Novel paper-based potentiometric combined sensors using coumarin derivatives modified with vanadium pentoxide nanoparticles for the selective determination of trace levels of lead ions.

Novel miniaturized Pb(II) paper-based potentiometric sensors are described using coumarin derivatives I and II as electroactive ionophores and nano vanadium pentoxide as a solid contact material for the sensitive and selective monitoring of trace lead ions. Density functional theory (DFT) confirms optimum geometries, electronic properties, and charge transfer behaviors of 1:2 Pb(II): coumarin complexes. The sensors are prepared by using two strips of 20 × 5 mm filter paper with two circular orifices. One orifice is coated with vanadium pentoxide (V2O5) nanoparticles in colloidal conductive carbon as a solid-contact, covered by a PVC membrane containing coumarin ionophore to act as a sensing probe. The other orifice is treated with Ag/AgCl in a polyvinyl butyral (PVB) film, to act as a reference electrode. Sensors with ionophores (I) and (II) exhibit Nernstian slopes of 27.7 ± 0.2 and 30.2 ± 0.2 mV/decade over the linear concentration range 4.5 × 10-7 to 6.2 × 10-3 M and 8.5 × 10-8 to 6.2 × 10-3 M, with detection limits of 1.3 × 10-7 M (26.9 ppb) and 2.1 × 10-8 M (4.4 ppb), respectively. The sensors are satisfactorily used for accurate determination of lead ions in drinking water, lead-acid battery wastewater, and electronic waste leachates. The results compare favourably well with data obtained by flameless atomic absorption spectrometry.

A novel potentiometric screen-printed electrode based on crown ethers/nano manganese oxide/Nafion composite for trace level determination of copper ion in biological fluids.

Copper levels in biological fluids are associated with Wilson's, Alzheimer's, Menke's, and Parkinson's diseases, making them good biochemical markers for these diseases. This study introduces a miniaturized screen-printed electrode (SPE) for the potentiometric determination of copper(II) in some biological fluids. Manganese(III) oxide nanoparticles (Mn2O3-NPs), dispersed in Nafion, are drop-casted onto a graphite/PET substrate, serving as the ion-to-electron transducer material. The solid-contact material is then covered by a selective polyvinyl chloride (PVC) membrane incorporated with 18-crown-6 as a neutral ion carrier for the selective determination of copper(II) ions. The proposed electrode exhibits a Nernstian response with a slope of 30.2 ± 0.3 mV/decade (R2 = 0.999) over the linear concentration range 5.2 × 10-9 - 6.2 × 10-3 mol/l and a detection limit of 1.1 × 10-9 mol/l (69.9 ng/l). Short-term potential stability is evaluated using constant current chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). A significant improvement in the electrode capacitance (91.5 µF) is displayed due to the use of Mn2O3-NPs as a solid contact. The presence of Nafion, with its high hydrophobicity properties, eliminates the formation of the thin water layer, facilitating the ion-to-electron transduction between the sensing membrane and the conducting substrate. Additionally, it enhances the adhesion of the polymeric sensing membrane to the solid-contact material, preventing membrane delamination and increasing the electrode's lifespan. The high selectivity, sensitivity, and potential stability of the proposed miniaturized electrode suggests its use for the determination of copper(II) ions in human blood serum and milk samples. The results obtained agree fairly well with data obtained by flameless atomic absorption spectrometry.

Synthesis and characterization of bio-nanocomposite based on chitosan and CaCO3 nanoparticles for heavy metals removal.

Water is a vital component of life; therefore, it is critical to have access to pure water for various life-sustaining activities including agriculture and human consumption. An eco-friendly nanocomposite based on chitosan (Cs) and nanomaterials (CaCO3-NPs) were combined to amalgamate the advantages of biopolymers and nanomaterials to overcome the problems of instability, poor mechanical properties, and low removal percentage of biopolymers. The as-prepared samples were characterized and were used for the removal of heavy metal from wastewater. X-ray diffractometer, Fourier transform infrared spectroscopy, and transmission electron microscope were used to distinguish the prepared absorbents. The absorption of the heavy metals by as-prepared samples was examined at different conditions. The kinetic and isotherm models of the adsorption process were also studied. The data showed that the removal percentages of Cd, Cu, Pb, Zn, Cr and Ni by the composite were 98.0, 94.8, 99.0, 97.9, 97.4 and 98.3 %, respectively. The kinetic and isothermal studies showed that the absorption of these metal ions by the samples obeyed a pseudo-second-order mechanism and Langmuir isotherm model, respectively. In addition, the maximum adsorption capacities of Cd, Cu, Pb, Zn, Cr, and Ni ions by as-prepared nanocomposite were 83.33, 47.84, 98.03, 89.28, 62.11, and 63.69 mg/g, respectively.

Characterization of Some "Hashish" Samples in the Egyptian Illicit Trafficking Market Using a Thermal Separation Probe and Gas Chromatography-Mass Spectrometry.

Drugs that are illegal have long been a part of Egyptian society. The most widely misused form of narcotic is marijuana, also known as "bango", and other cannabis-related products like "hashish". The chemical profile of some available "hashish" in the local Egyptian illegal market and its possible country of origin are investigated using a gas chromatography-mass spectrometry technique in conjunction with a thermal separation probe (TSP/GC/MS). The TSP/GC/MS method reveals the presence of 23 different terpenes, of which caryophylla-4(12),8(13)-dien-5α-ol, isoaromadendrene epoxide, caryophyllene, and alloaromadendrene oxide-(1) are detected in high relative proportions. Ten cannabinoid components are also detected. These are cannabiorcochromene (CBC-C1), tetrahydrocannabivarin (THCV), delta-8-tetrahydrocannabinol (delta-8-THC), exo-THC, cannabichromene, cannabidiol (CBD), cannabielsoin (CBE), dronabinol (delta-9-THC), cannabigerol (CBG), and cannabinol (CBN). Phenotypic index (THC % + CBN %)/CBD %) is measured for the test samples to identify both the nature of the samples (fiber- or drug-type cannabis) and the country of origin.

All-solid-state paper-based potentiometric combined sensor modified with reduced graphene oxide (rGO) and molecularly imprinted polymer for monitoring losartan drug in pharmaceuticals and biological samples.

A cost-effective, highly selective and sensitive paper-based potentiometric combined sensor for losartan potassium drug (LOS) is fabricated, characterized and used for the drug monitoring. The sensor consists of 2 strips of filter paper (20 × 5 mm each) as platform, each imprinted with 4 mm diameter circular spot of carbon. One carbon spot is covered by a reduced graphene oxide (rGO) for use as a substrate for the recognition sensor and the other without rGO is used for the reference electrode. LOS molecularly imprinted drug polymer (MIP) is applied onto the graphene oxide containing strip to act as a drug recognition sensing material and a solid-state polyvinyl butyral (PVB) is applied onto the second carbon spot to act as a reference electrode. Performance characteristics of the combined sensor are examined with chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). Increase effect of rGO on the interfacial double-layer capacitance of the sensing membrane and consequently on the potential stability is confirmed. The developed combined sensor (strip cell) displays a Nernstian slope of -58.2 ± 0.3 mV/decade (R2 = 0.9994) over the linear range 8.5 × 10-7 - 6.9 × 10-2 M with a detection limit of 2.7 ± 0.3 × 10-7 M. The sensor shows remarkable selectivity toward various related compounds especially those commonly used by the COVID-19 patients such as paracetamol, ascorbic acid and dextromethorphan. The assay method is validated and proved to be satisfactory for direct potentiometric determination of LOS-K in some pharmaceutical formulations and in spiked human urine samples. An average recovery of 96.3 ± 0.3-98.7 ± 0.6% of the nominal or spiked concentration and a mean relative standard deviation of ±0.6% are obtained. The use of an indicating and a reference electrodes combined into a single flexible disposable paper platform enables applications to a minimum sample volume due to the close proximity of the responsive membrane and the liquid junction. The efficiency of the proposed sensor in complex urine matrix suggests its application in hospitals for rapid diagnosis of overdose patients and for quality control/quality assurance tests in pharmaceutical industry.

Fabrication and characterization of electrospun nanofibers using biocompatible polymers for the sustained release of venlafaxine.

Recently, drug-controlled release nanotechnology has gained special attention in biomedicine. This work focuses on developing novel electrospun polymeric nanofibers (NFs) for buccal delivery of VEN to avoid the hepatic metabolism and enzymatic degradation in the GIT and develop an effective control of drug release. The optimized NFs were obtained by blending polylactic acid (PLA), and poly (ɛ-caprolactone) (PCL) fixed at a ratio of 1:1. It was characterized for morphology, drug-loading, FTIR, XRD, DSC, and in vitro drug release. Ex vivo permeability of the blend NFs was assessed using chicken pouch mucosa compared to VEN suspension, followed by histopathological examination. Further, the cytotoxic effect in three different cell lines using WST-1 assay. SEM morphologies refer to defect-free uniform NFs of PLA, PCL, and PLA/PCL mats. These fibers had a diameter ranging from 200 to 500 nm. The physico-thermal characterization of NFs depicted that the drug was successfully loaded and in an amorphous state in the PLA/PCL NFs. In vitro release of NFs substantiated a bi-phasic profile with an initial burst release of about 30% in the initial 0.5 h and a prolonged cumulative release pattern that reached 80% over 96 h following a non-Fickian diffusion mechanism. Ex vivo permeation emphasizes the major enhancement of the sustained drug release and the noticeable decrease in the permeability of the drug from NFs. Cytotoxicity data found that IC50 of VEN alone was 217.55 µg/mL, then VEN-NFs recorded an IC50 value of 250.62 µg/mL, and plain NFs showed the lowest toxicity and IC50 440.48 µg/mL in oral epithelial cells (OEC). Histopathology and cell toxicity studies demonstrated the preserved mucosal architecture and the preclinical safety. The developed PLA/PCL NFs can be promising drug carriers to introduce a step-change in improved psychiatric treatment healthcare.

A novel screen-printed potentiometric electrode with carbon nanotubes/polyaniline transducer and molecularly imprinted polymer for the determination of nalbuphine in pharmaceuticals and biological fluids.

A novel screen-printed electrode (SPE) for potentiometric determination of nalbuphine (NAL) is described. Carboxylated multi-walled carbon nano tubes/polyaniline (f-MWCNTs/PANI) nanocomposite is used as an ion-to- electron transducer and is covered by a selective polyvinyl chloride (PVC) membrane incorporated with molecularly imprinted drug polymer (MIP) beads as a recognition receptor for potentiometric determination a synthetic narcotic, nalbuphine (NAL). The SPE displays a Nernstian response with a slope of 60.3 ± 1.2 mV/decade (R2 = 0.999) over the concentration range 2.4 × 10-7 - 5.0 × 10-2 mol/L and a detection limit of 1.1 × 10-7 mol/L (0.04 µg/mL) with response time less than 20 s (<20 s). The interfacial capacitance of the proposed SPE is measured using chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). The use of the f-MWCNTs/PANI nanocomposite layer improved the interfacial capacitance reached 52.5 µF. Besides, it eliminated the formation of the undesired thin water-layer between the sensing membrane and the conducting substrate. This prevents membrane delamination and increases potential stability. The obtained high selectivity, sensitivity and potential stability offered a great applicability of the proposed SPE for the determination of nalbuphine in hospitals for rapid diagnosis of overdose patients and for quality control/quality assurance in pharmaceutical industry.

Removal of Uranium-238, Thorium-232, and Potassium-40 from Wastewater via Adsorption on Multiwalled Carbon Nanotubes.

The optimum conditions for the removal of uranium-238, thorium-232, and potassium-40 from wastewater and the discharge of nuclear facilities using multiwalled carbon nanotubes (CNTs) are described. The adsorption mechanism is mainly attributed to chemical interactions between the metal ions and surface functional groups of the CNTs. Batch adsorption experiments are carried out in order to study the effect of different parameters such as pH, contact time, initial metal ion concentration, adsorbent dose, and temperatures. Maximum metal removal (>98%) from solutions containing 20-120 Bq/L metal ions is achieved using a contact time of 15 min, a pH of 6.0, and 10 mg/L CNTs. The effect of temperature on the kinetics and equilibrium of adsorption on CNT particles is examined. Consistent with an exothermic reaction, an increase in the temperature resulted in an increase in the adsorption rate. Langmuir, Freundlich, and Dubinin-Radushkevich isotherms are applied to the data obtained at various temperatures. The Langmuir adsorption model is the best for data interpretations. The kinetics of adsorption reveals a pseudo-second-order mechanism. Thermodynamic parameters at 293 K (ΔG°, ΔH°, and ΔS°) for U-238, Th-232, and K-40 are -14590.7 kJ/mol, -6.66 kJ/mol, and 26.47 J/(mol K), -96,96.5 kJ/mol, -2.48 kJ/mol, and 14.17 J/(mol K), and -3922.09 kJ/mol, -1.32 kJ/mol, and 6.12 J/(mol K), respectively.

Novel magnetic nickel ferrite nanoparticles modified with poly(aniline-co-o-toluidine) for the removal of hazardous 2,4-dichlorophenol pollutant from aqueous solutions.

Chlorinated organic and phenolic compounds are still purely studied by many researchers because of their severe damage to the aquatic environment and their carcinogenic effect on many living organisms. Therefore, there is a great interest in removing these environmental pollutants from aqueous mediums by easy and inexpensive methods. Herein, novel nickel ferrite (NiFe2O4) nano composite modified with poly(aniline-co-o-toluidine) (PAOT) is prepared, characterized, and used for the removal of 2,4-dichlorophenol (2,4-DCP) as an organic chlorinated environmental pollutant. The morphological properties of the composite are characterized by Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and Brunauer-Emmett-Teller (BET) methods. The prepared composite is tested for the removal of the hazardous dichlorophenol pollutant from aqueous solutions. Under optimized conditions and with effective control of parameters including, contact time, pH of the test solution, adsorbent dose, and temperature, over 83% of the pollutant is adsorbed and removed. The adsorption capacity is 162 mg g-1. Adsorption kinetics, adsorption isotherm and some physicochemical parameters of the reaction are evaluated. The Redlich-Peterson isothermal model is the appropriate model for describing the adsorption process. These results indicate that NiFe2O4/PAOT nanocomposites are promising adsorbents for the removal of persistent organic pollutants (e.g., DCP) from aqueous solutions. The results also reveal that modification of NiFe2O4 particles with poly(aniline-co-o-toluidine) (PAOT) significantly enhances the adsorption capacity of the adsorbent. This is probably due to the electrostatic attraction and non-covalent interactions (e.g. π-π) between the aromatic rings in both dichlorophenol and poly(aniline-co-o-toluidine) copolymer. Advantages offered by using NiFe2O4/PAOT nanocomposites are the high stability, reasonable efficiency, reusability for at least five adsorption-desorption cycles and the ability to remove the adsorbent from aqueous solutions for reuse using an external magnetic field.

Lean and obese microbiota: differences in in vitro fermentation of food-by-products.

The aim of the study was to investigate the potential prebiotic effects of food-by-products (cassava bagasse (n=3), orange bagasse (n=2) and passion fruit peel (n=3)) using an in vitro model simulating the proximal colon, and to assess possible differences in fermentation when using faecal microbiota from lean or obese people. Fermentation of the by-products was compared to a control medium and the prebiotic inulin. The effects of the by-products on the dynamics of the gut microbiota differed according to the type of microbiota, as well as the type of by-product used. Principal Coordinate Analysis of the microbiota showed evidence of a clear separate clustering of lean and obese microbiota before the addition of substrates, which disappeared after fermentation, and instead, distinct clusters due to primary carbohydrate composition of the by-products (starch, fructan and pectin) were present. This is evidence that the substrates drove the obese microbiota to a healthier profile, more similar to that of the lean microbiota. Cassava bagasses enriched the beneficial genus Bifidobacterium in the obese microbiota. The production of total SCFA by cassava bagasses by the obese microbiota was higher than for control medium and inulin. Orange bagasses stimulated the growth of the butyrate-producing genus Coprococcus. Passion fruit peels were poorly fermented and generated negligible amounts of intermediate metabolites, indicating slow fermentation. Nevertheless, passion fruit peel fermentation resulted in a microbiota with the highest diversity and evenness, a positive trait regarding host health. In conclusion, the use of food-by-products could be an important step to tackle obesity and decrease the waste of valuable food material and consequently environmental pollution. They are an inexpensive and non-invasive way to be used as a dietary intervention to improve health, as they were shown here to drive the composition of the obese microbiota to a healthier profile.

A New Validated Potentiometric Method for Sulfite Assay in Beverages Using Cobalt(II) Phthalocyanine as a Sensory Recognition Element.

A simple potentiometric sensor is described for accurate, precise, and rapid determination of sulfite additives in beverages. The sensor is based on the use of cobalt phthalocyanine as a recognition material, dispersed in a plasticized poly(vinyl chloride) matrix membrane. o-Nitrophenyl octyl ether (o-NPOE) as a membrane solvent and tri-dodecylmethyl- ammonium chloride (TDMAC) as ion discriminators are used as membrane additives. Under the optimized conditions, sulfite ion is accurately and precisely measured under batch and flow injection modes of analysis. The sensor exhibits fast and linear response for 1.0 × 10-2-1.0 × 10-6 M (800-0.08 µg/mL) and 1.0 × 10-1-5.0 × 10-5 M (8000-4 µg/mL) sulfite with Nernstian slopes of -27.4 ± 0.3 and -23.7 ± 0.6 mV/concentration decade under static and hydrodynamic modes of operation, respectively. Results in good agreement with the standard iodometric method are obtained.Validation of the assay method is examined in details including precision, accuracy, bias, trueness, repeatability, reproducibility, and uncertainty and good performance characteristics of the method are obtained. The sensor response is stable over the pH range of 5 to 7 without any significant interference from most common anions. The advantages offered by the proposed sensor (i.e., wide range of assay, high accuracy and precision, low detection limit, reasonable selectivity, long term response stability, fast response, and long life span and absence of any sample pretreatment steps) suggest its use in the quality control/quality assurance routine tests in beverages industries, toxicological laboratories and by inspection authorities.

CuFe2O4/Polyaniline (PANI) Nanocomposite for the Hazard Mercuric Ion Removal: Synthesis, Characterization, and Adsorption Properties Study.

Copper ferrite nano-particles (CuFe2O4) were synthesized, characterized, modified with polyaniline to form CuFe2O4/PANI nano-composite. They were used as new adsorbents for the removal of the hazardous mercuric ions from aqueous solutions. High resolution transmission electron microscope (HR-TEM), X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) and Brunauer-Emmett-Teller (BET) were used for the characterization of the synthesized CuFe2O4 nano-particles (NPs) in presence and absence of PANI nano-composite. The synthesized CuFe2O4NPs were of spherical shape with an average size of 10.8 nm. XRD analysis displayed crystal peaks for CuFe2O4NPs and amorphous peaks CuFe2O4/PANI nano-composite due to the existence of polyaniline layer. Contact time, adsorbent dose, solution pH, adsorption kinetics, adsorption isotherm and recyclability were studied. The method at the optimum conditions exhibited high performance with high mercury removal percentage of up to 99% with a maximum adsorption capacity 12.5 and 157.1 mg/g for CuFe2O4 and CuFe2O4/PANI, respectively. The adsorption processes were fitted to Langmuir isotherms. The adsorption behavior of CuFe2O4@PANI composite towards Hg2+ ions is attributed to the soft acid-soft base strong interaction between PANI and Hg(II) ions. High stability and enhanced re-usability are offered using CuFe2O4@PANI composite due to its enhanced removal efficiency. No significant removal decrease was noticed after five adsorption-desorption cycles. In addition, it possesses an easy removal from aqueous solutions by external magnetic field after adsorption experiments. These indicated the enhancement of polyaniline to the surface of CuFe2O4 toward the adsorption of mercury from aqueous solutions.

Imprinted Polymeric Beads-Based Screen-Printed Potentiometric Platforms Modified with Multi-Walled Carbon Nanotubes (MWCNTs) for Selective Recognition of Fluoxetine.

Herein, we present a new validated potentiometric method for fluoxetine (FLX) drug monitoring. The method is based on the integration of molecular imprinting polymer (MIP) beads as sensory elements with modified screen-printed solid contact ion-selective electrodes (ISEs). A multi-walled carbon nanotube (MWCNT) was used as a nanomaterial for the ion-to-electron transduction process. The prepared MIP beads depend on the use of acrylamide (AAm) and ethylene glycol dimethacrylic acid (EGDMA) as a functional monomer and cross-linker, respectively. The sensor revealed a stable response with a Nernstian slope of 58.9 ± 0.2 mV/decade and a detection limit of 2.1 × 10-6 mol/L in 10 mmol/L acetate buffer of pH 4.5. The presented miniaturized sensors revealed good selectivity towards FLX over many organic and inorganic cations, as well as some additives encountered in the pharmaceutical preparations. Repeatability, reproducibility and stability have been studied to evaluate the analytical features of the presented sensors. These sensors were successfully applied for FLX assessment in different pharmaceutical formulations collected from the Egyptian local market. The obtained results agreed well with the acceptable recovery percentage and were better than those obtained by other previously reported routine methods.

Cost-Effective Potentiometric Platforms Modified with Multi-Walled Carbon Nanotubes (MWCNTs) and Based on Imprinted Receptors for Fluvoxamine Assessment.

A simple, efficient and reliable analytical method was developed and used for the determination of the fluvoxamine drug (FLV) in pharmaceutical preparations and biological fluids. The method is based on the cost-effective screen-printed platform for the potential transduction of the drug. Host-tailored molecular imprinting polymer (MIP) was integrated with the potentiometric platform as a recognition receptor, in which FLV, acrylamide (AAm), ethylene glycol dimethacrylate (EGDMA) and acetonitrile were used as a template, functional monomer, cross-linker, and solvent, respectively. MIP particles were dispersed in plasticized poly (vinyl chloride) (PVC) and the membrane was drop-casted on carbon screen-printed electrode. The MIP, in addition to non-imprinted polymers (NIP), was characterized and the binding experiment revealed high affinity and adsorption capacity of MIP towards FLV. The proposed sensor displayed near-Nernstian cationic slope of 55.0 ± 0.8 mV/decade (r2 = 0.999) with a low detection limit of 4.8 × 10-6 mol/L over a wide pH range (3.0-8.5). The electrochemical features of the proposed sensors including electrochemical impedance spectroscopy (EIS) and chronopotentiometry measurements (CP) in the presence of multi-walled carbon nanotubes (MWCNTs) as a solid contact transducer were also investigated. The applications of the proposed sensor for the determination of FLV in different dosage forms with recovery values (98.8%-101.9%) and (97.4%-101.1%), respectively compared with the reference HPLC method with acceptedFandt-student tests values at the 95% confidence level.

Paper Strip and Ceramic Potentiometric Platforms Modified with Nano-Sized Polyaniline (PANi) for Static and Hydrodynamic Monitoring of Chromium in Industrial Samples.

Screen-printed membrane sensors based on the use of paper and ceramic substrates are fabricated, characterized, and used for rapid batch and continuous monitoring of CrIII in the form of CrO42- in some industrial products and wastewater samples. Strips of paper and ceramic platforms (15 × 5 mm) were covered with conductive carbon paint and then modified with polyaniline (PANI) film, to act as an ion-to-electron transducer, followed by a drop casting of plasticized poly (vinyl chloride) (PVC) Rhodamine-B chromate membrane as a recognition sensing material. In a 5.0 mmol L-1 Trizma buffer solution of pH ~8, the fabricated paper and ceramic based membrane sensors exhibited a near Nernstian response for CrVI ion with slopes of -29.7 ± 0.5 and -28.6 ± 0.3 mV decade-1, limit of detection 2.5 × 10-5 and 2.4 × 10-6 mol L-1 (1.3-0.12 µg mL-1), and linear concentration range 7.5 × 10-3-5.0 × 10-5 and 7.5 × 10-3-1.0 × 10-5 mol L-1 (390-0.5 µg mL-1), respectively. Both sensors exhibited fast and stable potentiometric response, excellent reproducibility, and good selectivity with respect to a number of common foreign inorganic species. Impedance spectroscopy and chronopotentiometry data revealed a small resistance and a larger double layer capacitance due to the presence of the intermediate polyaniline (PAN) conductive layer. Furthermore, the formation of a water layer between the ion selective membrane (ISM) and the underlying conductor polymer and between the conducting polymer and the carbon conducting surface was greatly reduced. The developed disposable solid-contact potentiometric sensors offer the advantages of simple design, long term potential stability, flexibility, miniaturization ability, short conditioning time, and cost effectiveness that enable mass production. The sensors were successfully used for static and hydrodynamic measurements of total chromium in some leather tanning wastewater and nickel-chrome alloy samples. The results compare favorably with data obtained by atomic absorption spectrometry.

A SnO2/CeO2 Nano-Composite Catalyst for Alizarin Dye Removal from Aqueous Solutions.

A new SnO2/CeO2 nano-composite catalyst was synthesized, characterized and used for the removal of alizarin dyes from aqueous solutions. The composite material was prepared using a precipitation method. X-ray powder diffractometry (XRD), high resolution transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller methodology (BET) and Fourier Transform Infrared Spectrometry (ATR-FTIR) were utilized for the characterization of the prepared composite. The prepared nano-composite revealed high affinity for the adsorption and decomposition of alizarin dyes. The adsorption capacity under different experimental conditions (adsorbate concentration, contact time, adsorbent dose and pH) was examined. Under optimized experimental conditions, the removal of alizarin yellow, alizarin red and alizarin-3-methylimino-diacetic acid dyes from aqueous solutions was about 96.4%,87.8% and 97.3%, respectively. The adsorption isotherms agreed with the models of Langmuir, Freundlich and Temkin isotherms.

Improved Solid-Contact Nitrate Ion Selective Electrodes Based on Multi-Walled Carbon Nanotubes (MWCNTs) as an Ion-to-Electron Transducer.

Possible improvement of the performance characteristics, reliability and selectivity of solid-contact nitrate ion-selective electrodes (ISE) (SC/NO3--ISE) is attained by the application of a nitron-nitrate (Nit+/NO3-) ion association complex and inserting multi-walled carbon nanotubes (MWCNTs) as an ion-to-electron transducer between the ion sensing membrane (ISM) and the electronic conductor glassy carbon (GC) substrate. The potentiometric performance of the proposed electrode revealed a Nernstian slope -55.1 ± 2.1 (r² = 0.997) mV/decade in the range from 8.0 × 10-8-1 × 10-2 M with a detection limit of 2.8 × 10-8 (1.7 ng/mL). Selectivity, repeatability and reproducibility of the proposed sensors were considerably improved as compared to the coated disc electrode (GC/NO3--ISE) without insertion of a MWCNT layer. Short-term potential stability and capacitance of the proposed sensors were tested using a current-reversal chronopotentiometric technique. The potential drift in presence of a MWCNT layer decreased from 167 µVs-1 (i.e., in absence of MWCNTs) to 16.6 µVs-1. In addition, the capacitance was enhanced from 5.99 µF (in absence of MWCNTs) to 60.3 µF (in the presence of MWCNTs). The presented electrodes were successfully applied for nitrate determination in real samples with good accuracy.

Gold Plate Electrodes Functionalized by Multiwall Carbon Nanotube Film for Potentiometric Thallium(I) Detection.

Solid-contact potentiometric ion-selective electrodes (SC-ISEs) for thallium determination have been designed using multiwall carbon nanotubes (MWCNTs) as the ion-to-electron transducer. Dispersed MWCNTs were drop-casted over a gold plate electrode. Two different crown ethers were used in the sensing membrane for the recognition of thallium (I). Sensorsbased on dibenzo-18-crown-6 (DB18C6) as a neutral carrier and NaTPB as an anionic additive exhibited a near Nernstian response of 57.3 mV/decade towards Tl+ ions over the activity range 4.5 × 10-6-7.0 × 10-4 M, with a limit of detection of 3.2 × 10-7 M. The time required to achieve 95% of the steadyequilibrium potential was <10 s. The complex formation constant (log ßML) between dibenzo-18-crown-6 and thallium (I) (i.e., 5.99) was measured using the sandwich membrane technique. The potential response was pH independent over the range 3.0-9.5. The introduction of MWCNTs as an electron-ion-transducer layer between gold plate and the sensing membrane lead to a smaller membrane resistance and a large double layer capacitance, which was proven using impedance spectra and chronopotentiometry (i.e., 114.9 ± 12 kΩ, 52.1 ± 3.3 pF, 200 ± 13.2 kΩ, and 50 ± 4.2 µF). Additionally, reduction ofthe water layer between the sensing membrane and the underlying conductor wastested. Thus, it is clear that MWCNTs can be used as a transducing layer in SC-ISEs. The proposed sensor was introduced as an indicator electrode for potentiometric titration of single and ternary mixtures of I-, Br-, and S2- anions.

Single-Walled Carbon Nanotubes (SWCNTs) as Solid-Contact in All-Solid-State Perchlorate ISEs: Applications to Fireworks and Propellants Analysis.

Herein, we present reliable, robust, stable, and cost-effective solid-contact ion-selective electrodes (ISEs) for perchlorate determination. Single-walled carbon nanotubes (SWCNTs) were used as solid-contact material and indium (III) 5, 10, 15, 20-(tetraphenyl) porphyrin chloride (InIII-porph) as an ion carrier. The sensor exhibited an improved sensitivity towards ClO4- ions with anionic slope of -56.0 ± 1.1 (R2 = 0.9998) mV/decade over a linear range 1.07 × 10-6 - 1.0 × 10-2 M and detection limit of 1.8 × 10-7 M. The short-term potential stability and the double-layer capacitance were measured by chronopotentiometric and electrochemical impedance spectroscopy (EIS) measurements, respectively. The sensor is used for ClO4- determination in fireworks and propellant powders. The results fairly agree with data obtained by ion chromatography.

Novel Potentiometric 2,6-Dichlorophenolindo-phenolate (DCPIP) Membrane-Based Sensors: Assessment of Their Input in the Determination of Total Phenolics and Ascorbic Acid in Beverages.

In this work, we demonstrated proof-of-concept for the use of ion-selective electrodes (ISEs) as a promising tool for the assessment of total antioxidant capacity (TAC). Novel membrane sensors for 2,6-dichlorophenolindophenolate (DCPIP) ions were prepared and characterized. The sensors membranes were based on the use of either CuII-neocuproin/2,6-dichlorophenolindo-phenolate ([Cu(Neocup)2][DCPIP]2) (sensor I), or methylene blue/2,6-dichlorophenolindophenolate (MB/DCPIP) (sensor II) ion association complexes in a plasticized PVC matrix. The sensors revealed significantly enhanced response towards DCPIP ions over the concentration range 5.13 × 10-5-1.0 × 10-2 and 5.15 × 10-5-1.0 × 10-2 M at pH 7 with detection limits of 6.3 and 9.2 µg/mL with near-Nernstian slope of -56.2±1.7 and -51.6±2 mV/decade for sensors I and II, respectively. The effects of plasticizers and various foreign common ions were also tested. The sensors showed enhanced selectivity towards DCPIP over many other phenolic and inorganic ions. Long life span, high potential stability, high reproducibility, and fast response were also observed. Method validation was also verified by measuring the detection limit, linearity range, accuracy, precision, repeatability and between-day-variability. The sensors were introduced for direct determination of TAC in fresh and canned juice samples collected from local markets. The obtained results agreed fairly well with the data obtained by the standard method.