All-Solid-State Potentiometric Platforms Modified with a Multi-Walled Carbon Nanotubes for Fluoxetine Determination.

Novel cost-effective screen-printed potentiometric platforms for simple, fast, and accurate assessment of Fluoxetine (FLX) were designed and characterized. The potentiometric platforms integrate both the FLX sensor and the reference Ag/AgCl electrode. The sensors were based on the use of 4'-nitrobenzo-15-crown-5 (ionophore I), dibenzo-18-crown-6 (ionophore II), and 2-hydroxypropyl-ß-cyclodextrin (2-HP-ß-CD) (ionophore III) as neutral carriers within a plasticized PVC matrix. Multiwalled carbon nanotubes (MWCNTs) were used as a lipophilic ion-to-electron transducing material and sodium tetrakis [3,5-bis(trifluoromethyl)phenyl] borate (NaTFPB) was used as an anionic excluder. The presented platforms revealed near-Nernstian potentiometric response with slopes of 56.2 ± 0.8, 56.3 ± 1.7 and 64.4 ± 0.2 mV/decade and detection limits of 5.2 × 10-6, 4.7 × 10-6 and 2.0 × 10-7 M in 10 mM Tris buffer solution, pH 7 for sensors based on ionophore I, II, and III, respectively. All measurements were carried out in 10 mM tris buffer solution at pH 7.0. The interfacial capacitance before and after insertion of the MWCNTs layer was evaluated for the presented sensors using the reverse-current chronopotentiometry. The sensors were introduced for successful determination of FLX drug in different pharmaceutical dosage forms. The results were compared with those obtained by the standard HPLC method. Recovery values were calculated after spiking fixed concentrations of FLX in different serum samples. The presented platforms can be potentially manufacturable at large scales and provide a portable, rapid, disposable, and cost-effective analytical tool for measuring FLX.

New Potentiometric Screen-Printed Platforms Modified with Reduced Graphene Oxide and Based on Man-Made Imprinted Receptors for Caffeine Assessment.

Caffeine is a psychoactive drug that is administered as a class II psychotropic substance. It is also considered a component of analgesics and cold medicines. Excessive intake of caffeine may lead to severe health damage or drug addiction problems. The assessment of normal caffeine consumption from abusive use is not conclusive, and the cut-off value for biological samples has not been established. Herein, new cost-effective and robust all-solid-state platforms based on potentiometric transduction were fabricated and successfully utilized for caffeine assessment. The platforms were modified with reduced graphene oxide (rGO). Tailored caffeine-imprinted polymeric beads (MIPs) based on methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) were prepared, characterized, and used as recognition receptors in the presented potentiometric sensing devices. In 50 mM MES buffer, the sensors exhibited a slope response of 51.2 ± 0.9 mV/decade (n = 6, R2 = 0.997) over the linear range of 4.5 × 10−6−1.0 × 10−3 M with a detection limit of 3.0 × 10−6 M. They exhibited fast detection of caffeinium ions with less than 5 s response time (<5 s). The behavior of the presented sensors towards caffeinium ions over many common organic and inorganic cations was evaluated using the modified separate solution method (MSSM). Inter-day and intra-day precision for the presented analytical device was also evaluated. Successful applications of the presented caffeine sensors for caffeine determination in commercial tea and coffee and different pharmaceutical formulations were carried out. The data obtained were compared with those obtained by the standard liquid chromatographic approach. The presented analytical device can be considered an attractive tool for caffeine determination because of its affordability and vast availability, particularly when combined with potentiometric detection.

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.

Synthesis and Characterization of CuFe2O4 Nanoparticles Modified with Polythiophene: Applications to Mercuric Ions Removal.

In this research, CuFe2O4 nanoparticles were synthesized by co-precipitation methods and modified by coating with thiophene for removal of Hg(II) ions from aqueous solution. CuFe2O4 nanoparticles, with and without thiophene, were characterized by x-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), energy dispersive x-ray (EDX), high-resolution transmission electron microscopy (HRTEM) and Brunauer-Emmett-Teller (BET). Contact time, adsorbent dose, solution pH, adsorption kinetics, adsorption isotherm and recyclability were studied. The maximum adsorption capacity towards Hg2+ ions was 7.53 and 208.77 mg/g for CuFe2O4 and CuFe2O4@Polythiophene composite, respectively. Modification of CuFe2O4 nanoparticles with thiophene revealed an enhanced adsorption towards Hg2+ removal more than CuFe2O4 nanoparticles. The promising adsorption performance of Hg2+ ions by CuFe2O4@Polythiophene composite generates from soft acid-soft base strong interaction between sulfur group of thiophene and Hg(II) ions. Furthermore, CuFe2O4@Polythiophene composite has both high stability and reusability due to its removal efficiency, has no significant decrease after five adsorption-desorption cycles and can be easily removed from aqueous solution by external magnetic field after adsorption experiments took place. Therefore, CuFe2O4@Polythiophene composite is applicable for removal Hg(II) ions from aqueous solution and may be suitable for removal other heavy metals.

Modified Potentiometric Screen-Printed Electrodes Based on Imprinting Character for Sodium Deoxycholate Determination.

Potentiometric sensors have a great influence on the determination of most various compounds in their matrices. Therefore, efficient and new sensors were introduced to measure sodium Deoxycholate (NaDC) as a bile acid salt. These sensors are based on NaDC imprinted polymer (MIP) as sensory element. The MIP beads were synthesized using thermal polymerization pathway, in which acrylamide (AAm), ethylene glycol dimethacrylate (EGDMA), NaDC, and benzoyl peroxide (BPO) were used as the functional monomer, cross-linker, template, and initiator, respectively. The proposed sensors were fabricated using a coated screen-printed platform and the sensing membrane was modified by single-walled carbon nanotubes (SWCNTs) as an ion-to-electron transducer. The sensors exhibited high sensitivity that reached 4.7 × 10-5 M of near-Nernestian slope (-60.1 ± 0.9 mV/decade, r2 = 0.999 (n= 5)). In addition, the sensors revealed high selectivity, long lifetime, high potential stability, and conductivity that ensure reproducible and accurate results over a long time. MIP characterization was performed using Fourier Transform-Infrared (FT-IR) and a scanning electron microscope (SEM). Regarding the interaction of NaDC with serum albumin (SA), albumin is determined in human serum samples as human serum albumin (HSA), which was collected from different volunteers of different ages and gender.

Potentiometric PVC-Membrane-Based Sensor for Dimethylamine Assessment Using A Molecularly Imprinted Polymer as A Sensory Recognition Element.

A new simple potentiometric sensor is developed and presented for sensitive and selective monitoring of dimethylamine (DMA). The sensor incorporates a molecularly imprinted polymer, with a pre-defined specific cavity suitable to accommodate DMA. The molecularly imprinted polymer (MIP) particles were dispersed in an aplasticized poly(vinyl chloride) matrix. The MIP is synthesized by using a template molecule (DMA), a functional monomer (acrylamide, AM), cross-linker (ethylene glycol dimethacrylate, EGDMA) and initiating reagent (benzoylperoxide, BPO). Using Trizma buffer solution (5 mmol L-1, pH 7.1), the sensor exhibits a rapid, stable and linear response for 1.0 × 10-5 to 1.0 × 10-2 mol L-1 DMA+ with a calibration slope of 51.3 ± 0.3 mV decade-1, and a detection limit of 4.6 × 10-6 mol L-1 (0.37 µg mL-1). The electrode exhibited a short response time (10 s) and stable potential readings (± 0.5 mV) for more than 2 months. Potentiometric selectivity measurements of the sensor reveal negligible interferences from most common aliphatic and aromatic amines. High concentration levels (100-fold excess) of many inorganic cations do not interfere. The sensor is successfully used for quantification of low levels of DMA down to 0.5 µg mL-1. Verification of the presented method was carried out after measuring the detection limit, working linearity range, ruggedness of the method, accuracy, precision, repeatability and reproducibility. Under flow-through conditions, the proposed sensor in its tubular form is prepared and introduced in a two-channel flow injection setup for hydrodynamic determination of DMA. The sampling rate is 50-55 samples h-1. The sensor is used to determine DMA in different soil samples with an accuracy range of 97.0-102.8%.

Novel Aminoacridine Sensors Based on Molecularly Imprinted Hybrid Polymeric Membranes for Static and Hydrodynamic Drug Quality Control Monitoring.

Novel biomimetic potentiometric ion-selective electrodes (ISEs) were fabricated and designed for the assessment of aminoacridine (ACR) based on newly synthesized imprinted polymer (MIP) membranes. Thermal polymerization of methacrylic acid (MAA) or acrylamide (AM) as function monomer, aminoacridine as a template and ethylene glycol dimethacrylate (EGDMA) as across-linker, were utilizedto give the molecular recognition part. The membranes of sensors I andII consist of MIP based MAA and AM, respectively, dispersed in a poly(vinyl chloride) membrane plasticized with dioctyl phthalate (DOP) in the ratio of 3.0 wt%, 32.2 wt% and 64.8 wt%, respectively. Sensors III and IV were similarly prepared with added 1.0 wt% tetraphenyl borate (TPB-) as an anionic discriminator. Sensors I and II exhibited near-Nernstian potential response to ACR+ with slopes of 51.2 ± 1.3 and 50.5 ± 1.4 mV/decade in a 0.01 M phosphate buffer of pH 6.0. The linear response coversthe concentration range of 5.2 × 10-6 to 1.0 × 10-3 M with a detection limit of 0.05 and 0.17 µg/mL for sensors I and II, respectively. The performance characteristics of these sensors were evaluated under static and hydrodynamic mode of operations. They were used for quality control assessment of aminoacridine in some pharmaceutical preparations and biological samples.

Single-Piece All-Solid-State Potential Ion-Selective Electrodes Integrated with Molecularly Imprinted Polymers (MIPs) for Neutral 2,4-Dichlorophenol Assessment.

A novel single-piece all-solid-state ion-selective electrode (SC/ISE) based on carbon-screen printed is introduced. Polyaniline (PANI) is dissolved in a membrane cocktail that contains the same components used for making a conventional ion-selective polyvinyl chloride (PVC) matrix membrane. The membrane, having the PANI, is directly drop-casted on a carbon substrate (screen-printed-carbon electrode). PANI was added to act as an intermediary between the substrate and the membrane for the charge transfer process. Under non-equilibrium sensing mechanism, the sensors revealed high sensitivity towards 2,4-dichlorophenol (DCP) over the linearity range 0.47 to 13 µM and a detection limit 0.13 µm. The selectivity was measured by the modified separate solution method (MSSM) and showed good selectivity towards 2,4-DCP over the most commonly studied ions. All measurements were done in 30 mm Tris buffer solution at a pH 5.0. Using constant-current chronopotentiometry, the potential drift for the proposed electrodes was checked. Improvement in the potential stability of the SPE was observed after the addition of PANI in the sensing membrane as compared to the corresponding coated-wire electrode (membrane without PANI). The applicability of the sensor has been checked by measuring 2,4-DCP in different water samples and the results were compared with the standard HPLC method.

Tailor-Made Specific Recognition of Cyromazine Pesticide Integrated in a Potentiometric Strip Cell for Environmental and Food Analysis.

Screen-printed ion-selective electrodes were designed and characterized for the assessment of cyromazine (CYR) pesticide. A novel approach is to design tailor-made specific recognition sites in polymeric membranes using molecularly imprinted polymers for cyromazine (CR) determination (sensor I). Another sensor (sensor II) is the plasticized PVC membrane incorporating cyromazine/tetraphenyl borate ion association complex. The charge-transfer resistance and water layer reached its minimal by incorporating Polyaniline (PANI) solid-contact ISE. The designed electrodes demonstrated Nernstain response over a linear range 1.0 × 10-2-5.2 × 10-6 and 1.0 × 10-2-5.7 × 10-5 M with a detection limit 2.2 × 10-6 and 8.1 × 10-6 M for sensors I and II, respectively. The obtained slopes were 28.1 ± 2.1 (r2 = 0.9999) and 36.4 ± 1.6 (r2 = 0.9991) mV/decade, respectively. The results showed that the proposed electrodes have a fast and stable response, good reproducibility, and applicability for direct measurement of CYR content in commercial pesticide preparations and soil samples sprayed with CYR pesticide. The results obtained from the proposed method are fairly in accordance with those using the standard official method.

Non-Equilibrium Potential Responses towards Neutral Orcinol Using All-Solid-State Potentiometric Sensors Integrated with Molecularly Imprinted Polymers.

Molecularly imprinted polymer (MIP) receptors have been synthesized, characterized, and applied as new selective receptors in solid-contact ion selective electrodes (ISEs) towards non-dissociated 3,5-dihydroxytoluene (orcinol). Two monomers, namely methacrylic acid (MAA) and acrylamide (AA), were used in the preparation of MIP receptors. Graphene (Gr) was used as the solid contact material between the sensing membrane and the electrical contact substrate. Based on non-equilibrium sensing mechanism, the proposed sensors reveal observably enhanced detection sensitivity towards orcinol with detection limits 1.7 × 10-5 and 3.3 × 10-6 M for sensors based on MIP/MAA and MIP/AA, respectively. The selectivity coefficients measured by the modified separate solution method (MSSM) for the proposed sensors showed good selectivity towards orcinol over most common other phenols and inorganic anions. All measurements were made in the presence of 30 mM phosphate buffer solution (PBS) with a pH of 7.0. Potential stability for the proposed sensors was tested by constant-current chronopotentiometry. No water films were formed between the sensing membrane and the electron conductor substrate. The applicability of MIP/MAA incorporated ISE has been checked by recovery test of orcinol in the presence of soil matrix and by standard addition method.

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.

Screen-printed Microsensors Using Polyoctyl-thiophene (POT) Conducting Polymer As Solid Transducer for Ultratrace Determination of Azides.

Two novel all-solid-state potentiometric sensors for the determination of azide ion are prepared and described here for the first time. The sensors are based on the use of iron II-phthalocyanine (Fe-PC) neutral carrier complex and nitron-azide ion-pair complex (Nit-N3-) as active recognition selective receptors, tetradodecylammonium tetrakis(4-chlorophenyl) borate (ETH 500) as lipophilic cationic additives and poly(octylthiophene) (POT) as the solid contact material on carbon screen-printed devices made from a ceramic substrate. The solid-contact material (POT) is placed on a carbon substrate (2 mm diameter) by drop-casting, followed, after drying, by coating with a plasticized PVC membrane containing the recognition sensing complexes. Over the pH range 6-9, the sensors display fast (< 10 s), linear potentiometric response for 1.0 × 10-2⁻1.0 × 10-7 M azide with low detection limit of 1.0 × 10-7 and 7.7 × 10-8 M (i.e., 6.2⁻4.8 ng/ml) for Fe-PC/POT/and Nit-N3-/POT based sensors, respectively. The high potential stability and sensitivity of the proposed sensors are confirmed by electrochemical impedance spectroscopy (EIS) and constant-current chronopotentiometry measurement techniques. Strong membrane adhesion and absence of delamination of the membrane, due to possible formation of a water film between the recognition membranes and the electron conductor are also verified. The proposed sensors are successfully applied for azide quantification in synthetic primer mixture samples. Advantages offered by these sensors are the robustness, ease of fabrication, simple operation, stable potential response, high selectivity, good sensitivity and low cost.

Single-Piece Solid Contact Cu2+-Selective Electrodes Based on a Synthesized Macrocyclic Calix[4]arene Derivative as a Neutral Carrier Ionophore.

Herein, a facile route leading to good single-walled carbon nanotubes (SWCNT) dispersion or poly (3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) based single-piece nanocomposite membrane is proposed for trace determination of Cu2+ ions. The single-piece solid contact Cu2+-selective electrodes were prepared after drop casting the membrane mixture on the glassy-carbon substrates. The prepared potentiometric sensors revealed a Nernstian response slope of 27.8 ± 0.3 and 28.1 ± 0.4 mV/decade over the linearity range 1.0 × 10-3 to 2.0 × 10-9 and 1.0 × 10-3 to 1.0 × 10-9 M with detection limits of 5.4 × 10-10 and 5.0 × 10-10 M for sensors based on SWCNTs and PEDOT/PSS, respectively. Excellent long-term potential stability and high hydrophobicity of the nanocomposite membrane are recorded for the prepared sensors due to the inherent high capacitance of SWCNT used as a solid contact material. The sensors exhibited high selectivity for Cu2+ ions at pH 4.5 over other common ions. The sensors were applied for Cu2+ assessment in tap water and different tea samples. The proposed sensors were robust, reliable and considered as appealing sensors for copper (II) detection in different complex matrices.