Highly selective thiocyanate poly(vinyl chloride) membrane electrode based on a cadmium–Schiff’s base complex

A PVC membrane electrode based on a cadmium–salen (N,N′-bis-salicylidene-1,2ethylenediamine) complex as an anion carrier is described. The electrode has an anti-Hofmeister selectivity sequence with a preference for thiocyanate at pH 1.5–11.0. It has a linear response to thiocyanate from 1.0 × 10^–6 to 1.0 × 10^–1 mol L^–1 with a slope of 59.1 ± 0.2 mV per decade, and a detection limit of 7 × 10^–7 mol L^–1. This electrode has high selectivity for thiocyanate relative to many common organic and inorganic anions. The proposed sensor has a fast response time of approximately 15 s. It was applied to the determination of thiocyanate in a milk sample. Received: 1 December 2000 / Revised: 19 April 2001 / Accepted: 30 April 2001     

Determination of thiocyanate ions at nanolevel in real samples using coated graphite electrode based on synthesised macrocyclic Zn(II) complex

The electrode characteristics and selectivities of PVC-based thiocyanate selective polymeric membrane electrode (PME) incorporating the newly synthesized zinc complex of 6,7:14,15-Bzo₂-10,11-(4-methylbenzene)-[15]-6,8,12,14-tetraene-9,12-N₂-1,5-O₂ (I ₁ ) and zinc complex of 6,7:14,15-Bzo₂-10,11-(4-methylbenzene)-[15]-6,14-diene-9,12-dimethylacrylate-9,12-N₂-1,5-O₂ (I ₂ ) are reported here. The best response was observed with the membrane having a composition of I₂:PVC:o-NPOE:HTAB in the ratio of 6:33:59:2 (w/w; milligram). This electrode exhibited Nernstian slope for thiocyanate ions over working concentration range of 4.4 × 10⁻⁷ to 1.0 × 10⁻² mol L⁻¹ with detection limit of 2.2 × 10⁻⁷ mol L⁻¹. The performance of this electrode was compared with coated graphite electrode (CGE), which showed better response characteristics w.r.t Nernstian slope 59.0 ± 0.2 mV decade⁻¹ activity, wide concentration range of 8.9 × 10⁻⁸ to 1.0 × 10⁻² mol L⁻¹ and detection limit of 6.7 × 10⁻⁸ mol L⁻¹. The response time for CGE and PME was found to be 8 and 10 s, respectively. The proposed electrode (CGE) was successfully applied to direct determination of thiocyanate in biological and environmental samples and also as indicator electrode in potentiometric titration of SCN⁻ ion.     

<Emphasis Type="Italic">S,S,S</Emphasis>-Tris(2-ethylhexyl) phosphorotrithioate as an effective solvent mediator for a mexiletine-sensitive membrane electrode

S,S,S-Tris(2-ethylhexyl) phosphorotrithioate proved to be an effective solvent mediator for constructing a mexiletine-sensitive membrane electrode in combination with an ion-exchanger, sodium tetrakis[3,5-bis(2-methoxyhexafluoro-2-propyl)phenyl]borate. Among a series of phosphorus compounds containing phosphoryl (P=O) groups, this solvent mediator showed the highest sensitivity to mexiletine in phosphate-buffered physiological saline containing 0.15 mol L⁻¹ NaCl and 0.01 mol L⁻¹ NaH₂PO₄/Na₂HPO₄ (pH 7.4), giving a detection limit of 2 × 10⁻⁶ mol L⁻¹ with a slope of 58.8 mV decade⁻¹. This is the best reported detection limit of any mexiletine-sensitive electrode developed to date. Owing to its high selectivity toward inorganic cations, the electrode was used to determine the level of mexiletine in saliva, the monitoring of which is quite effective for controlling the dose of this drug noninvasively. The mexiletine concentrations determined with the mexiletine-sensitive electrode compared favorably with those determined by high-performance liquid chromatography.     

Determination of rutin using a CeO2 nanoparticle-modified electrode

CeO₂ nanoparticles approximately 12 nm in size were synthesized and subsequently characterized by XRD, TEM and UV-vis spectroscopy. Then, a gold electrode modified with CeO₂ nanoparticles was constructed and characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The modified electrode demonstrated strong catalytic effects with high stability towards electrochemical oxidation of rutin. The anodic peak currents (measured by differential pulse voltammetry) increased linearly with the concentration of rutin in the range of 5.0 × 10⁻⁷–5.0 × 10⁻⁴ mol · L⁻¹. The detection limit (S/N = 3) was 2.0 × 10⁻⁷ mol · L⁻¹. The relative standard deviation (RSD) of 8 successive scans was 3.7% for 5.0 × 10⁻⁶ mol · L⁻¹ rutin. The method showed excellent sensitivity and stability, and the determination of rutin in tablets was satisfactory.     

Platinum electrode coated with a bentonite–carbon composite as an environmental sensor for detection of lead

A Pt wire coated with a bentonite–carbon composite in a poly(vinyl chloride) membrane was used for detection of lead. The sensor has a Nernstian slope of 29.42±0.50 mV per decade over a wide range of concentration, 1.0×10⁻⁷ to 1.0×10⁻³ mol L⁻¹ Pb(NO₃)₂. The detection limit is 5.0×10⁻⁸ mol L⁻¹ Pb(NO₃)₂ and the electrode is applicable in the pH range 3.0–6.7. It has a response time of approximately 10 s and can be used at least for three months. The electrode has good selectivity relative to nineteen other metal ions. The practical analytical utility of the electrode is demonstrated by measurement of Pb(II) in industrial waste and river water samples.     

Determination of Selenium in Biological Materials Using an Ion-Selective Electrode

A method was developed for determining selenium with a self-made ion-selective electrode was developed. This electrode was made by using Ag₂Se as electroactive material. Optimal working conditions and interferences were investigated. The electrode exhibits good potentiometric response for Se²⁻ ions over the concentration range from 6 × 10⁻⁷ mol · L⁻¹ to 1 × 10⁻⁴ mol · L⁻¹ with a Nernstian slope of 28 ± 1 mV per decade and a detection limit of about 4.5 × 10⁻⁷ mol · L⁻¹. It was used over six months and exhibits good selectivity and sensitivity towards Se²⁻. The method was applied to determine selenium in biological materials. The recovery ranges between 92% and 105.5%, and the relative standard derivation is less than 3.6% (n = 6).     

Determination of human serum albumin using aurothiomalate as electroactive label

A new electroactive label has been used to monitor immunoassays in the determination of human serum albumin (HSA) using glassy-carbon electrodes as supports for the immunological reactions. The label was a gold(I) complex, sodium aurothiomalate, which was bound to rabbit IgG anti-human serum albumin (anti-HSA-Au). The HSA was adsorbed on the electrode surface and the immunological reaction with gold-labelled anti-HSA was then performed for one hour by non-competitive or competitive procedures. The gold(I) bound to the anti-HSA was electrodeposited in 0.1 mol L⁻¹ HCl at −1.00 V for 5 min then oxidised in 0.1 mol L⁻¹ H₂SO₄ solution at +1.40 V for 1 min. Silver electrodeposition at −0.14 V for 1 min followed by anodic stripping voltammetry were then performed in aqueous 1.0 mol L⁻¹ NH₃–2.0×10⁻⁴ mol L⁻¹ AgNO₃. For both non-competitive and competitive formats, calibration plots in the ranges 5.0×10⁻¹⁰ to 1.0×10⁻⁸ mol L⁻¹ and 1.0×10⁻¹⁰ to 1.0×10⁻⁹ mol L⁻¹ HSA, respectively, with estimated detection limits of 1.5×10⁻¹⁰ mol L⁻¹ (10 ng mL⁻¹) and 1.0×10⁻¹⁰ mol L⁻¹ (7 ng mL⁻¹), respectively, were obtained. Levels of HSA in two healthy volunteer urine samples were also evaluated, using both immunoassay formats.     

Preconcentration and Voltammetric Determination of the Antihypertensive Doxazosin on a C8 Modified Carbon Paste Electrode

 An electrochemical study of the doxazosin oxidative process at carbon paste electrodes using different voltammetric techniques has been carried out. The process is irreversible and controlled by adsorption, giving rise to an oxidation wave around 1.0 V in citric acid-citrate buffer (pH 3.0). A mechanism based on the oxidation of the amine group is postulated. Two methods based on adsorptive stripping (AdS) of doxazosin at the C₈-modified carbon paste electrode (C₈-MCPE), before its voltammetric determination, are studied, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. By means of AdS-DPV and C₈-MCPE, doxazosin can be determined over the 1.0 × 10⁻⁹ to 3.0 × 10⁻⁸ mol L⁻¹ range with a variation coefficient of 2.2% (2.0 × 10⁻⁸ mol L⁻¹) and a limit of detection of 7.4 ×10⁻¹⁰ mol L⁻¹. If AdS-SWV is used, a linear range from 1.0 × 10⁻⁹ to 4.0 × 10⁻⁸ mol L⁻¹ is obtained, the variation coefficient being 2.8% (2.0 × 10⁻⁸ mol L⁻¹, and the limit of detection reached 7.7 × 10⁻¹⁰ mol L⁻¹. The AdS-DPV procedure was applied to the determination of doxazosin in urine and formulations. Received March 13, 1999. Revision December 23, 1999.     

Catalytic adsorptive stripping voltammetric determination of copper(II) on a carbon paste electrode

A catalytic adsorptive stripping voltammetric method for the determination of copper(II) on a carbon paste electrode (PCE) in an alizarin red S (ARS)-K₂S₂O₈ system is proposed. In this method, copper(II) is effectively enriched by both the formation and adsorption of a copper(II)-ARS complex on the PCE, and is determined by catalytic stripping voltammetry. The catalytic enhancement of the cathodic stripping current of the Cu(II) in the complex results from a redox cycle consisting of electrochemical reduction of Cu(II) ion in the complex and subsequent chemical oxidation of the Cu(II) reduction product by persulfate, which reduces the contamination of the working electrode from Cu deposition and also improves analytical sensitivity. In Britton-Robinson buffer (pH 4.56±0.1) containing 3.6×10⁻⁵ mol L⁻¹ ARS and 1.6×10⁻³ mol L⁻¹ K₂S₂O₈, with 180 s of accumulation at −0.2 V, the second-order derivative peak current of the catalytic stripping wave was proportional to the copper(II) concentration in the range of 8.0×10⁻¹⁰ to ∼3.0×10⁻⁸ mol L⁻¹. The detection limit was 1.6×10⁻¹⁰ mol L⁻¹. The proposed method was evaluated by analyzing copper in water and soil.     

Simultaneous determination of silicic acid, Ca, Mg and Al in mineral water and composite tablets by Ion chromatography

Summary A simple, selective and sensitive ion-chromatography method was investigated for simultaneously determining silicic acid, Ca²⁺, Mg²⁺, Al³⁺ and anions (Cl⁻ and NO ₃ ⁻ ) in real samples. It involved a single-column ion-chromatograph with sodium hydroxide-methanol-water eluent and conductometric detection. Cations were converted to complex anions by adding EDTA to the sample solution. A set of well-defined peaks of silicic acid, Ca²⁺, Mg²⁺, Al³⁺, Cl⁻ and NO ₃ ⁻ were obtained. Detection limits using 3.3σ (σ=standard deviation of blank solution) were 1.25×10⁻⁶ M for H₃SiO ₄ ⁻ , 1.32×10⁻⁶ M for Ca²⁺, 1.28×10⁻⁶ M for Mg²⁺, 1.33×10⁻⁶ M for Al³⁺, 1.31×10⁻⁶ M for Cl⁻ and 1.24×10⁻⁶ M for NO ₃ ⁻ . The method was successfully applied to analysis of mineral water and composite tablets.     

PVC membrane sensor based on periodate—Cetylpyridinium ion pair for the potentiometric determination of periodate

A new plasticized membrane sensor has been proposed for the determination of periodate based on periodate-cetylpyridinium ion pair complex. The electrode shows a linear, reproducible and stable potentiometric response with anionic Nernstian slope of 58.1 ± 0.5 mV/decade over a wide range of concentrations 10⁻⁵–10⁻² M and a detection limit of 2.0 × 10⁻⁶ M of IO₄⁻. The membrane exhibits a fast response time of 30–40 s which is independent of pH in the range 2.0–9.0. The selectivity coefficients indicate excellent selectivity for periodate over a large number of anions, e.g. iodide, bromide, chloride, iodate, bromate, nitrate, sulfate, phosphate, thiocyanate, chromate, thiosulfate, sulfite, perchlorate, citrate, acetate, oxalate, and nitrate. The prepared sensor has been successfully used for the determination of periodate (IO₄⁻) and iodate (IO₃⁻) ions with an average recovery of 99.84 ± 0.34% and 98.22 ± 0.43%, respectively. It is also applied to the determination of hydrazine compounds and aminophenol derivatives with an average recovery of 98.66 ± 0.53% and 98.40 ± 0.56%, respectively. Also, the proposed sensor was used for the determination of potassium iodate in iodized table salt and hydrazine in steam boiler feed water and p-aminophenol. The results obtained are in good agreement with those obtained by standard methods.     

Determination of vitamin B<Subscript>1</Subscript> in seawater and microalgal fermentation media by high-performance liquid chromatography with fluorescence detection

A highly sensitive high-performance liquid chromatographic method with fluorescence detection has been developed for determination of vitamin B₁. Vitamin B₁ was converted into a fluorescent compound by treatment with hydrogen peroxide–horseradish peroxidase and the derivative was subsequently analyzed by HPLC on a Waters Spherisorb ODS2 column (250 mm×4.6 mm ID, 5 μm) with 40:60 methanol–pH 8.5 acetate buffer solution as mobile phase and fluorescence detection at 440 nm (with excitation at 375 nm). The calibration graph was linear from 5.00×10⁻¹⁰ mol L⁻¹ to 5.00×10⁻⁷ mol L⁻¹ for vitamin B₁ with a correlation coefficient of 0.9991 (n=9). The detection limit was 1.0×10⁻¹⁰ mol L⁻¹. The method was successfully used for determination of vitamin B₁ at pg mL⁻¹ levels in microalgal fermentation media and seawater after solid-phase extraction. Recovery was from 89 to 110% and the relative standard deviation was in the range 1.1 to 4.3%.     

Determination of dopamine in rat striatum by microdialysis and high-performance liquid chromatography with electrochemical detection on a functionalized multi-wall carbon nanotube electrode

High performance liquid chromatography coupled with microdialysis sampling and electrochemical detection (HPLC–ECD) has been used to determine dopamine (DA). In the HPLC–ECD a multi-wall carbon nanotube electrode chemically modified with carboxyl groups (MWNT-COOH CME) was used as the working electrode for determination of DA. The results indicated that the MWNT-COOH CME enabled efficient electrocatalytic oxidation of DA with relatively high sensitivity and stability and long life. Peak currents for dopamine were linearly dependent on concentration in the range 5.0×10⁻⁹ to 5.0×10⁻⁵ mol L⁻¹ and the calculated detection limit (S/N=3) was 2.5×10⁻⁹ mol L⁻¹. The method had been successfully used to measure dopamine in rat striatal microdialysate. To study the physiological effect of nitric oxide (NO) on striatal release of DA, 0.5 mmol L⁻¹ sodium nitroprusside (SNP) was a continuously perfused into rat striatum. This resulted in a 46% increase in DA basal level.     

Trace determination of clenbuterol with an MWCNT-Nafion nanocomposite modified electrode

A method for the determination of trace clenbuterol is described. Multi-walled carbon nanotubes (MWCNTs)-Nafion composite was used to modify the glassy carbon electrode (GCE). The modified electrode showed high sensitivity and good selectivity for clenbuterol detection. It offered a linear range of 1.0 × 10⁻⁹–1.0 × 10⁻⁶ mol · L⁻¹ with a detection limit of 5.0 × 10⁻¹⁰ mol · L⁻¹ in pH = 1.2 solution. The oxidation mechanism of clenbuterol on the electrode was also investigated. Correspondence: Xiao-Ya Hu, Department of Chemistry, Yang Zhou University, Yang Zhou, Jiang Su, P.R. China     

Study and Application of Electrochemical Behavior of Calcium-ARS on a Mercury Film Electrode

A sensitive complex absorptive wave of Ca-ARS was obtained by using differential pulse voltammetry when a mercury film glass carbon electrode was immersed in 0.1 mol L⁻¹ KOH and 4.5×10⁻⁴ mol L⁻¹ ARS solution. The peak potential obtained was −1.17 V (vs Ag-AgCl). The peak current was proportional to the concentration of calcium in the range of 5.0×10⁻⁸−4.2×10⁻⁵ mol L⁻¹. The detection limit was 2.0×10⁻⁸ mol L⁻¹. This method was applied successfully to determining traces of calcium in blood serum. The electrochemical behavior of the system was also studied by cyclic voltammetry, and the experiment results showed that the electrode process was an irreversible absorptive with two electrons participating. Translated from Journal of Beijing Normal University (Natural Science Edition), 2005, 41(2) (in Chinese)     

Application of cadmium sulfide nanoparticles as oligonucleotide labels for the electrochemical detection of NOS terminator gene sequences

A mercaptoacetic acid (MAA)-modified cadmium sulfide (CdS) nanoparticle was synthesized in aqueous solution and used as an oligonucleotide label for the electrochemical detection of nopaline synthase (NOS) terminator gene sequence. The carboxyl groups on the surface of the CdS nanoparticle can be easily covalently linked with NH₂-modified NOS oligonucleotide probe sequences. The target ssDNA sequence was fixed onto the electrode surface by covalently linking to a mercaptoethanol self-assembled gold electrode, and the DNA hybridization of target ssDNA with probe ssDNA was accomplished on the electrode surface. The CdS nanoparticles anchored on the hybrids were dissolved in the solution by the oxidation with HNO₃ and further detected by a sensitive differential pulse anodic stripping voltammetric method. The detection results can be used for monitoring the hybridization, and the NOS target sequence was satisfactorily detected in the approximate range from 8.0 × 10⁻¹² to 4.0 × 10⁻⁹ mol L⁻¹ with a detection limit of 2.75 × 10⁻¹² mol L⁻¹ (3σ). The established method extended the nanoparticle-labeled electrochemical DNA analysis to genetically modified organisms (GMOs) specific sequence samples with higher sensitivity and selectivity.     

FAD-modified SiO2/ZrO2/C ceramic electrode for electrocatalytic reduction of bromate and iodate

SiO₂/ZrO₂/C carbon ceramic material with composition (in wt%) SiO₂ = 50, ZrO₂ = 20, and C = 30 was prepared by the sol–gel-processing method. A high-resolution transmission electron microscopy image showed that ZrO₂ and the graphite particles are well dispersed inside the matrix. The electrical conductivity obtained for the pressed disks of the material was 18 S cm⁻¹, indicating that C particles are also well interconnected inside the solid. An electrode modified with flavin adenine dinucleotide (FAD) prepared by immersing the solid SiO₂/ZrO₂/C, molded as a pressed disk, inside a FAD solution (1.0 × 10⁻³ mol L⁻¹) was used to investigate the electrocatalytic reduction of bromate and iodate. The reduction of both ions occurred at a peak potential of −0.41 V vs. the saturated calomel reference electrode. The linear response range (lrr) and detection limit (dl) were: BrO₃ ⁻, lrr = 4.98 × 10⁻⁵–1.23 × 10⁻³ mol L⁻¹ and dl = 2.33 μmol L⁻¹; IO₃ ⁻, lrr = 4.98 × 10⁻⁵ up to 2.42 × 10⁻³ and dl = 1.46 μmol L⁻¹ for iodate.     

Electrogeneration of polyluminol and chemiluminescence for new disposable reagentless optical sensors

A performant reagentless electrochemiluminescent (ECL) detection system for H₂O₂ is presented, based on an electropolymerized polyluminol film prepared under near-neutral conditions. Such an original polyluminol electrodeposition is reported for the first time and on a screen-printed electrode (SPE) surface. Electropolymerized luminol acts as an active luminophore of the electrochemiluminescent reaction, as the monomer does. Polymerization conditions have been optimized in order to obtain the best ECL responses to H₂O₂. By performing electrodeposition in a potentiostatic mode, at 425 mV vs. Ag|AgCl, in 0.1 mol L⁻¹ phosphate/0.1 mol L⁻¹ KCl pH 6 and 1 mmol L⁻¹ luminol, with a total charge of 0.5 mC, the linear range for H₂O₂ detection extends from 7.9 × 10⁻⁸ mol L⁻¹ to 1.3 × 10⁻³ mol L⁻¹. Such performant disposable reagentless easy-to-use miniaturized systems based on SPEs should be applicable to the electrochemiluminescent detection of many oxidase-substrate compounds. Figure An original polyluminol electrodeposition process on a screen-printed electrode surface is reported for the first time. The polymeric structure is demonstrated to behave as an electrochemiluminescent luminophore, allowing disposable reagentless easy-to-use optical sensors for hydrogen peroxide detection to be designed.     

Chemometrics to evaluate the quality of water sources for human consumption

Multilayer films of multiwalled carbon nanotubes (MWNTs) were homogeneously and stably assembled on a glassy carbon (GC) electrode using the layer-by-layer (LBL) method based on electrostatic interaction between MWNTs (negatively charged) and a biopolymer chitosan (CHIT) (positively charged). Scanning electron microscopy (SEM) image of the resulting {CHIT/MWNTs}₉ film indicated that the substrate was mostly covered with MWNTs in the form of small bundles or single nanotubes. The multilayer film was used to study the electrocatalytic oxidation of NADH. The assembled {CHIT/MWNTs}₉/GC electrode could decrease the oxidation overpotential of NADH by more than 350 mV. The {CHIT/MWNTs}₉/GC electrode exhibited a wide linear response range of 8 × 10⁻⁷ to 1.6 × 10⁻³ mol · L⁻¹ with a correlation coefficient of 0.997 for the detection of NADH. The response time and detection limit (S/N = 3) were determined to be 3 s and 0.3 × 10⁻⁶ mol · L⁻¹, respectively. Another attractive characteristic was that the method was simple and the assembled {CHIT/MWNTs}₉/GC electrode was highly stable.     

Electrocatalytic oxidation of nitric oxide at nano-TiO2/Nafion composite film modified glassy carbon electrode

A novel nanocrystalline TiO₂ (nano-TiO₂) and Nafion composite film modified glassy carbon electrode has been developed for the determination of nitric oxide (NO) radical in an aqueous solution. This modified electrode can be employed as a NO sensor with a low detection limit, fast response, high sensitivity and selectivity. Two apparent anodic peaks were observed at 0.67 and 0.95 V at the nano-TiO₂ modified glassy carbon electrode by differential pulse voltammetry (DPV). After further modification with a thin film of Nafion, which was capable of preventing some anionic interference such as nitrite and ascorbic acid, only one peak appeared and the peak current enhanced greatly. The chronocoulometric experimental results showed NO was oxidized by one-electron transfer reaction at the composite film modified electrode. The amperometric responses increased linearly with the concentrations of NO ranging from 3.6×10⁻⁷ mol/L to 5.4×10⁻⁵ mol/L. The detection limit was estimated to be 5.4×10⁻⁸ mol/L. In this sensor system, the modification film provides complete selectivity for NO over nitrite anions (NO₂⁻).