Investigations on adsorption potentiometry Part I. Derivative adsorption chronopotentiometry of the iron(III)-2-(5′-bromo-2′-pyridylazo)-5-diethylaminophenol system

An electroanalytical method, based on derivative chronopotentiometry of the iron complex with 2-(5′-bromo-2′- pyridylazo)-5-diethylaminophenol (5-Br-PADAP) accumulated adsorptively on the surface of a hanging mercury drop electrode, for determining trace iron in food has been developed. The dependences of the peak height on the dt/dE vs. E curve on the preconcentration time, preconcentration potential and electrode area are discussed. Optimum experimental conditions include 0.005 mol 1^?1 NH₃NH₄Cl, 2 × 10^?7 mol 1^?1 5-Br-PADAP and a preconcentration potential of ?0.40 V (vs. SCE). Under these conditions, the detection limit and the linear range are 2 × 10^?9 and 6.7 × 10^?9?1.7 × 10^?7 mol 1^?1, respectively. The relative standard error of the method is 1.5% for 6.7 × 10^?8 mol 1^?1 Fe(III). The method was applied to samples of microwave digested food.     

Spectrofluorimetric method for the determination of 1-(3,4-dimethoxyphenyl)-4-methyl-5-ethyl-7,8-dimethoxy-5H-2,3-benzodiazepine (tofisopam)

The method described is based on the reaction of tofisopam in dimethyl sulphoxide in the presence of an alkali metal hydroxide at 90–100°C to give 1-ethyl-4-(3,4-dimethoxyphenyl)-6,7-dimethoxy-2-naphthol, which shows intensive fluorescence. The method is suitable for the determination of 5 × 10^?8?5 × 10^?5 g ml^?1 of tofisopam.     

Investigations on Adsorption Potentiometry Part V Derivative Adsorption Chronopotentiometry of Beryllium(II)-4-[(4-diethylamino-2-hydroxypheanyl)-azo]-5-hydroxy-naphthalene-2,7-disurphonic Acid System

Abstract

An electroanalytical methood, based on derivative chronopotentiometry of the complex of beryllium(II) with 4-[(4-diethylamino-2-hydroxy-phenyl)-azo]-5-hydroxy-naphthalene-2,7-disurphonic acid (Beryllon II) accumulated adsorptively on the surface of a hanging mercury drop electrode, has been developed for determining trace beryllium in food. The dependences of the peak height on the dt/dE vs. E curve on the pre-concentration time, preconcentration potential and the constant reducing current are discussed. In 0.15 mol/1 NH_s+0.05 mol/1 NH₄Cl, 4×10^?7 mol/l Beryllon II, and at a preconcentration potential of -0.30 V (ve. SCE), the limit of detection and linear range are 1 × l0^?10 mol/l and 3 × 10^?10 -2 × l0^?7 mol/l, Iwpectively. The relative standard error of the method is 2.3% for 6 × 10^?8 mol/l Be(II). The method WBB applied to samples of food. The electrode procees hae been diecueeed.     

Bis[2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulpho propylamino)phenolato]cobaltate(III) as a counter ion for the extraction and spectrophotometric determination of long-chain quaternary ammonium salts and tertiary alkylamines in the presence of each other

The singly charged complex anion bis[2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulphopropylamino)phenolato]cobaltate(III) is intensely purple-violet and is stable over the pH range 1–13. Its absorption spectrum remains the same over this pH range. At pH2, it forms extractable ion pairs with long-chain quaternary ammonium ions and protonated alkylamines. Only the quaternary ammonium ions are extracted into chloroform at pH 11, hence separate extractions allow both types to be determined. The absorbance of the organic phase is measured at 594 nm. The apparent molar absorptivity is 7.0 × 10⁴ l mol^?1 cm^?1. Calibration graphs for zephiramine, benzethonium and hexadecylpyridinium ions are linear over the range 0.1–2 × 10^?6 M. The only interference found was from anionic surfactants. The method is applied to hair and fabric conditioners.     

Voltammetric determination of mercury(II) using a modified pencil graphite electrode with 4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl

A sensitive and selective method for determination of mercury(II) with “4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl (TKO)-modified pencil graphite electrode” was developed. All factors affecting determination process were optimized. Differential pulse voltammetry with 4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl-modified electrode showed a linear response between 1.0 × 10^?5 and 1.0 × 10^?3 M (R ² = 0.9994). The detection limit of this electrode was found as 5.85 × 10^?7 M (S/N = 3). The effects of different cations on the determination of mercury(II) were investigated and found that modified electrode is highly selective. The developed method was applied for mercury determination in different water samples.     

Structure and properties of 2-[(E)-2-(4-dipropylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3H-indolium chloride

The structure of styryl dye, 2-[(E)-2-(4-dipropylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3H-indolium chloride (I), was investigated using methods such as UV-VIS, fluorescence spectroscopy, and NMR (¹H, ¹³C, APT, HMQC, COSY) and also by examining its electrochemical properties. A study of the acid-base properties revealed the existence of three different forms of the dye. The mechanisms of protolysis and hydrolysis are discussed. The reagent exists in a reactive single-charged form I ⁺ over a wide range of acidity (pH 4–11). The optimum analytical wavelength of the singlecharged form is 550 nm, where the molar absorptivity is 5.51 × 10⁴ L mol^?1 cm^?1. The values of the optimum analytical wavelength and molar absorptivity of the protolysed and hydrolysed forms are: λ _max(I-H²⁺) = 380 nm, ?(I-H²⁺) = 2.01 × 10⁴ L mol^?1 cm^?1; λ _max(I-OH) = 320 nm, ?(I-OH) = 1.12 × 10⁴ L mol^?1 cm^?1. A theoretical study of the spectral and chemical properties of I was carried out by performing quantum chemical calculations.     

Flow-injection spectrophotometric determination of palladium in catalysts and dental alloys with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropyl-amino)aniline

2-(5-Bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)aniline rapidly forms a water-soluble complex with palladium in an acetate-buffered medium at pH 3.2.The molar absorptivity of the complex is 9.84×10⁴l mol^?1 at 612 nm. The calibration graph is linear over the range of 10–100 μg l^?1 palladium; the detection limit is 2 μg l^?1 and the relative standard deviation is 0.6% for 100 μg l^?1 palladium. The sample throughput is 50 h^?1. Divalent transition metals (Fe, Ni, Co) do not interfere at levels from 2 to 10 mg l^?1. Interference from copper is prevented by adding 10^?3 M EDTA solution to the carrier stream. Palladium in solutions of catalysts and dental alloys can be determined selectively, sensitively and rapidly.     

Molecular imprinting polymer electrosensor based on gold nanoparticles for theophylline recognition and determination

An electrochemical sensor for theophylline (ThPh) was prepared by electropolymerizing o-phenylenediamine on a glassy carbon electrode in the presence of ThPh via cyclic voltammetry, followed by deposition of gold nanoparticles using a potentiostatic method. The effects of pH, ratio between template molecule and monomer, number of cycles for electropolymerization, and of the solution for extraction were optimized. The current of the electro-active model system hexacyanoferrate(III) and hexacyanoferrate(IV) decreased linearly with successive addition of ThPh in the concentration range between 4.0?×?10^?7?~?1.5?×?10^?5 mol·L^?1 and 2.4?×?10^?4?~?3.4?×?10^?3 mol·L^?1, with a detection limit of 1.0?×?10^?7 mol·L^?1. The sensor has an excellent recognition capability for ThPh compared to structurally related molecules, can be regenerated and is stable.

Analytical applications of 4-(4′-methyl-2′-thiazolylazo)-2-methyl-resorcinol: Spectrophotometric determination of vanadium

4-(4′-Methyl-2′-thiazolylazo)-2-methyl-resorcinol reacts with vanadium (V) to produce a bluish-violet 1:1 complex (λ_max = 560 nm, ? = 2.50 × 10⁴M^?1 · cm^?1, 50% methanol-water medium), which allows the spectrophotometric determination of 0.1 to 1.4 ppm of vanadium. The method has been applied to the determination of vanadium in several low-alloy steels.     

Simultaneous Determination of Nickel and Cobalt as Chelates with 1-(2-Pyridylazo)-2-naphthol Using an LC Switching Column Method

A simple liquid chromatographic method was developed for the separation and simultaneous determination of cobalt and nickel as chelates with 1-(2-pyridylazo)-2-naphthol (PAN). The method, using a switching column technique for the on-line purification and separation, enables to reach the sub-microgram per litre concentration level excluding off-line sample treatment with the exception of the derivatization reaction. Two small-sized columns packed with CN- and C₄-bonded stationary phases were selected and used considering their complementary behaviour with respect to chelated Co and Ni ions. The analysis was performed within 10 min using an optimised eluent (water–acetonitrile–methanol–tetrahydrofuran, 40:45:10:5, v/v/v/v) containing Tween 40 (10^?3 M) and acetate buffer (5 × 10^?3 M, pH 4.8). Detection was performed by UV-vis spectrophotometry (λ = 565 nm) permitting to reach quantification limits of 0.9 and 0.5 μg L^?1 for Co and Ni, respectively.     

Sensitive spectrophotometric determination of La(III) with 1-(2-pyridylazo)-2-naphthol

A simple and sensitive method for spectrophotometric determination of lanthanum has been developed. At pH 9.6, in presence of 50% ethanol, lanthanum reacts with 1-(-2-pyridylazo)-2-naphthol (PAN) to form a red complex which has two absorption maxima, at 545 and 510 nm. The molar absorptivity at 545 nm is 0.55 × 10⁴ liters · mol^?1 cm^?1. On the other hand, lanthanum reacts with PAN in pure ethanol to form a red complex at 530 nm, with high molar absorptivity (8 × 10⁴ liters · mol^?1 cm^?1).     

Potentiometric sensors based on organic ion exchangers for determining tetraalkylammonium salts

Potentiometric sensors with plasticized polymer membranes based on organic ion exchangers, tetraalkylammonium dodecyl sulfates (benzyldimethyldodecylammonium, benzyldimethyltetradecylammonium, dimethyldistearylammonium), have been proposed for the determination of quaternary ammonium salts in model solutions and KATAPAV technical solutions. The thermal stability, composition, and solubility product have been estimated. It has been shown that ion associates are stable to 60?C70°C, K _S varies in the range from 2 × 10^?8 to 5 × 10^?10. The basic electrochemical parameters of the sensors have been determined as well, such as linearity ranges of the electrode function (5 × 10^?5 (5 × 10^?6)?1 × 10^?2 (1 × 10^?3) M) and slopes of the electrode functions (47?C59 mV/pc), response time (60?C90 sec), potential drift (2?C3 mV/day), operation period (3?C4 months), limits of detection for tetramethylammonium salts (1 × 10^?5?4 × 10^?7 M).     

A multivariate calibration procedure for the tensammetric determination of detergents

A multivariate calibration procedure based on singular value decomposition (SVD) and the Ho-Kashyap algorithm is used for the tensammetric determination of the cationic detergents Hyamine 1622, benzalkonium chloride (BACl), N-cetyl-N,N,N-trimethylammonium bromide (CTABr) and mixtures of CTABr and BACl. The sensitivity and accuracy depend strongly on the nature of the detergent. Acceptable accuracy is obtained with a two-step calculation procedure in which calibration constants for the total concentration range of interest are used to guide the choice of a more specific set of calibration constants which are valid for a much smaller concentration span. For Hyamine 1622, concentrations in the range 5 × 10^?6?2 × 10^?4 M could be determined with an accuracy of ± 10^?6 M. For CTABr, these numbers were 3 × 10^?6?2 × 10^?4 M and ± 5 × 10^?7 M; for BACl, they were 2 × 10^?3?9 × 10^?2 g l^?1 and ± 1 × 10^?3 g l^?1. In the mixtures of CTABr and BACl, the accuracies were ± 3 × 10^?6 M and × 1 × 10^?3 g l^?1, respectively.     

Extractive-spectrophotometric determination of traces of copper(II) with 4-(p-nitrophenylazo)-2-amino-3-pyridinol

A new extractive-spectrophotometric method for determination of copper(II) with 4-(p-nitrophenylazo)-2-amino-3-pyridinol is proposed. The established stoichiometry and extraction constant are 2:1 ligand:metal and ?1.55, respectively. The molar absorptivity of the complex is 5.19 × 10⁴ liters mol^?1 cm^?1 at 560 nm and Sandell's sensitivity is 1.2 ng cm^?2. The best conditions for determination and effect of other ions are studied. The method proposed is applied in the determination of copper in whisky, liver of fish, and seawater.     

Spectrophotometric determination of titanium with Chrome Azurol S (or Eriochrome Cyanine R) in the presence of some cationic surfactants

A new sensitive spectrophotometric method for titanium determination, based on the ternary Ti-Chrome Azurol S (CAS)-cetyltrimethylammonium (CTA) system, was developed. The molar absorptivity is 7.3 × 10⁴ liters mol^?1 cm^?1 at λ_max = 565 nm. The maximum absorbance is attained in 5 min at pH 1.3 ± 0.1 and at CAS and CTA concentrations of 1.5 × 10^?4 and 5 × 10^?4M, respectively. Zirconium and hafnium in the presence of ascorbic acid are the only interfering metals. Hydrogen peroxide and EDTA interfere with the titanium determination as well. The proposed method was applied to the determination of titanium (about 1 × 10^?2%) in aluminum metal. The method, based on the Ti-Eriochrome Cyanine R-CTA system, is similar to the above method. Among other cationic surfactants, cetylpyridinium chloride (CP) and zephiramine were examined. The color effects when using CP, and especially zephiramine, are worse than in the presence of CTA.     

Effect of biogenic photochromic electron acceptors on chlorophyll fluorescence

It is shown that the photophysical properties of chlorophyll a (Chl) depend on the nature and relative amounts of 2-methyl-1,4-naphthoquinone (MNQ) and nicotinamide adenine dinucleotide phosphate (NADP). Photoinduced charge separation occurs in aqueous ethanol solutions of Chl (1 × 10^?5 M) and NADP (5 × 10^?6–5 × 10^?4 M), resulting in the dynamic quenching of Chl fluorescence. Coordination interaction between Chl and NADP is established at an NADP concentration of ≥5 × 10^?4 M. The nonlinear Stern-Volmer dependence in this range is due to the input from static quenching. It is shown that the quenching of Chl fluorescence in an MNQ solution at Chl and MNQ concentrations of 1 × 10^?5 M and 6.7 × 10^?5–1 × 10^?4 M, respectively, is described by a linear dependence in the Stern-Volmer coordinates; no complex formation is observed for Chl and MNQ under these conditions, and electron transfer is of the dynamic type. Static or mixed-type energy transfer from MNQ to Chl dominates at elevated MNQ concentrations.     

Direct potentiometric titration of thiosulfate,thiourea, and ascorbic acid with lodate using an iodide ion-selective electrode

A potentiometric method has been developed for the semi-automatic direct titration of thiourea, thiosulfate, and ascorbic acid with potassium iodate in strongly acidic solutions using an iodide ion-selective electrode to monitor the reaction and locate the endpoint. The method is simple, fast, precise, and accurate. Amounts ranging from 0.15–1.5 mg of thiourea (3.9 × 10^?4–3.9 × 10^?3, M), 0.3–3.0 mg of thiosulfate (5.4 × 10^?4–5.4 × 10^?3, M), and 0.5–5.0 mg of ascorbic acid (5.7 × 10^?4–5.7 × 10^?3, M) have been determined with an average error of about 1%. The method has been applied to the determination of ascorbic acid in tablets. Results checked closely with those obtained with a standard titrimetric method.     

Precipitation of copper(II) by formation of a complex with 2,4-dioxo-4-(4-hydroxy-6-methyl-2-pyrone-3-yl) butyric acid ethyl ester

Mononuclear copper(II) complex with 2,4-dioxo-4-(4-hydroxy-6-methyl-2-pyrone-3-yl) butyric acid ethyl ester is readily precipitated in ethanolic medium. The metal to ligand ratio in the crystalline species was found to be 1:2. On the basis of the spectroscopic data collected so far, the site of coordination could not be identified. The detection limit of the precipitation of the binuclear complex in aqueous buffer, pH 7.00, solution is at a 2 × 10^?5 mol dm^?3 copper(II) concentration. By radiometric measurements with ⁶⁴Cu isotope, the time neccessary for a quantitative precipitation, the amount of copper(II) in the precipitate and in the solution, the amount of ligand needed for the optimal precipitation yield, and the solubility product of the complex were determined.The precipitate separated from the supernatant can be dissolved in ethanol and copper(II) determined by absorbance measurement at 374 nm. The sensitivity of this procedure lies at the detection limit of the complex precipitation. The calibration diagram, a straight line (b = 0.00677; s_b = 0.00003; s² = 0.00146), confirms the validity of Beer's law in the range of 2 × 10^?5? 4 × 10^?4 mol dm^?3 copper(II) concentrations, with a systematic error of 7 × 10^?6 mol dm^?3 arising from solubility loss of the precipitate remaining constant.Concentrations exceeding 10^?6 mol dm^?3 of nickel(II) cause too high values and those exceeding 10^?5 mol dm^?3 of aluminium, zinc, iron(II), thorium(IV), or vanadium(V) too low values in copper determinations.     

Untersuchungen über (1:1)-Chelate des Curcumins mit Borsäure und Phenylborsäuren

The existence of 1∶1 boron-curcumin chelates in solution has been proved by the straight-line method of Asmus. The compounds with boric resp. phenylboronic acid propably exist as diacetato-resp. phenylacetato-boron chelates of curcumin. The dissociation constants of the 1∶1 complexes of curcumin and boron are K _D =4×10^?5 with boric acid in acetic acid and 3×10^?4 in dioxan, 1×10^?3 with phenylboronic acid in dioxan and 1×10^?4 when stabilized with phenol, 7×10^?5 with diphenylborinic acid in dioxan solution. All boron-curcumin chelates are formed from the quinonoid protonized form of curcumin, which can be stabilized by phenol.     

Determination of Dopamine Using 2-(4-Boronophenyl)quinoline-4-carboxylic Acids as Fluorescent Probes

The selective identification of dopamine is a significant issue because this compound is an important neurotransmitter closely related to Parkinson’s disease and other mental disorders. 2-(4-Boronophenyl)quinoline-4-carboxylic acid (PBAQA) has been previously reported as a water-soluble fluorescent probe for catechol. However, there are no significant differences in the binding constants between catechol and catecholamines, such as dopamine or levodopa. Here a series of bis-boronic acid compounds based on PBAQA were synthesized and the binding activities were characterized. As a representative compound, the binding constant of 4-(4-((3-(3-borono-4-chlorobenzamido)propyl)carbamoyl)quinolin-2-yl)boronic acid to dopamine is up to 10⁴?L?mol^?1 and much higher than previously reported boronic acid probes. Dopamine selectivity may be achieved by the variation of the substituents in the probe molecules. 4-(4-((3-(3-Borono-4-methoxybenzamido)propyl)carbamoyl)quinolin-2-yl)boronic acid has a stronger binding affinity to dopamine (K_a=5204?±?106?L?mol^?1) than catechol (K_a=2588?±?273?L?mol^?1) or levodopa (K_a=2383?±?273?L?mol^?1). This fluorescence response was used for determining dopamine in a range from 5?×?10^?5?mol?L^?1 to 5?×?10^?4?mol?L^?1 with a detection limit of 7.7?×?10^?6?mol?L^?1. This compound has been successfully used for the assay of dopamine in rabbit plasma, exhibiting excellent specificity. It is believed that synthesized compounds hold great promise as practical platforms to monitor dopamine levels.