Anodic stripping voltammetric determination of silver ion at a carbon paste electrode modified with carbon nanotubes

A carbon paste electrode (CPE) was modified with multi-wall carbon nanotubes and successfully applied to the determination of silver ion by differential pulse anodic stripping voltammetry. Compared to a conventional CPE, a remarkably improved peak current response and sensitivity is observed. The analytical procedure consisted of an open circuit accumulation step for 2?min in ?0.4?V, this followed by an anodic potential scan between +0.2 and?+?0.6?V to obtain the voltammetric peak. The oxidation peak current is proportional to the concentration of silver ion in the range from 1.0?×?10^?8 to 1.0?×?10^?5?mol?L^?1, with a detection limit of 1.8?×?10^?9?mol?L^?1 after an accumulation time of 120?s. The relative standard deviation for 7 successive determinations of Ag(I) at 0.1???M concentration is 1.99%. The procedure was validated by determining Ag(I) in natural waters.

Glutamate sol-gel amperometric biosensor based on co-immobilised NADP+ and glutamate dehydrogenase

In this work the preparation and electrochemical characterisation of a new glutamate amperometric sol-gel biosensor is described. A carbon paste electrode was electrochemically modified with the phenothiazine dye methylene green (MG). The NADP⁺ and glutamate dehydrogenase were co-immobilised in a sol-gel matrix. When coupled to a flow injection system (FIA) the biosensor showed good electrocatalytic activity towards NADPH oxidation at the potential of + 0.3 V vs. Ag/AgCl; KCl sat., which represents a strong overpotential reduction. The biosensor yielded a linear response from 5.0 × 10^?5 to 1.0 × 10^?2 M glutamate concentration, with a detection limit of 5 × 10^?6 M and reproducibility of results better than 2.3% (RSD). Moreover, the implemented biosensor showed to be still useful after 7 months, 500 determinations.     

Electrochemical determination of acetaminophen in the presence of propranolol using an electrode modified with a Schiff base from 2-hydroxy-1-naphthaldehyde and ethylenediamine and multi-walled carbon nanotubes

A carbon paste electrode, modified with N,N′-bis-(2-hydroxy-1-naphthalidene)ethylenediamine and multi-walled carbon nanotubes (HNED-MWCNPE), was used for the determination of acetaminophen (ACOP) and propranolol (PP). Cyclic voltammetry (CV), chronocoulometry, chronoamperometry and differential pulse voltammetry (DPV) techniques were employed to study electro-oxidation of ACOP. The results revealed that the modified electrode showed an electrocatalytic activity toward the anodic oxidation of acetaminophen by a marked enhancement in the current response in buffered solution at pH 8.0. Some kinetic parameters such as the electron transfer coefficient (α) were also determined for the ACOP oxidation. The linear concentration range of 1 × 10^?3?1 × 10^?6 M with a detection limit of 4.6 × 10^?8 M (n = 16) for ACOP was obtained using DPV (pH 8.0). The modified electrode shows good sensitivity, selectivity and stability. The prepared electrode was also applied for the determination of ACOP in human blood serum.     

Electrochemical determination of paraquat using a DNA-modified carbon ionic liquid electrode

Deoxyribonucleic acid (DNA) was electrochemically deposited on a carbon ionic liquid electrode to give a biosensor with excellent redox activity towards paraquat as shown by cyclic voltammetry and differential pulse voltammetry. Experimental conditions were optimized with respect to sensing paraquat by varying the electrochemical parameters, solution pH, and accumulation time of DNA. Under the optimized conditions, a linear relation exists between the reduction peak current and the concentration of paraquat in the range from 5?×?10^?8 mol L^?1 to 7?×?10^?5 mol L^?1, with a detection limit of 3.6?×?10^?9 mol L^?1. The utility of the method is illustrated by successful analysis of paraquat in spiked real water samples.

Voltammetric detection of guanosine and adenosine using a carbon paste electrode modified with 1-ethyl-3-methylimidazolium ethylsulfate

A novel kind of carbon paste electrode (CPE) was prepared by mixing graphite powder, liquid paraffin and the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate. The resulting electrode was used for the simultaneous determination of guanosine and adenosine by differential pulse voltammetry. Compared to a conventional CPE, the oxidation peak currents are largely increased, and the oxidation peak potentials are negatively shifted. The electrochemical responses to guanosine and adenosine were investigated. Under optimized conditions, the calibration curves are linear in the concentration range from 1.0?×?10^-6?mol?L^-1 to 1.6?×?10^-4?mol?L^-1 for guanosine, and from 1.0?×?10^-6?mol?L^-1 to 2.7?×?10^-4?mol?L^-1 for adenosine at pH 3.5. Substances potentially interfering in the biological matrix do no interfere. The method was successfully applied to detect adenosine and guanosine in human urine without sample treatments.

Dipyrrolylquinoxaline-bridged hydrazones: a new class of chemosensors for copper(II)

Novel 2,3-bis(1H-pyrrol-2-yl)quinoxaline-functionalized hydrazones were prepared and characterized as new chemosensors for copper(II) ion. The binding properties of the compounds 4, 5, 6 and 7 for cations were examined by UV–vis, fluorescence spectroscopy, and linear sweep voltammetric experiments (LSV). The results indicate that a 1:1 stoichiometric complex is formed between compound 4 (or 5, 6, 7) and copper(II) ion, and the association constant is 1.3?×?10⁵ M^?1 for 4, 2.1?×?10⁶ M^?1 for 5, 4.1?×?10⁵ M^?1 for 6 and 8.0?×?10⁵ M^?1 for 7, respectively. The recognition mechanism between compound 4 (or 5, 6, 7) and metal ion was discussed based on their electrochemical properties, absorbance changes, and the fluorescence quenching effect when they interact with each other. Control experiments revealed that compound 4 (or 5, 6, 7) has a highly selective response to copper (II) ion.     

Sensitive and efficient determination of gabapentin in human serum based on capillary electrophoresis with laser-induced fluorescence detection

A sensitive and efficient analytical method for gabapentin (GBP) in human serum based on capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection has been established. 6-Oxy-(N-succinimidyl acetate)-9-(2′-methoxycarbonyl) fluorescein (SAMF), a new synthesized fluorescent reagent, was used for precolumn derivatization of the non-fluorescent drug in serum. γ-Aminobutyric acid (GABA) was used as an internal standard (I.S.). The best derivative condition was obtained in phosphate buffer (pH 8) at room temperature for 10 min. Optimal separation and detection were obtained with a background electrolyte (BGE) of 3.5 × 10^?2 M phosphate buffer (pH 5.5) and laser-induced fluorescence detection excited at 473 nm. The method developed for GBP was linear over the concentration range of 4.0 × 10^?9 to 4.0 × 10-7 M. The concentration limit of detection was 2.0 × 10^?10 M (signal-to-noise ratio = 3). The sensitive method was used for the determination of GBP in serum samples.     

Method for determination of fluoroquinolones based on the plasmonic interaction between their fluorescent terbium complexes and silver nanoparticles

We report on a fluorometric method for the determination of the fluoroquinolones levofloxacin (LEV) and moxifloxacin (MOXI). It is based on the Tb(III)-sensitized luminescence that is plasmonically enhanced by silver nanoparticles (Ag NPs). The emission of the Tb(III) complexes has maximum at 545?nm after excitation at 284?nm and is strongly enhanced in the presence of the colloidal Ag NPs. Under optimum experimental conditions, luminescence intensity increases linearly with the concentration in the range from 4.16?×?10^-17-3.59?×?10^-15?M of LEV, and from 4.98?×?10^-17-2.49?×?10^-15?M for MOXI with correlation coefficients of 0.9996 and 0.9996, respectively. The limits of detection are 7.19?×?10^-18?M and 8.47?×?10^-18?M, respectively, and the relative standard deviations are 1.3 and 1.5% for 5 replicate measurements at 6.08?×?10^-14?M of LEV and 5.48?×?10^-14?M of MOXI. The method was successfully applied to the determination of LEV and MOXI in pharmaceutical samples, in urine and in serum.

Ion selective electrode for uranium based on composite multiwalled carbon nanotube-benzo-15-crown-5 in PVC matrix coated on graphite rod

Development of a composite multiwalled carbon nanotube (MWNT) polyvinyl chloride (PVC) with benzo-15-crown-5 (B15C5) as ionophore sensor responsive to uranyl ion is described. The composite MWNT-PVC membrane containing the active ingredients was casted on the surface of a graphite rod. The sensor incorporates B15C5 as electroactive material, ortho-nitrophenyl octyl ether (o-NPOE) as a plasticizer and sodium tetraphenyl borate (NaTPB) as an ion discriminator. The sensor displays a rapid and linear response over the concentration range of 1 × 10^?1 to 1 × 10^?7 M with a slope of 29.9 ± 0.4 mV per decade. The detection limit of this electrode was found to be 5.4 × 10^?8 M and the working pH range is from 2.5 to 4.5. Interference from many inorganic cations viz. Na⁺, K⁺, Sr²⁺, Zn²⁺ and Fe³⁺ is negligible for the sensor. Application to the determination of uranium in ores and effluent samples gives results with good correlation which are comparable with data obtained by inductively coupled plasma atomic emission spectrometry. The electrode has been characterized using surface techniques.     

Self-assembly of ultra-small gold nanoparticles on an indium tin oxide electrode for the enzyme-free detection of hydrogen peroxide

A novel enzyme-free electrochemical sensor for H₂O₂ was fabricated by modifying an indium tin oxide (ITO) support with (3-aminopropyl) trimethoxysilane to yield an interface for the assembly of colloidal gold. Gold nanoparticles (AuNPs) were then immobilized on the substrate via self-assembly. Atomic force microscopy showed the presence of a monolayer of well-dispersed AuNPs with an average size of ~4 nm. The electrochemical behavior of the resultant AuNP/ITO-modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. This non-enzymatic and mediator-free electrode exhibits a linear response in the range from 3.0?×?10^?5 M to 1.0?×?10^?3 M (M?=?mol?·?L^?1) with a correlation coefficient of 0.999. The limit of detection is as low as 10 nM (for S/N?=?3). The sensor is stable, gives well reproducible results, and is deemed to represent a promising tool for electrochemical sensing.

Voltammetric determination of theophylline in pharmaceutical formulations using aligned carbon nanotubes (ACNTs) film modified electrode

A novel rapid, convenient and sensitive electrochemical method has been described for the determination of theophylline in pharmaceutical formulations, based on the extraordinary properties of an aligned carbon nanotubes (ACNTs) thin film. The voltammetric results suggest that the ACNTs-coated glass carbon electrode can exhibit excellent electrochemical activity for direct electrochemical oxidation of theophylline. Various experimental parameters such as solution pH value, amount of ACNTs suspension, accumulation conditions and scan rate were optimized for the determination of theophylline. Furthermore, it was found that the peak current increased linearly with the concentration of theophylline in the range of 8.0 × 10^?8?1.0 × 10^?5 M and the detection limit was 1.6 × 10^?8 M using differential pulse voltammetry. This newly proposed method has been applied successfully to the determination of theophylline in drugs.     

Ultra-sensitive electrochemical DNA biosensor based on signal amplification using gold nanoparticles modified with molybdenum disulfide,graphene and horseradish peroxidase

We have developed an ultra-sensitive electrochemical DNA biosensor by assembling probe ssDNA on a glassy carbon electrode modified with a composite made from molybdenum disulfide, graphene, chitosan and gold nanoparticles. A thiol-tagged DNA strand coupled to horseradish peroxidase conjugated to AuNP served as a tracer. The nanocomposite on the surface acts as relatively good electrical conductor for accelerating the electron transfer, while the enzyme tagged gold nanoparticles provide signal amplification. Hybridization with the target DNA was studied by measuring the electrochemical signal response of horseradish peroxidase using differential pulse voltammetry. The calibration plot is linear in the 5.0?×?10^?14 and 5.0?×?10^?9 M concentration range, and the limit of detection is 2.2?×?10^?15 M. The biosensor displays high selectivity and can differentiate between single-base mismatched and three-base mismatched sequences of DNA. The approach is deemed to provide a sensitive and reliable tool for highly specific detection of DNA.

A thin poly(acridine orange) film containing reduced graphene oxide for voltammetric simultaneous sensing of ascorbic acid and uric acid

We have fabricated, in a single step, carbon ceramic electrodes modified with a poly(acridine orange) film containing reduced graphene oxide. They display electrocatalytic activity to ascorbic acid (AA) and uric acid (UA) at pH 4.5. The anodic peak potentials of AA and UA are separated by 276 mV so that they can be well resolved in cyclic voltammetry. UA and AA were simultaneously determined in a mixture at working potentials of 170 and 400 mV, respectively. Under optimized conditions, the calibration curves for AA and UA cover the 0.8–5,000 μM and 0.6–900 μM concentration range, respectively, while detection limits are 0.3 μM and 0.2 μM. The electrode was applied to determine AA and UA in urine samples.

Preparation of an amperometric sensor for norfloxacin based on molecularly imprinted grafting photopolymerization

A sensitive amperometric sensor for norfloxacin (NF) was introduced. The receptor layer was prepared by molecularly imprinted photopolymerization of acrylamide and trimethylolpropane trimethacrylate on the surface of a gold electrode. The binding mechanism of the molecularly imprinted polymer was explored by ultraviolet (UV) and infrared (IR) spectroscopy. The chemosensor was characterized by cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance (EI), and scanning electron microscopy (SEM). The electrode prepared by photopolymerization has a better recognition ability to template molecules than that of electropolymerization and NIP. Some parameters affecting sensor response were optimized. Norfloxacin was detected by measurements of an amperometric i–t curve. The linear relationships between current and logarithmic concentration are obtained from 1.0?×?10^?9 to 1.0?×?10^?3?mol?L^?1. The detection limit of the sensor was 1.0?×?10^?10?mol?L^?1. The proposed method is sensitive, simple, and cheap, and is applied to detect NF in human urine successfully.

The electrochemistry of uric acid at a gold electrode modified with L-cysteine, and its application to sensing uric urine

The electrochemistry of uric acid at a gold electrode modified with a self-assembled film of L-cysteine was studied by cyclic voltammetry and differential pulse voltammetry. Compared to the bare gold electrode, uric acid showed better electrochemical response in that the anodic peak current is stronger and the peak potential is negatively shifted by about 100 mV. The effects of experimental conditions on the oxidation of uric acid were tested and a calibration plot was established. The differential pulse response to uric acid is linear in the concentration range from 1.0?×?10^?6 to ~?1.0?×?10^?4 mol?L^?1 (r?=?0.9995) and from 1.0?×?10^?4 to ~?5.0?×?10^?4 mol?L^?1 (r?=?0.9990), the detection limit being 1.0?×?10^?7 mol?L^?1 (at S/N?=?3). The high sensitivity and good selectivity of the electrode was demonstrated by its practical application to the determination of uric acid in urine samples.

Properties of ion-selective electrodes with polymeric membranes for ketoprofen determination

The aim of the research was to create electrodes based on PVC membrane with solid contact. The membranes were plasticized with bis(2-ethylhexyl)sebacate, (DOS), dibutylphthalate (DBP) diisobutylphthalate (DIBP), tris(2-ethylhexyl) phosphate (TEHP), and 2-nitrophenyloctyl ether (o-NPOE) in which the active substance tetraoctylammonium 3-benzoyl-??-methylbenzeneacetate (KET-TOA) was dissolved. The basic analytical parameters of the ketoprofen electrode such as measuring range, detection limit, response time, lifetime, and selectivity coefficients for some organic and inorganic anions were determined. For all electrodes similar potentiometric responses were obtained: measuring range 1 × 10^?4 ?1 × 10^?1 M, and Nernstian slope of characteristics of about 55?C60 mV/decade. The electrode was used to determine ketoprofen in the synthetic sample and pharmaceutical preparations, in injections, tablets and capsules in the concentration range of 0.025?C25 mg/mL in aqueous solution at pH 5.5?C8.5.     

Electrochemical determination of NADH using a glassy carbon electrode modified with Fe3O4 nanoparticles and poly-2,6-pyridinedicarboxylic acid, and its application to the determination of antioxidant capacity

We have prepared a glassy carbon electrode modified with poly-2,6-pyridinedicarboxylic acid and with magnetic Fe₃O₄ nanoparticles. This modification enhances the effective surface area and the electrocatalytic oxidation of nicotinamide adenine dinucleotide (NADH) in addition to providing positively charged groups for electrostatic assembly of the phosphate group of NADH. The modified electrode responds linearly to NADH in the range from 5?×?10^?8 to 2.5?×?10^?5?M and gives a lower detection limit of 1?×?10^?8?M. It displays satisfactory selectivity and reproducibility. The sensor was applied to rapid screening of plant extracts for their antioxidant properties.

Through bond mechanism versus exciplex formation in the photochemistry of fullerene / ferrocene donor-bridge-acceptor dyads

A systematic fluorescence and flash photolytic investigation of a series of covalently linked fullerene / ferrocene based donor-bridge-acceptor dyads is reported as a function of the nature of the bridge between the donor site and acceptor site. The fluorescence of the investigated dyads 2 (Φ_rel = 0.17 × 10^?4, 3 (Φ_rel = 0.78 × 10^?4), 4 (Φ_rel = 1.5 × 10^?4), 5 (Φ_rel = 0.7 × 10^?4), and 6 (Φ_rel = 2.9 × 10^?4) were substantially quenched, relative to N-methyl fulleropyrrolidine (1) (Φ_rel = 6.0 × 10^?4). Photolysis of N-methyl fulleropyrrolidine (1) in toluene revealed formation of the excited singlet state which was followed by a rapid intersystem crossing to the excited triplet state. On the other hand, the fate of the excited singlet state of 2, 3, 4, 5, and 6 was found to be governed by rapid intramolecular quenching, with rate constants of 28×10⁹ s^?1, 6.9×10⁹ s^?1, and 3.4×10⁹ s^?1, 14×10⁹ s^?1, 2.3×10⁹ s^?1 respectively. The electron transfer process and the charge separation were confirmed by monitoring the characteristic π-radical anion bands at λ_max = 400 and 1055 nm in degassed benzonitrile with τ_1/2 = 1.8 μs (3) and 2.5 μs (4).     

The unimolecular thermal decomposition of oxetane and its methyl derivatives: An Ab initio and RRKM calculations

Quantum mechanical and Rice-Ramsperger-Kassel-Marcus (RRKM) calculations are carried out to study the thermal unimolecular decomposition of oxetane (1), 2-methyloxetane (2), and 2,2-dimethyloxetane (3) at the MPW1PW91/6-311 + G** level of theory. The results of the calculations reveal that decomposition reaction of compounds 1?C3 yields formaldehyde and the corresponding substituted olefin. The predicted high-pressure-limit rate constants for the decomposition compounds 1?C3 are represented as 6.61 × 10¹³exp(?32472/T), 9.33 × 10¹³exp(?29873/T), and 4.79 × 10¹³exp(?27055/T) s^?1, respectively. The fall-off pressures for the decomposition of compounds 1?C3 are found to be 9.42 × 10^?2, 3.67 × 10^?3, and 7.26 × 10^?4 mm Hg, respectively. As the fall-off pressure of the decomposition process of compounds 1?C3 are in the following order: P _1/2(1) > P _1/2(2) > P _1/2(3); therefore the decomposition rates are as follow: rate(1) < rate(2) < (3).     

Colorimetric and visual determination of melamine by exploiting the conformational change of hemin G-quadruplex-DNAzyme

We report on the detection of trace quantities of melamine (MA) by a colorimetric method that exploits the conformational change of hemin G-quadruplex-DNAzyme. The addition of MA to hemin G-quadruplex-DNAzyme structure containing thymine bases causes the thymine in the DNAzyme to interact with MA via a stable triple H-bond and leads to a conformational change. This, in turn, affects the peroxidase-like activity of hemin which is determined colorimetrically at 450 nm by adding 3,3’,5,5’-tetramethylbenzidine and hydrogen peroxide. The method was applied to the colorimetric determination of MA over a wide range of concentrations (0.2 to 24 μM) with a detection limit of 80 nM. The effect also can be detected with bare eyes. The method was successfully applied to the determination of MA in spiked milk powder.