Sharif Digital Repository

An anion-selective electrode based on rhodium(II) phthalocyanine (RhPc) as a neutral carrier is reported. The prepared electrode displays an anti-Hofmeister behavior with a high selectivity for thiocyanate. The potentiometric response characteristics and selectivities of the membrane electrodes with various ratios of cationic additive to ion-carrier indicate that the observed potentiometric response is based on the formation of a 1:1 complex between RhPc and thiocyanate as an axial ligand. The membrane electrodes containing ∼60 mol percent of cationic additive (relative to ionophore) exhibit a near-Nernstian response in a concentration range of thiocyanate between 1 × 10-6 M to 1 × 10-1 M, a... 

The potentiometric response properties of several PVC-based membrane electrodes using phthalocyanine complexes of aluminum (AlPc), nickel (NiPc) and copper (CuPc) as anion carriers, toward thiosalicylic acid (TSA) were investigated. The influences of lipophilic ionic additives (cationic and anionic) and the pH of the buffered solutions were used for the interpretation of the mechanism of the potentiometric response of sensors. The sensitivity, linear range, detection limit, and potentiometric selectivity of the membrane sensors show a considerable dependence on the nature of central metal of the ionophore. The membrane electrodes based on AlPc demonstrate sub-Nernstian responses toward TSA... 

A metallophthalocyanine complex with zirconium(IV) ion in the center (as an oxo-zirconium, Zr=O, group) was used in poly vinyl chloride (PVC) membranes for the selective detection of 5-sulfosalicylic acid (SSA). The resulting electrodes demonstrate Nernstian responses over a wide range of sulfosalicylic acid concentration (10-6 to 10-1 mol dm-3) with a slope of about -29 mV per decade. The influence of lipophilic ion-exchanger sites on the response properties of the electrodes was investigated. The optimal potentiometric response was observed for the electrode in the presence of about 150 mol% of cationic additive (relative to ionophore) in the phase membrane. The electrodes have a fast... 

The voltammetric behavior of thioglycolic acid (TGA) was studied at a carbon paste electrode modified with cobalt phthalocyanine (CoPc). The CoPc-modified electrode shows high electrocatalytic activity toward oxidation of TGA, lowering substantially the overpotential of anodic reaction. Results of the cyclic voltammetry show that TGA undergoes a two-step oxidation (each step with one electron) resulting the dimer of thiol. Enhancement of the rate of electron transfer results in a near-Nernstian behavior of modified electrode to the concentration of TGA and makes it as a suitable potentiometric sensor for the detection of this compound. This electrode shows a near-Nernstian response in a wide... 

Salicylate selective electrodes based on oxo(phthalocyanato)-vanadium(IV) [VO(Pc), vanadyl phthalocyanine] and oxo(phthalocyanato)molybdenum(IV) [MoO(Pc), molybdenyl phthalocyanine] are described. The electrodes were prepared by incorporating the ionophores into plasticized poly(vinyl chloride) membranes, which were directly coated on the surface of graphite electrodes. The resulting electrodes demonstrate Nernstian responses over a wide linear range (10-7-10-1 M) salicylate. The electrodes have a fast response time, submicromolar detection limit, and could be used over the pH range of 6-9. The proposed sensors revealed selectivity for salicylate over a number of common inorganic and organic... 

A novel ion selective electrode is fabricated for naltrexone HCl and used in pharmaceutical analysis and drug determination in biological fluids without complicated pretreatments and extractions, using direct potentiometry. The naltrexone complex with sodium tetraphenyl borate (NaTPB) is obtained by in situ soaking PVC membrane electrode in an 1 × 10 -3 M naltrexone solution. The sensor exhibited fast, reproducible and linear sub-Nernstian response over concentration range of 1 × 10 -5 - 1 × 10 -3 M with a detection limit of 5 × 10 -6 M. The membrane sensor was successfully applied to the determination of naltrexone in capsules as well as for its determination in urine and plasma samples  

The voltammetric performance of edge-plane pyrolytic graphite (EPG) electrode via adsorptive stripping voltammetry was investigated for study of the electrochemical behavior of omeprazole (OMZ) in aqueous solution. The results revealed that the oxidation of OMZ is an irreversible pH-dependent process that proceeds with the transfer of one electron and one proton in an adsorption-controlled mechanism. The determination conditions, such as the pH values of the supporting electrolyte, accumulation time and scan rate were optimized. Simplicity, high reproducibility and low detection limit (3 nM) of the electrode response as well as wide linear range (0.01 to 4.0 µM) can be stated as significant... 

The electrooxidation of clozapine (CLZ) was studied on the surface of a glassy carbon electrode (GCE) modified with a thin film of multiwalled carbon nanotubes (MWCNTs)/new coccine (NC) doped polypyrrole (PPY) by using linear sweep voltammetry (LSV). The pH of the supporting electrolyte (D), drop size of the cast MWCNTs suspension (E) and accumulation time of CLZ on the surface of modified electrode (F) was considered as effective experimental factors and the oxidation peak current of CLZ was selected as the response. By using factorial-based response-surface methodology, the optimum values of factors were obtained as 5.44, 10 μL and 300 s for D, E and F respectively. Under the optimized... 

The electrochemical oxidation of sumatriptan on the surface of carbon paste electrode modified with multi-walled carbon nanotube and cobalt methyl-salophen complex is studied by using cyclic voltammetry and polarization studies. The results indicate that the drug is irreversibly oxidized in a one electron oxidation mechanism. It was found that the peak potential shifted negatively with increasing pH, confirms that H + participate in the oxidation process. The electrode is shown to be very effective for the detection of sumatriptan in the presence of other biological reductant compounds. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of... 

A simple electrodeposition method is employed to construct a thin film modifier of palladium-gold nanoparticles (Pd-AuNPs) decorated multi-walled carbon nanotube (MWCNT) on the surface of glassy carbon electrode (GCE). Morphology and property of Pd-AuNPs-MWCNT have been examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Electrochemical performance of Pd-AuNPs-MWCNT/GCE for detection of ceftazidime (CFZ) has been investigated by cyclic voltammetry (CV). This nanostructured film modified electrode effectively exhibited enhanced properties for detection of ceftazidime (CFZ). The effects of various experimental variables such as, the amount of casted MWCNT,... 

Urea and inorganic ions are present in some of the physiological systems, e.g. urine. Understanding the interactions in urea/salt/water is a preliminary step to shed light on more complicated behavior of multi-component physiological systems. State-of-the-art models as well as thermophysical properties can be applied to understand the interactions in these systems. In order to determine such interactions densities, mean ionic activity coefficients (MIACs), osmotic coefficients, and solubility were measured in aqueous solutions of urea and different salts. Densities were determined at temperatures 293.15, 303.15, and 313.15K for urea concentrations up to 3molal and up to 1molal for NaCl.... 

In this research, thermodynamic modeling and activity coefficient prediction of KCl in the (water + formamide/glucose/proline) mixed solvent systems were reported. Thermodynamic study was performed using the potentiometric data based on extended ion interaction Pitzer-Archer model in various mixed solvent systems containing 0, 10, 20, 30 and 40% mass fractions of formamide and glucose at T = 298.2 K and 0, 2.5, 5.0, 7.5 and 10.0% mass fractions of proline at T = 308.2 K and ambient pressure over ionic strength ranging from 0.0014 to 3.9579 mol·kg- 1. The adjustable parameters were determined and the obtained results were then interpreted based on extended ion interaction Pitzer-Archer model.... 

Artificial neural networks were used to predict the oxidation peaks potentials of 7 monosaccharides under linear sweep voltammetry regime. Two sets of descriptors, one based on molecular properties calculated through DFT and another based on simple geometric distributions of hydroxyl groups and asymmetric carbon atoms along molecular chains, were employed to introduce the molecules to networks. Relatively, simple networks of (3,3,1) and (3,3,3,1) structures with the number of epochs not exceeding 15 through training process were capable of correctly predicting the peaks positions with R values in the range of 0.97-0.99. © 2008 Elsevier Ltd. All rights reserved  

Electrochemical oxidation of catechol in the presence of 3-mercapto-1,2,4-triazole (MTA) as a nucleophile in aqueous buffered solutions was studied by cyclic voltammetry and controlled-potential coulometry. The mechanism of electrochemical reaction is confirmed by spectrophotometric tracing in various times of controlled-potential coulometry. The voltammetric and spectrophotometric foundations indicate that a 1,4 Michael addition of MTA from its thiol moiety to the electrochemically derived o-quinone is occurred. The electrochemical synthesis of Michael addition product has been successfully accomplished by controlled-potential coulometry in a divided H-type cell and the reaction product was... 

A carbon paste electrode (CPE) modified with 2,2′-[1,2 butanediylbis(nitriloethylidyne)]-bis-hydroquinone (BBNBH) and TiO2 nanoparticles was used for the sensitive voltammetric determination of epinephrine (EP). The electrochemical response characteristics of the modified electrode toward EP and acetaminophen (AC) were investigated by cyclic and differential pulse voltammetry (CV and DPV). The results showed an efficient catalytic activity of the electrode for the electrooxidation of EP, which leads to a reduction in its overpotential by more than 270 mV. The effects of pH and potential sweep rate on the mechanism of the electrode process were investigated. The modified electrode exhibits an... 

Biosensors could be used as digital devices to measure the sample infield. Consequently, computational programming along with experimental achievements are required. In this study, a novel biosensor/artificial neural network (ANN) integrated system was developed. Poly (3,4-ethylenedioxy-thiophene)(PEDOT), graphene oxide nano-sheets (GONs) and laccase (Lac) were used to construct a biosensor. The simple and one-pot process was accomplished by electropolymerizing 3,4-ethylenedioxy-thiophene (EDOT) along with GONs and Lac as dopants on glassy carbon electrode. Scanning electron microscopy (SEM) and electrochemical characterization were conducted to confirm successful enzyme entrapment. The... 

Herein, we present a novel, simple, and ultrasensitive electrochemical DNA (E-DNA) sensor based on hollow carbon spheres (HCS) decorated with polyaniline (PANI). A thiolated 21-mer oligonucleotide, characteristic of HBV DNA, is immobilized via electrodeposited gold nanoparticles on HCS-PANI. Cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS) are used to characterize the electrochemical properties of the prepared nanocomposite. Scanning electron microscopy is employed to investigate the morphological texture of the fabricated modifier. An enhanced intrinsic signal of PANI is probed to evaluate the biosensing ability of the prepared... 

A fiber coating from polyaniline (PANI) was electrochemically prepared and employed for solid phase microextraction (SPME) of some polycyclic aromatic hydrocarbons (PAHs) from water samples. The PANI film was directly electrodeposited on the platinum wire surface in sulfuric acid solution using cyclic voltammetry (CV) technique. The applicability of this coating was assessed employing a laboratory-made SPME device and gas chromatography with mass spectrometry (GC-MS) for the extraction of some PAHs from the headspace of aqueous samples. Application of wider potential range in CV led to a PANI with more stability against the temperature. The homogeneity and the porous surface structure of the... 

An aniline-based polymer was electrochemically prepared and applied as a new fiber coating for solid phase microextraction (SPME) of some priority phenols from water samples. The polyaniline (PANI) film was directly electrodeposited on the platinum wire surface in sulfuric acid solution using cyclic voltammetry (CV) technique. The efficiency of new coating was investigated using a laboratory-made SPME device and gas chromatography with flame ionization detection for the extraction of some phenols from the headspace of aqueous samples. The scanning electron microscopy (SEM) images showed the homogeneity and the porous surface structure of the film. The results obtained proved the ability of... 

For the first time, a new platform based on electrochemical growth of Au nanoparticles on aligned multi-walled carbon nanotubes (A-MWCNT) was developed for sensitive lable-free DNA detection of the TP53 gene mutation, one of the most popular genes in cancer research. Electrochemical impedance spectroscopy (EIS) was used to monitor the sequence-specific DNA hybridization events related to TP53 gene. Compared to the bare Ta or MWCNT/Ta electrodes, the synergistic interactions of vertically aligned MWCNT array and gold nanoparticles at modified electrode could improve the density of the probe DNA attachment and resulting the sensitivity of the DNA sensor greatly. Using EIS, over the extended...