Xerogels modified with l-(2-Pyridylazo)-2-naphthol and dimethylglyoxime: Indicator tubes for determining nickel

A simple and rapid sol-gel method was proposed for preparing xerogels modified with l-(2-pyrilylazo)-2-naphthol and dimethylglyoxime. Reactions between nickel and xerogels modified with l-(2-pyrilylazo)-2-naphthol and dimethylglyoxime were studied by solid-phase spectrophotometry, and the optimal conditions were found. Procedures for determining nickel in solution by solid-phase spectrophotometry and tests based on indicator tubes containing powdered xerogel modified with l-(2-pyrilylazo)-2-naphthol were developed. The analytical ranges for nickel in the above methods were 0.1–2 and 0.2–30 mg/L, respectively. The interference from cobalt(II) was eliminated by its adsorption on hydrophobic C₁₆ and C_phenyl silica gels modified with l-(2-pyrilylazo)-2-naphthol. The interference of copper(II) and iron(III) was eliminated by the addition of a mixture of Na₂S₂O₃ and NH₄F.     

Modifying Silicic Acid Xerogels and Accelerating Heterogeneous Reactions with Their Participation with the Use of Microwave Radiation

The use of microwave radiation for drying wet silicic acid gels significantly shortens the time of preparation of dry gels, or xerogels. The specific surface area of xerogels increases from 492 to 963 m²/g as the power of microwave radiation is increased from 300 to 1000 W. The effect of microwave radiation on the rate of heterogeneous reactions with the participation of analytical reagents incorporated into silicic acid xerogels was studied. It was found that, in a microwave field of a power of 600 W, the reactions between immobilized Bromobenzothiazo and cadmium, immobilized 1-(2-pyridylazo)-2-naphthol and cobalt(II), and immobilized phosphomolybdic heteropoly acid and hydrazine are essentially accelerated. For the reaction of cobalt(II) with 1-(2-pyridylazo)-2-naphthol incorporated into xerogel, microwave radiation accelerates both the outside and inside diffusion. The use of microwave radiation shortens the time of determining metal ions and hydrazine by solid-phase spectrophotometry.     

流动注射光度法直接测定海水中的微量苯胺

基于苯胺与亚硝酸盐的重氮化反应及反应产物与甲萘酚的显色,借助流动分析技术,实现了海水中苯胺含量的分析测定。体系以30.9g/L的NaCl做载液、人工海水配制标准样品,对各个影响因素进行了优化。苯胺浓度在0.01～1.0mg/L范围内与相对峰高呈线性关系,线性方程ΔH(mV)=200.53ρ+1.0728(n=8,ρ为苯胺浓度mg/L),相关系数R2=0.9982。方法的检出限(3σ)为0.005mg/L,相对标准偏差(RSD)为4.8%(n=11)。考察了共存离子、不同盐度样品对分析测定的影响。用于实际海水样品的分析,回收率为95.8%～106.6%。     

Indicator Tubes and Indicator Powders for Determining Fluoride and Chloride Ions

Noncovalent immobilization of Arsenazo I, Alizarin Red, Xylenol Orange, and diphenylcarbazone by incorporation into silicic acid xerogels and modification of silica gels was studied, and procedures for determining fluoride and chloride ions by solid-phase spectrophotometry and test methods were developed. Reactions of immobilized reagents with aluminum(III), zirconium(IV), and mercury(II) were studied. The possibility of using immobilized reagent–metal ion–halide ion systems for the determination of halide ions was assessed. Indicator powders were proposed for determining 0.5–10 mg/L fluoride ions and 1–30 mg/L chloride ions, and indicator tubes were developed for determining 20–200 mg/L chloride ions. The determination of fluoride and chloride ions is based on exchange complexation reactions proceeding in the systems immobilized Xylenol Orange–zirconium(IV) and immobilized diphenylcarbazone–mercury(II), respectively. Performance characteristics of the developed procedures were estimated. The procedures were verified by determining halide ions in Narzan mineral water.     

Xerogels Modified with 4-(2-Pyridylazo)-Resorcinol and Cetylpyridinium Chloride: Determination of Zinc in Solutions by Solid-Phase Spectrophotometry

Silicon dioxide-based xerogels modified with 4-(2-pyridylazo)-resorcinol (PAR) and cetylpyridinium chloride (CP) were synthesized. The concentration of PAR and CP in the hydrolyzed mixture in the ranges (0.6–3.10) × 10^–3 and (5–12) × 10^–3 M, respectively, does not affect the rate of gel formation as well as the specific surface area and average pore diameter of xerogels obtained upon drying in a microwave oven with a power of 600 Wt. It was found that the retention of PAR can be significantly improved in the presence of CP. Reactions of zinc with modified xerogels were studied by solid-phase spectrophotometry at different concentrations of PAR and CP, pH of the solution, and equilibrium time. A procedure was developed for determining 0.1–4.5 mg/L zinc in solutions by solid-phase spectrophotometry. Results of determining zinc in acid soil extracts and milk ash are given.     

A green analytical procedure for sensitive and selective determination of iron in water samples by flow-injection solid-phase spectrophotometry

A greener analytical procedure based on flow-injection solid-phase spectrophotometry is proposed for iron determination. Iron(II) is reversibly retained on 1-(2-thiazolylazo)-2-naphthol immobilized on C18-bonded silica, yielding a brown complex. The metal ion is eluted as iron(II) with a small volume of a diluted acid solution without removing the immobilized reagent, which can be used for at least 100 determinations. Other chemicals (buffer and reducing agent) were carefully selected taking into account the analytical performance and toxicity. The developed procedure is 10-fold more sensitive in comparison to the analogous procedure based on measurements in solution, being suitable for the determination of iron in water samples with good accuracy and precision. The detection limit (99.7% confidence level), sampling rate and coefficient of variation (n = 10) were estimated as 15 μg L⁻¹, 25 measurements per hour and 4.0%, respectively. The proposed procedure involves a reduced effluent generation (3.6 mL per determination) and consumes micro amounts of reagents.     

Modified Xerogel-Based Indicator Powders for Determining Ascorbic Acid and Hydrazines by Solid-Phase Spectrophotometry and Visual Tests

The effect of Cu(II), Ti(IV), Bi(III), and Fe(III) on the reduction of the Vavele reagent (a mixture of series 12 and 18 phosphomolybdic acids) with ascorbic acids and hydrazines was studied. It was found that, in the presence of copper(II), the Vavele reagent both nonimmobilized and immobilized on silicic acid xerogel is reduced in 10–15 min. Procedures were developed for determining ascorbic acid and hydrazines by solid-phase spectrophotometry and in visual tests using silicic acid xerogel modified with the Vavele reagent and copper(II) as an indicator powder. The precision, accuracy, and selectivity of the developed procedures were estimated. The results of determining ascorbic acids in dry fruit drinks were presented. The procedure proposed for the test determination of hydrazines in process solutions was certified by the State Committee for Standards and Metrology of Russian federation and recorded in the register of test systems under the number TS 7-99.     

Silica-based xerogels modified with cobalt(III): Determination of naphthols in solutions by solid-phase spectrophotometry

Silica-based xerogels modified with various concentrations of cobalt ions were prepared. The redox and complexing properties of immobilized cobalt ions were studied. Modified xerogels were used for determining naphthols in solutions by solid-phase spectrophotometry after their nitrosation. The effects of various factors on the absorbance of xerogels were studied. These factors are the average pore diameter in powdered xerogels, the concentration of cobalt(III), the pH of the test solution, and the concentration of CH₃COOH and NaNO₂ at the stage of nitrosation. The best conditions for determining naphthols were found. The developed procedure was used in the analysis of various samples.     

Solid-phase reagent for molecular spectroscopic determination of heavy metal speciation in natural water

A solid-phase reagent based on 1-(4-adamantyl-2-thiasolylazo)-2-naphthol adsorbed onto silica gel was prepared for Co(II) recovery and preconcentration prior to its sorption-spectroscopic detection. The immobilized reagent was applied to the determination of free cobalt ions in natural water. The solid-phase reagent and chemiluminescent method coupled with membrane filtration, gel-permeation and ion-exchange chromatography were applied to the study of the speciation of iron and cobalt in water from the Dnieper reservoirs and lakes of Kyiv City; their predominant forms were complexes of Fe(III) and Co(II) with dissolved organic matter and fulvic acids play a main role in their complexation.     

Determination of Cu(II) and Zn(II) using silica gel loaded with 1-(2-thiasolylazo)-2-naphthol

The silica gel with 1-(2-thiasolylazo)-2-naphthol adsorbed was obtained. The adsorption of Cu(II) and Zn(II) from an aqueous solution onto loaded silica gel was studied. The capabilities of 1-(2-thiasolylazo)-2-naphthol immobilized for Cu(II) and Zn(II) preconcentration, visual and diffusion reflectance spectroscopic detection was evaluated. The detection limits were 10 and 15 microg.l(-1), respectively. Visual test scales for metal ions determination in the range 0.65-13 microg per sample were worked out. The developed methods were applied to Cu(II) and Zn(II) determination in natural and tap water. The obtained results agreed well with the reported value.     

Solid Phase Spectrophotometry for the Determination of Cobalt in Pharmaceutical Preparations

 A new sensitive method exploiting solid-phase spectrophotometry is proposed for the determination of cobalt in pharmaceutical preparations. The chromogenic reagent 1-(2-thiazolylazo)-2-naphthol (TAN) was immobilized on C18 bonded silica loaded into a home-made cell with 1.5 mm of optical path for cobalt determination. Cobalt(II) reacts with TAN on C18 material, at pH 6.0–7.5, to give a coloured complex which has maximum absorption at 572 nm. In this way, the sample was passed through the cell and Co(II) ions were quantitatively retained on the solid-phase. After the direct measurement of light-absorption in the solid phase, only the cobalt was eluted with 0.1 mol L⁻¹ hydrochloric acid. The cell was washed with water and then another sample solution could be passed through the cell. The procedure allowed the determination of cobalt in the range of 10–160 μg L⁻¹ with coefficient of variation of 4.7% (n=10) and apparent molar absorptivity of 2.62 × 10⁶ L mol⁻¹ cm⁻¹ using sample volume of 3-mL. Received May 15, 2000. Revision August 28, 2000.     

A New Tetrasubstituted Imidazole Based Difunctional Probe for UV-spectrophotometric and Fluorometric Detecting of Fe3+ Ion in Aqueous Solution

Two new compounds,4-(2-bromophenxl-4,5-diphenyl-imidazol-1-yl)ani 1 ine(probe 1)and 4-[2,4,5-tris(4-bromopheny1)-1H-imidazol-1-y1]aniline(probe 2),were synthesized via a soft and high-efficiency one-pot microwave-assisted method under solvent-free conditions.Their sensing to different metal ions was detected by UV spectrophotometry and fluorescence spectrometry.Probe 2 revealed highly selective and sensitive UV and fluorescence response to Fe^3+ion.Upon the addition of Fe^3+ion,probe 2 showed obvious color change of the solution,conspicuous absorbance enhancement and relatively quick fluorescence quenching.The detection limit for Fe^3+ion was respectively calculated to be 0.72μmol/L(fluorescent detection)and 0.48μmol/L(UV-spectnim detection).Also,probe 2 was bound by Fe^3+ion to tonn a 1:1 complex.Moreover,preliminary application of probe 2 tor detecting Fe^3+ion in aqueous solution was attempted,and satisfying results were obtained.     

Hybridization detection of enzyme-labeled DNA at electrically heated electrodes

In this report we describe an electrochemical DNA hybridization sensor approach, in which signal amplification is achieved using heated electrodes together with an enzyme as DNA-label. On the surface of the heatable low temperature co-fired ceramic (LTCC) gold electrode, an immobilized thiolated capture probe was hybridized with a biotinylated target using alkaline phosphatase (SA-ALP) as reporter molecule. The enzyme label converted the redox-inactive substrate 1-naphthyl phosphate (NAP) into the redox-active 1-naphthol voltammetrically determined at the modified gold LTCC electrode. During the measurement only the electrode was heated leaving the bulk solution at ambient temperature. Elevated temperature during detection led to increased enzyme activity and enhanced analytical signals for DNA hybridization detection. The limit of detection at 53 °C electrode temperature was 1.2 nmol/L.     

Preparation of cyano-functionalized multiwalled carbon nanotubes as solid-phase extraction sorbent for preconcentration of phenolic compounds in environmental water

In the present work, we showed a novel method to synthesize cyano-functionalized multiwalled carbon nanotubes (MWCNTs-CN) and utilize it as a solid-phase extraction sorbent for preconcentration of phenolic compounds in environmental water samples. MWCNTs-CN was synthesized through surface functionalization of multiwalled carbon nanotubes (MWCNTs). The functional groups on the surface of modified MWCNTs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. The analytical procedure was based on a conventional solid-phase extraction step for which 100 mg of MWCNTs-CN were packed in a 3 mL polypropylene cartridge. Analytes were thus isolated and preconcentrated from the pretreated samples and subsequently detected on high-performance liquid chromatography-ultraviolet detection. The results showed the proposed method exhibited good sensitivity and precision for the extraction and elution of analytes. The limit of detections (S/N = 3) of the method were 0.45, 0.09, 0.08, and 3.00 ng mL(-1) for p-chlorophenol, 1-naphthol, 2-naphthol, and 2,4-dichlorophenol, respectively. The mean relative recoveries (n = 3) were between 80.28 and 103.13%, and the repeatability (RSD ≤ 5.10%) and reproducibility (RSD ≤ 7.68%) were accepted. This developed method was applied to determine phenolic compounds in environmental water samples. There is a positive result only for 2-naphthol with concentration of 0.38 ng mL(-1) in seawater sample.     

Spectrophotometric studies and analytical application of Ce(III) chelates with 1-(2-pyridylazo)-2-naphthol (PAN)

A sensitive procedure for spectrophotometric determination of cerium(III) has been developed. AtpH 10.2 cerium reacts with 1-(2-pyridylazo)-2-naphthol in 40% ethanol to form a red complex which has an absorption maximum at 545 nm. The molar absorptivity at 545 is 3.95·10³ mol^–1. Maximum stability of the complex was attained in pure ethanol. The stoichiometries and structures of the chelates were studied applying conductometric titration, visible spectrophotometry and IR spectrophotometry. The IR spectra revealed that coordination takes place through the N=N, C-OH and pyridyl group.

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Spektrophotometrische Untersuchungen und analytische Anwendung von Ce(III)-Chelaten mit 1-(2-Pyridylazo)-2-naphthol (PAN)

Zusammenfassung Es wurde eine empfindliche Methode zur spektrophotometrischen Bestimmung von Cer(III) entwickelt. Bei einempH von 10,2 reagiert Cer mit 1-(2-Pyridylazo)-2-naphthol in 40% Ethanol unter Bildung eines roten Komplexes mit einem Absorptionsmaximum bei 545 nm (=3 950). Der Komplex besitzt in reinem Ethanol ein Maximum an Stabilität. Die Stöchiometrien und Strukturen der gebildeten 1:1- und 1:2-Chelate wurden mittels konduktometrischer Titration, Elektronen- und IR-Spektrometrie untersucht. Die IR-Daten zeigen, daß die Koordination über N=N, C-OH und Pyridyl erfolgt.

     

Nickel and zinc determination by flow-injection solid-phase spectrophotometry exploiting different sorption rates

Flow-injection solid-phase spectrophotometry is applied for sequential determination of nickel and zinc, exploiting their different sorption rates on 1-(2-thiazolylazo)-2-naphthol (TAN) immobilized on C(18)-bonded silica. The Zn(II) sorption rate on the solid support is constant for flow rates ranging from 0.70 to 2.2 ml min(-1), but for Ni(II) the sorption rate decreases with increasing flow rate. A flow system was designed to perform sequential measurements at two different flow rates (0.85 and 1.9 ml min(-1)). The absorbance was measured at 595 nm, where both TAN-immobilized complexes showed maximum absorption. The coefficients of variation were estimated (n=10) as 1.1 and 1.7% (at 1.9 ml min(-1)) and 1.2 and 2.1% (at 0.85 ml min(-1)) for zinc and nickel, respectively. This strategy was applied to determine zinc and nickel in copper-based alloys and the results agreed with certified values at the 95% confidence level. The sample throughput was estimated as 36 h(-1).     

A New Spectrophotometry Method for the Determination of Aniline in Environmental Water Samples

ABSTRACT

A new spectrophotometric method has been established to determine trace aniline in water samples. A mixture solution of N-chlorosuccinimide and 8-hydroxyquinaldine in N, N-dimethylformamide (DMF) was used to react with the aniline in water at room temperature (20°C). When the solution was adjusted to pH 10-11 by adding 3 mol/L NaOH, a clear and blue-colored dye formed immediately with the maximum absorption wavelength at 615 nm. Molar absorptivity and detection limit were found to be 1.0×10⁴ L mol^?1 cm ^?1 and 30 μg/L, respectively. Linearity was excellent in the concentration range of 0.2 to 15 mg/L aniline in water sample. The proposed method has been used to analyze aniline in surface and sewage water samples with the recoveries 96-103% and relative standard deviation less than 3%. It's a promising method to be applied for routine analysis of aniline in water.     

Sorption–Chromatographic Determination of Aniline, 4-Chloroaniline, and 2,5-Dichloroaniline in Air

Conditions were found for the chemisorption preconcentration of aniline, 4-chloroaniline, and 2,5-dichloroaniline from air using tubes packed with silica gel with immobilized 4-chloro-5,7-dinitrobenzofurazan and for the subsequent HPLC determination with diode-array detection. The maximum analyte recoveries (98, 90, and 75% for aniline, 4-chloroaniline, and 2,5-dichloroaniline, respectively) were achieved at a 2-cm thickness of the adsorbent layer (silica gel with a grain size of 0.1–0.3 mm impregnated with 3 wt % 4-chloro-5,7-dinitrobenzofurazan), an aspiration rate of 0.6–0.8 L/min, and an aspirated air volume of 10 L. Taking into account a tenfold preconcentration of analytes after the desorption, the detection limit for aniline is equal to 0.0007 mg/m³.     

Organosilica composite for preconcentration of phenolic compounds from aqueous solutions

A new adsorbent is proposed for the solid-phase extraction of phenol and 1-naphthol from polluted water. The adsorbent (TX-SiO₂) is an organosilica composite made from a bifunctional immobilized layer comprising a major fraction (91%) of hydrophilic diol groups and minor fraction (9%) of the amphiphilic long-chain nonionic surfactant Triton X-100 (polyoxyethylated isooctylphenol) (TX). Under static conditions phenol was quantitatively extracted onto TX-SiO₂ in the form of a 4-nitrophenylazophenolate ion associate with cetyltrimethylammonium bromide. The capacity of TX-SiO₂ for phenol is 2.4 mg g⁻¹ with distribution coefficients up to 3.4 × 10⁴ mL g⁻¹; corresponding data for 1-naphthol are 1.5 mg g⁻¹ and 3 × 10³ mL g⁻¹. The distribution coefficient does not change significantly for solution volumes of 0.025–0.5 L and adsorbent mass less than 0.03 g; 1–90 μg analyte can be easily eluted by 1–3 mL acetonitrile with an overall recovery of 98.2% and 78.3% for phenol and 1-naphthol, respectively. Linear correlation between acetonitrile solution absorbance (A ₅₄₀) and phenol concentration (C) in water was found according to the equation A ₅₄₀ = (6 ± 1) × 10⁻² + (0.9 ± 0.1)C (μmol L⁻¹) with a detection range from 1 × 10⁻⁸ mol L⁻¹ (0.9 μL g⁻¹) to 2 × 10⁻⁷ mol L⁻¹ (19 μL g⁻¹), a limit of quantification of 1 μL g⁻¹ (preconcentration factor 125), correlation coefficient of 0.936, and relative standard deviation of 2.5%. A solid-phase colorimetric method was developed for quantitative determination of 1-naphthol on adsorbent phase using scanner technology and RGB numerical analysis. The detection limit of 1-naphthol with this method is 6 μL g⁻¹ while the quantification limit is 20 μL g⁻¹. A test system was developed for naked eye monitoring of 1-naphthol impurities in water. The proposed test kit allows one to observe changes in the adsorbent color when 1-naphthol concentration in water is 0.08–3.2 mL g⁻¹.     

Immunosensors for pollutants working in organic media. Study of performances of different tracers with luminescent detection

A comparative study of enzymatic and non-enzymatic labels combined with luminescence detection, developed for immunosensing of pesticide residues (carbaryl, 1-naphthol, irgarol 1051) in organic media, is presented. Peroxidase and alkaline phosphatase enzymes with fluorogenic (3-p-hydroxyphenylpropanoic acid) and luminogenic (AMPPD derivative) substrates, respectively, were assessed as enzymatic markers. As an alternative, terbium(III) chelate, with time-resolved fluorescence detection, was evaluated as a non-enzymatic label. The best sensitivity was achieved by use of alkaline phosphatase in an immunocomplex capture assay format (I ₅₀ values 0.06, 0.27, and 7.45 μg L⁻¹ in buffer, 1:1 methanol–buffer, and methanol, respectively). Results were also good (I ₅₀ 1.00 and 6.30 μg L⁻¹ for water and aqueous–organic mixture, respectively) for Tb(III) chelate in an immobilized conjugate assay format. Use of alkaline phosphatase label to measure carbaryl (100 ng L⁻¹) in different spiked river water samples, after solid-phase extraction and analyte elution with an ethyl acetate–methanol mixture, resulted in recoveries ranging from 81 to 98%, with acceptable precision (CV 4–14%, n=4).