Immobilization of Hexacyanoferrate on a Gold Self-Assembled Monolayer, and its Application as a Sensor for Ascorbic Acid

Hexacyanoferrate (II/III) (HCF) was immobilized on a gold electrode modified with cysteamine (CSTE). The Au/CSTE/HCF/PLL electrode was prepared with layer-by-layer (LBL) technique with HCF and poly-d-lysine (PLL). The Au/CSTE/HCF/PLL electrode presented the electrocatalytic activity for ascorbic acid oxidation. The maximum electrocatalytic current was reached at 0.28 V vs SCE in 0.01 mol L⁻¹ TRIS buffer, at pH 7.0. The Au/CSTE/HCF/PLL electrode response was stable under various oxidation–reduction cycles in TRIS medium, showing that the system is very stable. The solution pH has no effect on the anodic peak potential and anodic peak current in the range from 4 up to 10. The intensity of the anodic peak current varied with the concentration of ascorbic acid from 1 up to 910 μmol L⁻¹, with a sensitivity of 62.9 nA cm⁻² L μmol⁻¹, a detection limit of 0.65 μmol L⁻¹ and a quantification limit of 2.2 μmol L⁻¹. The developed sensor was successfully applied for ascorbic acid determination in pharmaceutical samples. The results compared to those obtained with a reference method were statistically the same with 95% of confidence level.     

Application of Nb2O5–SiO2 in Pre-Concentration and Determination of Copper and Cadmium by Flow System with Flame Atomic Absorption Spectrometry

 The use of niobium (V) oxide, chemically adsorbed on silica gel surface (Nb₂O₅–SiO₂), as an adsorbent in a pre-concentration system for copper (II) and cadmium (II) determination was proposed. The procedure is based on the large ion-exchange capacity for the adsorption of copper (II) and cadmium (II) ions on the mini-column packed with Nb₂O₅–SiO₂, followed by elution with 2.0 mol L⁻¹ nitric acid and determination by flame atomic absorption spectrometry. Chemical and flow variables were optimized. The results demonstrated that the sample solutions containing copper (II) or cadmium (II) in a concentration range of 3.0 to 600.0 μg L⁻¹ and 3.1 to 100.0 μg L⁻¹ respectively, in a solution of pH 5.0 could be determined using a pre-concentration time of 2 min. The enrichment factor when using a sample volume of 10.2 mL and 2 min of pre-concentration was 17.5 and 20.3 for copper (II) and cadmium (II), respectively. The limit of detection for copper (II) and cadmium (II) was 0.5 μg L⁻¹ and 1.0 μg L⁻¹, respectively. The relative standard deviation (RSD) was lower than 1.4% for copper (II) and cadmium (II) when using a concentration of 25.0 μg L⁻¹ for both metals. The method was tolerant to other ions usually present in water samples. Good accuracy was obtained by the analysis of water reference material and environment samples. Correspondence: Universidade Federal de Santa Catarina, Departamento de Química, Florianópolis SC, Brazil. e-mail: carasek@qmc.ufsc.br Received July 16, 2002; accepted October 25, 2002     

Microdialysis sampling and chemiluminescence detection for in vivo and real-time study of the lead metabolism in rabbit blood

The chemiluminescence (CL) system K₂MnO₄-luminol is shown to be useful for the determination of lead(II). The method is based on the catalytic effect of Pb(II) on the CL reaction. The linear range was 3 × 10⁻³–9 × 10⁻¹ mg L⁻¹ (r = 0.9971) and the relative standard deviation (R.S.D.) for 5 × 10⁻² mg L⁻¹ Pb(II) measurement was 0.7% (n = 11). The detection limit was 3 × 10⁻⁴ mg L⁻¹ (3σ) Pb(II). Based on this, an in vivo, on-line, real-time analytical system for monitoring the metabolism of free lead(II) in rabbit blood was developed. A microdialysis probe, implanted in the vein of a rabbit, was perfused with perfusate at a flow rate of 5 μL min⁻¹. The concentration of free lead(II) in the dialysate was determined on-line with a flow-injection CL system. This system included microdialysis sampling, on-line separation and chemiluminescence detection. The concentration-time curve of lead(II) was in accordance with the one-compartmental open model, T_1/2 (elimination half-life), T_max (peak time) and C_max (peak concentration) were 37.77 min, 85.20 min and 0.137 mg L⁻¹, respectively.     

Cloud point extraction procedure for flame atomic absorption spectrometric determination of lead(II) in sediment and water samples

The conditions for cloud point extraction of lead(II) from aqueous solutions were investigated and optimized. The procedure is based on the separation of Pb(II) – brillant cresyl blue (BCB) complexes into the micellar media by adding the surfactant Triton X-114. After phase separation, the surfactant-rich phase was dissolved with 1 mol L⁻¹ HNO₃ in ethanol and diluted with 1 mol L⁻¹ HNO₃ solution before lead was determined by flame atomic absorption spectrometry. Optimization of the pH, ligand and surfactant quantities, incubation time, temperature, viscosity, sample volume, and interfering ions was performed. The effects of the matrix ions were also examined. The detection limits for three times the standard deviations of the blank for lead were 7.5 μg L⁻¹ for water samples and 0.33 μg g⁻¹ for sediment samples. The validity of cloud point extraction was checked by employing certified reference samples of Lake Sediment IAEA-SL-1 and Sewage Sludge BCR-CRM 144R. The procedure was applied to natural waters and sediment samples with satisfactory results (recoveries >95%, relative standard deviations <6.4%).     

A novel kinetic determination of nitrite based on the perphenazine-bromate redox reaction

An extremely sensitive and selective kinetic method was developed for the determination of trace levels of nitrite based on its catalytic effect on the oxidation of perphenazine (PPZ) with bromate in a phosphoric acid medium. The reaction rate was monitored spectrophotometrically by tracing the formation of the red-colored oxidized product of PPZ at 525 nm within 30 sec of mixing. The optimum reaction conditions were 4.0 μmol L⁻¹ PPZ, 0.4 mol L⁻¹ H₃PO₄ and 30 mmol L⁻¹ bromate at 25 °C. Using the recommended procedure, nitrite could be determined with a linear calibration graph up to 4.50 ng mL⁻¹ and a detection limit of 0.07 ng mL⁻¹. The method was conveniently applied to the determination of nitrite in samples of rain, polluted well and formulated waste waters. Moreover, the published kinetic spectrophotometric methods for nitrite determination are reviewed.     

Selective Determination of Trace Mercury (II) after Preconcentration with 4-(2-Pyridylazo)-Resorcinol-Modified Nanometer-Sized SiO2 Particles from Sample Solutions

A rapid, selective method that utilize 4-(2-Pyridylazo)-resorcinol (PAR)-modified nanometer SiO₂ (nanometer SiO₂–PAR) as a new solid-phase extractant for preconcentration of trace mercury (II) has been developed. The adsorption property of nanometer SiO₂–PAR for metal ions was studied by selectively extracting different metal ions from aqueous solutions. The results revealed an excellent affinity of the nanometer SiO₂–PAR for mercury (II) in presence of interfering metal ions at pH 4. The main parameters of solid-phase extraction such as shaking time, elution and sample dilution effect were studied. The extractant shows rapid kinetic sorption, and the adsorption equilibrium of mercury (II) on nanometer SiO₂–PAR was achieved in less than 2 min. The adsorbed mercury (II) was easily eluted by 4 mL of 6 mol L⁻¹ HCl. The maximum preconcentration factor was 50. The maximum static adsorption capacity was 276 μmol g⁻¹ at pH 4. The detection limit (3σ) was 0.43 μg L⁻¹ for cold vapor atomic absorption spectrometry (CVAAS), and the relative standard deviation of the eight replicate determinations was 2.4% for the determination of 2.0 μg of Hg(II) in 100 mL water sample. The method was applied to the determination of trace mercury (II) in sample solutions with satisfactory results.     

Determination of Nickel in Fuel Ethanol Using a Carbon Paste Modified Electrode Containing Dimethylglyoxime

A mercury-free electrode chemically modified with carbon paste containing dimethylglyoxime was used for determination of nickel in fuel ethanol. The instrumental parameters and composition of the modified paste were optimized. The analytical curve for nickel determination from 5.0 × 10⁻⁹ to 5.0 × 10⁻⁷ mol L⁻¹ was obtained using 25 min of accumulation time. The detection limit and amperometric sensitivity obtained for this method were 2.7 × 10⁻⁹ mol L⁻¹ and 5.2 × 10⁸ μA mol⁻¹ L, respectively. The values for nickel concentration in four commercial samples of fuel ethanol were obtained in the range of 1.1 × 10⁻⁸ to 6.9 × 10⁻⁸ mol L⁻¹. A comparison to graphite furnace atomic absorption spectrometry (GFAAS) was performed for nickel determination in commercial samples of ethanol.     

Use of Benzoylthiourea Immobilized on Silica Gel for Separation and Preconcentration of Uranium(VI)

Benzoylthiourea immobilized on silica gel was prepared by two-step post-synthesis modification. The capacity of the chelating silica gel, which was characterized by FTIR, was 3.21 mmol · g⁻¹. The separation and enrichment of uranium(VI) from solutions was investigated. Effective extraction conditions were optimized in both batch and column methods prior to determination by spectrophotometry using arsenazo(III). The optimum pH range for quantitative adsorption is 4–7. Quantitative recovery of U(VI) was achieved by stripping with 0.1 mol · L⁻¹ HCl. The sorption capacity of modified silica gel was 0.85 mmol · g⁻¹ uranium(VI). Recovery of U(VI) was 99.1 ± 2.3% with a detection limit of 2 μg · L⁻¹. The preconcentration factor was 250, and the relative standard deviation was 1.53% for a 1 μg · L⁻¹ U(VI) solution. The method was used for the determination of uranium in synthetic samples and a soil sample.     

Indirect determination of free cyanide in water and industrial waste water by flow injection-atomic absorption spectrometry

A simple and rapid flow injection system is proposed for indirect determination of cyanide by flame atomic absorption spectrometry. It consists of a microcolumn of immobilized salen (N,N′-bis(salicylidene)ethylenediamine) on sodium dodecyl sulfate (SDS)-coated alumina saturated with silver ion and a carrier of dilute solution of sodium hydroxide (10⁻⁵ mol L⁻¹). The micro-column was located between the injection valve and nebulizer of atomic absorption spectrometry. Injection of 250 μL of aqueous cyanide standard or sample solution at pH range of 9–11 cause elution of silver as silver cyanide complexes, which was then measured by flame atomic absorption spectrometry. The absorbance was proportional to the concentration of cyanide in the sample. The graph of absorbance (as peak height) vs. cyanide concentration was linear over the concentration range of 0.1–10 mg L⁻¹ of cyanide, and the detection limit was 0.06 mg L⁻¹. The relative standard deviation at 1 and 3 mg L⁻¹ of cyanide concentration were 4.1 and 4.7%, respectively. The method was successfully applied to determination of cyanide in water and industrial waste waters, and the accuracy was examined through independent analysis by accepted method of pyridine-barbituric acid.     

Rapid, sensitive and selective spectrophotometric determination of phosphate as an ion associate of 12-molybdophosphate with Astra Phloxine

A highly sensitive and selective reaction of 12-molybdophosphate with the polymethine dye Astra Phloxine has been used for the spectrophotometric determination of phosphate. If the concentration of phosphate is less than 1 μmol L⁻¹, supersaturated solutions of ion associate (IA) are stable without the use of a surfactant. Under these conditions, a new band appears in the absorption spectrum at 574 nm. The color of the IA develops immediately after mixing of reagents and remains constant over several hours. The molar absorptivity of the IA is 1.54 × 10⁵ L mol⁻¹ cm⁻¹. The calibration graph is linear between 0.02 and 0.8 μmol L⁻¹ of phosphate. The limit of detection is 7 nmol L⁻¹. Phosphate was determined in pure chemicals and water samples, including Dead Sea water.     

Online preconcentration system for determining ultratrace amounts of Cd in vegetal samples using thermospray flame furnace atomic absorption spectrometry

A system has been developed for online preconcentration and determination of Cd using thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). It is based on the solid-phase extraction of Cd in an Amberlite XAD-2 minicolumn loaded with 2-(2-thiazolylazo)-5-dimethylaminophenol (TAM), and the metal ion is eluted with 1 mol L⁻¹ hydrochloridric acid, followed by its determination. The online system allows determining Cd with a detection limit of 8.0 ng L⁻¹ and a quantification limit of 25.0 ng L⁻¹. The precision (repeatability), calculated as the relative standard deviation (% RSD) in sample solutions containing 0.5 and 3.0 μg L⁻¹ of Cd, was 6.1 and 4.5%, respectively. The preconcentration factor obtained was 24. The system’s accuracy was confirmed by analyzing the following certified reference materials (CRMs): Rice flour NIES 10b, Apple leaves NIST 1515 and Orchard leaves NBS 1571. This procedure was applied to the determination of Cd in cabbage and powdered guarana samples.     

Flow injection on-line hydrophobic sorbent extraction for flame atomic absorption spectrometric determination of cadmium in water samples

A flow injection system was developed for on-line sorbent extraction preconcentration and flame atomic absorption spectrometric determination of cadmium in natural water samples. The non-charged cadmium complex with diethyl-dithiophosphate (DDPA) was formed on-line in 0.1 mol L⁻¹ HNO₃ and retained on the hydrophobic poly-chlorotrifluoroethylene (PCTFE) sorbent material. The adsorbed complex was eluted with isobutyl methylketone (IBMK) and injected directly into the nebulizer via a flow compensation unit. All major chemical and flow parameters affecting the complex formation adsorption and elution as well as interference were studied and optimized. By processing 2.4 mL of sample, the enhancement factor was 39 and the sampling frequency was 50 h⁻¹. For 30 s preconcentration time the detection limit was 0.3 μg L⁻¹ and the relative standard deviation at 5.0 μg L⁻¹ Cd concentration level was 2.9%. The calibration curve was linear in the range 0.8–40.0 μg L⁻¹. The accuracy of the method was estimated by analyzing a certified reference material NIST-CRM 1643d (Trace elements in water). Good recoveries were obtained for spiked natural-water and waste-water samples. Correspondence: Aristidis N. Anthemidis, Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, GR-Thessaloniki 54124, Greece     

Speciation Analysis of Inorganic Tin (Sn(II)/Sn(IV)) by Graphite Furnace Atomic Absorption Spectrometry Following Ion-Exchange Separation

A new method based on anion exchange resin separation and graphite furnace atomic absorption spectrometry (GFAAS) detection is proposed for the determination of inorganic tin species. The result showed that Sn(IV) was quantitatively retained on the resin when [HCl] = 9.0 mol · L⁻¹, but Sn(II) could not be adsorbed on the resin under the same condition. Thus, a separation of Sn(II) and Sn(IV) has been realized. When the concentration of NaOH solution was between 2.0–7.0 mol · L⁻¹, Sn(IV) that adsorbed on the resin could be eluated from the resin completely. Meanwhile, under the atmosphere and the nitrogen states, the translation between Sn(II) and Sn(IV) was investigated. Under the optimal conditions, the detection limit of Sn(IV) is 0.40 μg · L⁻¹ with RSD of 2.3% (n = 5, c = 2.0 μg · L⁻¹). The proposed method was applied to the speciation analysis of tin in different water samples and the recovery of total Sn was in the range of 98.7–101.7%. In order to verify the accuracy of the method, a certified reference water sample was analyzed and the results obtained were in good agreement with the certified value.     

Determination of chromium(VI) and total chromium in water by in-electrode coulometric titration in a porous glassy carbon electrode

Chromium(VI) is determined through its direct electrochemical reduction in the bulk of a porous glassy carbon electrode. An electrode filled with the acidified sample and Cr(VI) is reduced by means of a constant current whereas the potential of the electrode is monitored. The limits of detection and quantification were found to be 1.9 and 6.0 μg · L⁻¹, resp. The linear range, repeatability and reproducibility were found to be 5–500 μg · L⁻¹, 1.2, and 1.8%, resp. The influence of Fe(III), Ca(II), Mg(II), sulphates, nitrates, humic acids and surfactants was investigated. Total chromium was measured after chemical oxidation of Cr(III) to chromate by permanganate. The method was applied to analyses of water samples.     

Electrochemical determination of malachite green using a multi-wall carbon nanotube modified glassy carbon electrode

A multi-wall carbon nanotube (MWNT) film-modified electrode is described for the determination of malachite green (MG). The electrochemical profile of MG was examined using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), suggesting that the MWNT film facilitates the electron transfer of MG in terms of a potential shift and then significantly enhances the oxidation peak current of MG. The experimental parameters, such as supporting electrolyte, thickness of MWNT film, scan rate and accumulation time, were optimized. Consequently, a sensitive and convenient electrochemical method is proposed for the determination of MG. The oxidation peak current is proportional to the concentration of MG over the range from 5.0 × 10⁻⁸ to 8.0 × 10⁻⁶ mol L⁻¹ obeying the following equation: i_p = 0.09 + 1.19 × 10⁷ C (r = 0.995, i_p in μA, C in mol L⁻¹). The detection limit is 6.0 × 10⁻⁹ mol L⁻¹ (signal to noise = 3) after 5 min of accumulation. Moreover, this method possesses good reproducibility (RSD is 5.6%, n = 8) as well as long-term stability. Finally, the new method was employed to determine MG in fish samples. Correspondence: W. Huang, Department of Chemistry, Hubei Institute for Nationalities, Enshi 445000, P.R. China     

A Fast Sequential Injection Analysis System for the Simultaneous Determination of Ammonia and Phosphate

A flow system is described that is based on sequential injection analysis (SIA) and is suitable for the fast determination of ammonia and phosphate in river and marine waters. It is applicable to nutrient mapping in inhomogeneous coastal areas like the Wadden Sea, and was optimised on several cruises on the North Sea. The high sample throughput of 120 samples per analyte per hour and the low reagent consumption (ammonia: 62.5 μL; phosphate: 60 μL) were achieved using a home made programme written in the python programming language. The determination of free reactive phosphate is based on the reaction of phosphate with acidic molybdate to phosphomolybdate which forms nonfluorescent ion pairs with rhodamine 6G. The remaining rhodamine fluorescence is detected at 550 nm with an excitation at 470 nm. Ammonia is determined with the help of o-phthaldialdehyde and sodium sulfite. At 85 °C and a reaction time of at least one minute a fluorescent species (exc. 365 nm, em. 425 nm) is formed. The detection limits are (3σ) 0.3 μmol L⁻¹ for phosphate and 1 μmol L⁻¹ for ammonia.     

Highly selective determination of palladium(II) after preconcentration using Pd(II)-imprinted functionalized silica gel sorbent prepared by a surface imprinting technique

A novel Pd(II)-imprinted amino-functionalized silica gel sorbent was prepared with the help of a surface-imprinting technique for the preconcentration and separation of Pd(II) prior to its determination by inductively coupled plasma atomic emission spectrometry. Compared to the traditional solid sorbents and non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had a higher adsorption capacity and selectivity for Pd(II). The maximum static adsorption capacity of the imprinted and non-imprinted sorbent for Pd(II) was 26.71 mg g⁻¹ and 10.13 mg g⁻¹, respectively. The relative selectivity factor (α_r) of Pd(II)/Zn(II), Pd(II)/Au(III), Pd(II)/Ru(III), Pd(II)/Rh(III), Pd(II)/Pt(IV), Pd(II)/Ir(III), Pd(II)/Fe(III) and Pd(II)/Zn(II) is 39.0, 60.2, 92.0, 85.0, 50.0, 58.0 and 45.0, respectively. The detection limit (3σ) of the method is 0.36 μg L⁻¹. The relative standard deviation was 3.2% for eight replicate determinations of 10 μg of Pd²⁺ in 200 mL water sample. The method was validated by analyzing a standard reference material, and the results obtained were in good agreement with the standard values. The method was also applied to the determination of trace palladium in geological samples with satisfactory results.     

Fluorometric determination of DNA using nano-SiO2 particles as an effective dispersant and stabilizer for acridine orange

A sensitive fluorometric method for the determination of ctDNA (calf thymus DNA) is presented. It has good selectivity and sensitivity and uses nano-SiO₂ particles as an effective dispersant and stabilizer for acridine orange (AO). Compared to resonance light scattering (RLS) and the conventional method that uses organic dyes as fluorescence probe, the new method is more tolerant towards coexisting foreign substances and also more stable. With 20 mg nano-SiO₂ particles, 10 μmol L⁻¹ AO, at pH 8.01 and an ionic strength of 0.02 mol L⁻¹, the interaction of AO with nano-SiO₂ and ctDNA results in fluorescent signal enhancement. The extent of enhancement was in good proportion to the concentration of ctDNA at excitation/emission wavelengths of 490/523 nm, respectively. The calibration curve was linear over 0.66–55.60 μg mL⁻¹. The determination limit (3σ) was 15 μg mL⁻¹. The method was applied to the determination of ctDNA in synthetic samples with satisfactory results.     

Determination of As(III) and total as in water by graphite furnace atomic absorption spectrometry after electrochemical preconcentration on a gold-plated porous glassy carbon electrode

Arsenic(III) was preconcentrated in a flow-through electrochemical cell on a gold coated porous carbon electrode. On stripping, arsenic was eluted with diluted nitric acid and determined off-line by GF AAS. The deposition and stripping steps were optimized. The limit of detection and limit of quantification were found to be 1.9 μg L⁻1 and 6.4 μg L⁻¹, respectively. The repeatability and reproducibility were found to be 5.3 % and 9.3 %, respectively. Total arsenic was determined after a microwave assisted chemical reduction of As(V) to As(III) making the procedure suitable for speciation analysis. The method was applied in analysis of water samples.     

Preconcentration of Cd(II) and Cu(II) by solid phase extraction on cyanopropyl modified silica columns using 1,10-phenanthroline as the complexing agent

We describe the solid-phase extraction for the preconcentration and determination of Cd(II) and Cu(II) aqueous samples by inductively coupled plasma optical emission spectrometry. The preconcentration of analytes is accomplished by retention of their chelates with 1,10-phenanthroline in aqueous solution on a solid phase containing cyanopropylsilane bonded to silica gel in a column. The preconcentration factor is 80 for the cadmium ions and 120 for the copper ions with relative standard deviations of between 0.5 and 1.5%. The limits of detection (defined as “3 s” where “s” is the standard deviation of the blank determination) are 0.18 and 0.073 μg L⁻¹ for Cd(II) and Cu(II), respectively, and the corresponding limits of quantification (6 s) are 0.36 and 0.15 μg L⁻¹, respectively. As a result, a simple method was created for simultaneous preconcentration and determination of the metals in reference material and in plant sample material. Correspondence: Bożena Puzio, Institute of Chemistry, Silesian University, 40-006 Katowice, Poland