 10^? 5 M. The limit of detection was 8.3 × 10^? 8 M. The sensor exhibits high selectivity toward praseodymium ions in comparison with common metal ions. The proposed fluorescent sensor was successfully used for determination of Pr^3 + in water samples.     

Electrochemical sensor for uric acid based on a molecularly imprinted polymer brush grafted to tetraethoxysilane derived sol-gel thin film graphite electrode

Determination of uric acid in human serum and urine is useful to provide treatment guidelines to hyperuricemic patients. An electrochemical sensor was developed for selective and quantitative recognition of uric acid by using a preanodised sol-gel coated graphite electrode with a molecularly imprinted polymer brush of poly(melamine–co-chloranil) grafted to its exterior surface. During a preconcentration step at (+ 2.0 V versus saturated calomel electrode), the encapsulated analyte recapture involved hydrophobically induced hydrogen-bondings in outwardly exposed MIP cavities in aqueous environment (pH 7.0), instantly oxidised as dications, and then cathodically stripped off as corresponding lactam responding differential pulse, cathodic stripping voltammetric signal. The uric acid was selectively detected without any cross reactivity in the windows of 14.56–177.42 µg mL^? 1 (aqueous medium), 4.78–106.96 µg mL^? 1 (blood serum), and 7.81–148.42 µg mL^? 1 (urine) indicating detection limits in the range of 3.71–4.10 µg mL^? 1 (3σ, RSD = 1.9%).     

Characterization and determination of the thermodynamic and kinetic properties of the adsorption of molybdenum (VI) onto microcrystalline anthracene modified with 8-hydroxyquinoline

A reliable and effective method for the determination of trace molybdenum in effluents is proposed. Molybdenum (VI) is analyzed by Microwave Plasma Torch Optical Emission Spectrometry (MPT-OES) based on the adsorption collection onto microcrystalline anthracene modified with 8-hydroxyquinoline. The possible reaction mechanism was discussed in detail and the optimum conditions for adsorption of Mo (VI) were confirmed. The experimental data were fitted well with the pseudo-second-order kinetic model and Langmuir model at all studied temperatures. The calculated thermodynamic parameters (ΔG^?, ΔH^? and ΔS^?) showed that the adsorption of molybdenum onto microcrystalline anthracene was feasible, spontaneous and endothermic at 280–320 K. The recovery of this method is in the range of 96.5%–103.3% with preconcentration factor of 100 and the limit detection after preconcentration is 0.078 μg L^? 1. The proposed method has been successfully applied to the determination of trace Mo (VI) in environmental water samples with satisfactory results.     

Removal,preconcentration and spectrophotometric determination of picric acid in water samples using modified magnetic iron oxide nanoparticles as an efficient adsorbent

A simple, fast and sensitive spectrophotometric method is developed for removal, preconcentration and determination of trace amounts of picric acid in water samples. Magnetic iron oxide nanoparticles (MIONPs) were synthesized and characterized by transmission electron microscopy (TEM). The magnetic nanoparticles were coated with cetyltrimethylammonium bromide (CTAB) and were applied for fast separation, preconcentration and spectrophotometric determination of picrate anion (the ion of picric acid) in an aqueous solution. The separation, preconcentration procedure is fast and will be completed in 2 min. Methanol is used for desorption of adsorbed picrate anion. The effects of important parameters such as pH of aqueous medium, CTAB dosage, adsorbent amount, temperature, electrolyte concentration, desorbing solvent and interfering ions on the adsorption of picrate anion were investigated. The method showed good linearity for the determination of picric acid in the concentration range of 0.02–1.00 μg mL^? 1 with a regression coefficient of 0.999. The limit of detection (LOD) is obtained to be 0.007 μg mL^? 1. The relative standard deviation (RSD) for 0.03 μg mL^? 1 and 0.8 μg mL^? 1 of picric acid were 3.98% and 1.97% respectively. Picric acid was separated, preconcentrated and determined successfully in spiked samples of Karoon River water.     

Sensitive detection of mercury (II) ion using water-soluble captopril-stabilized fluorescent gold nanoparticles

In our work, a simple, facile, and green method was developed for the synthesis of water-soluble and well-dispersed fluorescent gold nanoparticles (Au NPs) within 5 min, using captopril as a capping agent. The as-prepared Au NPs showed strong emission at 414 nm, with a quantum yield of 5.5%. The fluorescence of the Au NPs can be strongly quenched by mercury (II) ion (Hg^2 +) due to the stronger interactions between thiolates (RS^?) and Hg^2 +. It was applied to the detection of Hg^2 + in water samples in the linear ranges of 0.033–0.133 μM and 0.167–2.500 μM, with a detection limit of 0.017 μM. Therefore, the as-prepared Au NPs can meet the requirement for monitoring Hg^2 + in environmental samples.     

Application of an exfoliated graphite nanoplatelet-modified electrode for the determination of quintozen

A chitosan–grafted exfoliated graphite nanoplatelet (xGnP) hybrid chemically modified electrode was developed and characterized for the determination of organochlorine pesticides with nitro groups using quintozen as a representative. The hybrid material was characterized by Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible spectroscopy (UV–VIS) and scanning electron microscopy (SEM). The electrochemical properties of the chitosan–xGnP modified electrode were characterized by a physical deposition method for depositing it on a graphite electrode. Because of the affinity of the xGnP for nitro groups, nitroaromatic organophosphate pesticides are attached to the surface, allowing the extraction of quintozen within a short time (4 min). The differential pulse response was linear over the quintozen concentration range of 10^?12–10^?6 M, and the current linearly increased with the quintozen concentrations in two concentration ranges: from 10^?12 to 10^?8 M with the linear regression equation of y = 0.0423x + 0.6451, R² = 0.9964 and from 10^?8 to 10^?6 M with the linear regression equation of y = 0.0085x + 0.303, R² = 0.9952, with a detection limit of 10^?11 M.     

In vitro and in vivo antimicrobial properties of silver-containing hydroxyapatite prepared via ultrasonic spray pyrolysis route

Hydroxyapatite (HAp), with its high biocompatibility and osteoconductivity, readily absorbs proteins, amino acids and other substances, which in turn favor the adsorption and colonization of bacteria. To prevent bacterial growth and biofilm formation on HAp discs, silver-containing (1–20 mol%) HAp (Ag-HAp) powders were synthesized using an ultrasonic spray pyrolysis (USSP) technique. The X-ray diffraction (XRD) peaks were very broad, indicating low crystallinity, and this induced the release of Ag⁺ ions from Ag-HAp powders. In addition, a gradual increase in Ca^2 + ion release was observed. These results suggest that dissolution of Ca^2 + ion in Ag-HAp triggered the release of Ag⁺ ions.The antimicrobial efficacy of Ag-HAp disc was tested against Staphylococcus aureus. Samples with Ag contents of more than 5 mol% were found to be highly effective against bacterial colonization and biofilm formation in vitro. In vivo antibacterial tests using bioluminescent strains also showed reductions in the viability of bacteria with Ag-HAp (5 mol%) discs. Biocompatibility tests using a modified Transwell® insert method showed that Ag-HAp (5 mol%) discs have negative effects on osteoblast proliferation. These results indicate that Ag-HAp (5 mol%) has effective antibacterial activity and good biocompatibility both in vitro and in vivo together with good biocompatibility, thus confirming its utility as a bactericidal material.     

Potentiometric detection of silver (I) ion based on carbon paste electrode modified with diazo-thiophenol-functionalized nanoporous silica gel

For the first time, triazene compound functionalized silica gel was incorporated into carbon paste electrode for the potentiometric detection of silver (I) ion. A novel diazo-thiophenol-functionalized silica gel (DTPSG) was synthesized, and the presence of DTPSG acted as not only a paste binder, but also a reactive material. The electrode with optimum composition, exhibited an excellent Nernstian response to Ag⁺ ion ranging from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a detection limit of 9.5 × 10^? 7 M and a slope of 60.4 ± 0.2 mV dec^? 1 over a wide pH range (4.0–9.0) with a fast response time (50 s) at 25 °C. The electrode also showed a long-time stability, high selectivity and reproducibility. The response mechanism of the proposed electrode was investigated by using AC impedance. Moreover, the electrode was successfully applied for the determination of silver ions in radiology films, and for potentiometric titration of the mixture solution of Cl^? and Br^? ions.     

An optical chemical sensor for thorium (IV) determination based on thorin

A selective method for the determination of thorium (IV) using an optical sensor is described. The sensing membrane is prepared by immobilization of thorin–methyltrioctylammonium ion pair on triacetylcellulose polymer. The sensor produced a linear response for thorium (IV) concentration in the range of 6.46 × 10^?6 to 9.91 × 10^?5 mol L^?1 with detection limit of 1.85 × 10^?6 mol L^?1. The regeneration of optode was accomplished completely at a short time (less than 20 s) with 0.1 mol L^?1 of oxalate ion solution. The relative standard deviation for ten replicate measurements of 2.15 × 10^?5 and 8.62 × 10^?5 mol L^?1 of thorium was 2.71 and 1.65%, respectively. The optode membrane exhibits good selectivity for thorium (IV) over several other ionic species and are comparable to those obtained in case of spectrophotometric determination of thorium using thorin in solution. A good agreement with the ICP-MS and spiked method was achieved when the proposed optode was applied to the determination of thorium (IV) in dust and water samples.     

Application of ionic liquid–TiO2 nanoparticle modified carbon paste electrode for the voltammetric determination of benserazide in biological samples

An ionic liquid–TiO₂ nanoparticle modified carbon paste electrode (IL–TiO₂/CPE) was used as a fast and sensitive tool for the investigation of the electrochemical oxidation of benserazide using voltammetry. This modified electrode has been fabricated using hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) as a binder. The modified electrode offers a considerable improvement in voltammetric sensitivity toward benserazide, compared to the bare electrode. Using differential pulse voltammetry (DPV), the electrocatalytic oxidation peak current of benserazide shows a linear calibration curve in the range of 1.0–600 μmol L^? 1 benserazide. The limit of detection was equal to 0.4 μmol L^? 1. The relative standard deviation (RSD%) for eight successive assays of 10 μmol L^? 1 benserazide was 1.1%. Finally, the proposed method was successfully applied to the determination of benserazide in real samples such as blood serum and urine.     

A Ho(III) potentiometric polymeric membrane sensor based on a new four dentate neutral ion carrier

In this research, we report a new Ho^3 +-PVC membrane electrode based on N-(4,5-dimethyl-2-(picolinamido)phenyl)picolinamide (H₂Me₂bpb) as a suitable ion carrier. Poly vinylchloride (PVC)-based membrane composed of H₂Me₂bpb with oleic acid (OA) as anionic additives, and o-nitrophenyloctyl ether (NPOE) as plasticized solvent mediator. The sensor exhibits a Nernstian slope of 20.1 ± 0.2 mV decade^? 1 over the concentration range of 1.0 × 10^? 6 to 1.0 × 1^? 2 mol L^? 1, and a detection limit of 5.0 × 10^? 7 mol L^? 1 of Ho^3 + ions. The potentiometric response of the sensor is independent of the solution pH in the range of 3.5–9.4. It has a very short response time, in the whole concentration range (< 10 s), and can be used for at least eight weeks. The proposed electrode shows a good selectivity towards Ho^3 + ions over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. To assess its analytical applicability the proposed Ho^3 + sensor was successfully applied as an indicator electrode in the titration of Ho^3 + ion solutions in certified reference materials, alloy samples and for the determination of the fluoride ion in two mouthwash preparations.     

Detection of anticancer drug tamoxifen using biosensor based on polyaniline probe modified with horseradish peroxidase

Amperometric biosensor based on horseradish peroxidase immobilized via glutaraldehyde on the polyaniline modified platinum electrode shows evidenced promising characteristics in detecting anticancer drug tamoxifen. The sensor was fabricated simply by adsorbing horseradish peroxidase enzyme on the electrode surface for which Cyclic Voltammetry was used to monitor the electro-catalytic reduction of tamoxifen under diffusion-adsorption controlled conditions. Fourier Transform Infrared Spectroscopy, Cyclic Voltammetry and Electrochemical Impedance Spectroscopic techniques are used to characterize the electrochemical interfacial properties of surface modified electrodes. The first-hand effort on modified biosensor within Platinum/Polyaniline/Horseradish peroxidase biosensor system has demonstrated excellent electro-analytical properties with biosensor sensitivity of 1.6 μA ng mL^? 1. The optimum limit of detection and limit of quantification are 0.07 ng mL^? 1 and 0.29 ng mL^? 1 respectively for the determination of anticancer drug tamoxifen. It is felt that the present study will help in improving our knowledge of cost-effective quantitative determination of tamoxifen in metabolized biological fluids and other pharmaceutical formulations.     

A highly sensitive and selective electrochemical sensor for determination of Cr(VI) in the presence of Cr(III) using modified multi-walled carbon nanotubes/quercetin screen-printed electrode

A novel screen-printed carbon electrode modified with quercetin/multi-walled carbon nanotubes was fabricated for determination of Cr(VI) in the presence of excess of Cr(III) without any pretreatment. The method is based on accumulation of the quercetin–Cr(III) complex generated in situ from Cr(VI) at the modified electrode surface in an open circuit followed by differential pulse voltammetry detection. The new method allowed selective determination of Cr(VI) in the presence of Cr(III). The influence of various parameters affecting the adsorptive stripping voltammetry performance was investigated. Under the optimum conditions, the calibration plot was found to be linear in the Cr(VI) concentration range from 1.0 to 200 μmol^? 1 with a limit of detection(S/N = 3) of 0.3 μmol L^– 1. The relative standard deviation (RSD%) of seven replicates of the current measurements for a 50 μmol^? 1 of Cr(VI) solution was 3.0%. The developed electrode displayed a very low or no sensitivity to alkali, alkali-earth and transition metal cations and was successfully applied for the determination of Cr(VI) in drinking water samples.