Sensitive Voltammetric Determination of Cadmium(II) with 8‐Hydroxyquinoline and Ionic Liquid Modified Carbon Paste Electrode

In this paper 8‐hydroxyquinoline (HQ) and ionic liquid (IL) modified carbon paste electrode was fabricated and used for the sensitive determination of cadmium(II) with differential pulse anodic stripping voltammetry (DPASV). The modified electrode was prepared by the addition of HQ and IL 1‐ethyl‐3‐methylimidazoliam ethylsulphate as the modifiers into the traditional carbon paste mixture. Cd(II) was preconcentrated and reduced on the surface of the modified electrode at the potential of ‐1.0 V (vs. SCE) by the co‐contributions from the formation of HQ‐Cd(II) complex and the accumulation effect of IL. Then the reduced Cd on the electrode surface was reoxidized by DPASV with a sensitive oxidation peak appeared at ‐0.79 V (vs. SCE). Under the optimal conditions the oxidation peak current was proportional to the Cd(II) concentration in the range from 0.03 to 2.0 mol/L with the detection limit as 5.0 nmol/L (3σ). The proposed method was successfully applied to the water samples detection with the recovery in the range from 95.6% to 96.6%.     

Simultaneous Determination of Antimony(III) and Molybdenum(VI) by Adsorptive Stripping Voltammetry Using Quercetin as Complexing Agent

A sensitive and selective voltammetric method for simultaneous determination of Sb(III) and Mo(VI) using Quercetin (Q) as complexing agent is described. Optimal conditions were found to be: pH 3.7, C_Q=6.0 µmol L^?1 and E_acc=?0.10 V. The LOD (3σ) for Sb(III) are 0.076 and 0.040 µg L^?1, whereas for Mo(VI) are 0.086 and 0.048 µg L^?1 with t_acc of 60 and 120 s, respectively. The method was validated using synthetic sea water (ASTM D665) and was applied to the determination of Sb(III) and Mo(VI) in natural waters with satisfactory results.     

Synthesis,Structure, and Fluorescent Properties of Lanthanide Complexes Based on 8‐Hydroxyquinoline‐7‐carboxylic Acid

The lanthanide complex [Eu₃(8‐HQCA)₃(COOH)(OH)₂(H₂O)₃]_n · nH₂O (8‐HQCA = 8‐hydroxyquinoline‐7‐carboxylic acid) was synthesized and characterized. Single‐crystal X‐ray diffraction shows that the trinuclear structures are linked by ligands to form 2D layers. The results of DFT calculation shows that energy can be transferred effectively from the ligand to Eu^III ions. A series of heteronuclear complexes {[(Eu_1–xY_x)₃(8‐HQCA)₃(COOH) (OH)₂(H₂O)₃]_n · nH₂O (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8)} were synthesized and their luminescent properties were studied. The results showed that the doping of Y^III ions could change the fluorescent intensity of the Eu^III complex, but could not change their positions.     

Kinetic and Thermodynamic Investigations of Zn(II) Adsorption on Microcrystalline Anthracene Modified with 8‐Hydroxyquinoline and Its Application to the Preconcentration and Determination of Trace Zinc

A new method that utilizes microcrystalline anthracene modified with 8‐hydroxyquinoline as an adsorbent has been developed for the preconcentration of trace Zinc(II). The possible reaction mechanism is discussed in detail. The influences of different parameters, such as acidity, other metal ions, the amounts of 8‐hydroxyquinoline and anthracene, etc. on the enrichment yield of Zn(II) have been studied to optimize the experimental conditions. The experimental data were fitted well with the pseudo‐second‐order kinetic model and Langmuir model at all studied temperatures and the maximum adsorption capacity was 32.58 mg·g^?1 (300 K). The thermodynamic parameters (ΔG^θ, ΔH^θ and ΔS^θ) showed the feasibility, exothermic and spontaneous nature of the adsorption at 280～320 K. Experiments indicate that Zn(II) can be completely separated from Cu(II), Co(II), Cd(II), Mn(II), Ni(II) in the eluent. The recovery of this method is in the range of 96.0%～105.0% with preconcentration factor of 100 and the limit of detection after preconcentration is 0.068 μg·L^?1. The proposed method has been successfully applied to the determination of trace Zn(II) in effluents and synthetic water sample having a composition similar to certified water sample SLRS‐4 (NRC, Canada). Analytical results obtained by this recommended method were very satisfactory.     

Determination of Aluminum by Adsorptive Cathodic Stripping Voltammetry with 1,2‐Dihydroxyanthraquinone‐3‐Sulfonic Acid (DASA): Effect of Thin Mercury Film Electrode

An analytical technique for aluminum (Al) based upon the complexation reaction between Al and the ligand – DASA (1,2‐dihydroxy‐anthraquinone‐3‐sulfonic acid) has previously been implemented successfully at the hanging mercury drop electrode (HMDE). There are several advantages of using mercury film electrodes (TMFE) over the HMDE, particularly if disposal of mercury is of concern. The novelty of using TMFE for adsorptive cathodic stripping voltammetry (ACSV) of Al – DASA is demonstrated in this paper. The peak potential used for the detection of Al in this system was at ?1.15 V (vs. Ag/AgCl). The method produced a limit of detection (LOD) of 1 μM (n=5) and a linear working range of 1–20 μM Al. Atomic force microscopy methods were used to investigate the nature of the TMFE and its interaction with DASA. The mercury droplets on the TMFE have a limited volume and this may lead to overloading of the electrode at relatively low concentrations of DASA. Interferences from Fe, Ca, Zn and Mg were investigated with only Fe appearing to interfere with the Al‐DASA system. Two masking agents (o‐phenanthroline and 2,2′‐bipyridyl) were shown to be effective at preventing the Fe interference.     

Electroanalytical Determination of Cadmium(II) and Lead(II) Using an Antimony Nanoparticle Modified Boron‐Doped Diamond Electrode

We report the simultaneous electroanalytical determination of Pb²⁺ and Cd²⁺ by linear sweep anodic stripping voltammetry (LSASV) using an antimony nanoparticle modified boron doped diamond (Sb‐BDD) electrode. Sb deposition was performed in situ with the analytes, from a solution of 1 mg L^?1 SbCl₃ in 0.1 M HCl (pH 1). Pb²⁺ inhibited the detection of Cd²⁺ during simultaneous additions at the bare BDD electrode, whereas in the presence of antimony, both peaks were readily discernable and quantifiable over the linear range 50–500 μg L^?1.     

Adsorptive Cathodic Stripping Voltammetric Determination of Uranium(VI) in Presence of N‐Phenylanthranilic Acid

N‐Phenylanthranilic acid was used as a complexing agent for determination of uranium(VI) by adsorptive cathodic stripping voltammetry. Under the optimal experimental conditions of the experimental parameters, the peak current was proportional to the concentration of U(VI) in the range 0.75–30 ng mL^?1 and the detection limit was 0.036 ng mL^?1. The influence of possible interferences was investigated. The method was applied for determination of uranium in waste water from uranium conversion facility and natural water samples. Application of the method for simultaneous determination of U(VI) and Cu(II) showed that these ions could be simultaneously determined in a single scan at relatively wide concentration range.     

Ex‐situ Antimony Screen‐printed Carbon Electrode for Voltammetric Determination of Ni(II)‐ions in Wastewater

An Ex‐situ antimony film screen‐printed carbon electrode (Ex‐situ SbSPCE) was successfully applied for the determination of Ni(II), by means of adsorptive stripping voltammetry using dimethylglyoxime as complexing agent, in a certified reference wastewater sample. This electrode is proposed as an alternative to more conventional antimony film electrodes. Ex‐situ SbSPCE was analytically characterized and the obtained parameters suggest that Ex‐situ SbSPCE behaves much better than both Ex‐situ BiSPCE and Bi_spSPE for Ni(II) determination. The results confirm the applicability of Ex‐situ SbSPCE for the determination of low concentration levels of Ni(II) in natural samples with a very high reproducibility and good trueness.     

Adsorptive Stripping Voltammetric Determination of Nanomolar Concentration of Cerium(III) at a Carbon Paste Electrode Modified by N′‐[(2‐Hydroxyphenyl)Methylidene]‐2‐Furohydrazide

The aim of this work was to obtain an adsorptive stripping voltammetric method for the Ce(III) determination at a carbon paste electrode, chemically modified with N'‐[(2‐hydroxyphenyl)methylidene]‐2‐furohydrazide (NHMF). The electroanalytical procedure comprised two steps: the Ce(III) chemical accumulation at ?200 mV followed by the electrochemical detection of the Ce(III)/NHMF complex, using anodic stripping voltammetry. The factors, influencing the adsorptive stripping performance, were optimized including the modifier quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The resulting electrode demonstrated a linear response over a wide range of Ce(III) concentration (5.0–90 nmol dm^?3). The detection limit was found to be 0.8 nmol dm^?3 on the basis of a signal to noise ratio of 3. The precision for six determinations of 10 and 55 nmol dm^?3 Ce(III) was 5.6% and 2.1% (relative standard deviation), respectively. Application of the procedure to the determination of cerium in phosphate rock and wastewater samples gave good results.     

Adsorptive Stripping Voltammetric Determination of Trace Uranium with a Bismuth‐Film Electrode Based on the U(VI)→U(V) Reduction Step of the Uranium‐Cupferron Complex

This work reports the use of adsorptive stripping voltammetry (AdSV) for the determination of uranium on a preplated rotating‐disk bismuth‐film electrode (BiFE). The principle of the method relied on the complexation of U(VI) ions with cupferron and the subsequent adsorptive accumulation of the complex on the surface of the BiFE. The uranium in the accumulated complex was then reduced by means of a cathodic voltammetric scan while the analytically useful U(VI)→U(V) reduction signal was monitored. The experimental variables as well as potential interferences were investigated and the figures of merit of the method were established. Using the selected conditions, the 3σ limit of detection for uranium was 0.1 μg L^?1 at a preconcentration time of 480 s and the relative standard deviation was 4.7% at the 5 μg L^?1 level for a preconcentration time of 120 s (n=8). The accuracy of the method was established by analyzing a reference sea water sample.     

8‐Hydroxyquinoline Functionalized PEG‐1000 Bridged Dicationic Ionic Liquid as a Novel Ligand for Copper‐catalyzed N‐Arylation of Imidazoles

A novel 8‐hydroxyquinoline functionalized PEG‐1000 bridged dicationic ionic liquid ([HQ‐PEG₁₀₀₀‐DIL][BF₄]) was synthesized and characterized. It was applied as an efficiently recyclable ligand for copper‐catalyzed N‐arylation of nitrogen‐containing heterocycles with aryl halides. The catalytic system could be easily recovered and reused for at least five runs without obvious loss of catalytic activity.     

Chemical Speciation of Antimony(III and V) in Water by Adsorptive Cathodic Stripping Voltammetry Using the 4‐(2‐Thiazolylazo) – Resorcinol

A simple adsorptive cathodic stripping voltammetry method has been developed for antimony (III and V) speciation using 4‐(2‐thiazolylazo) – resorcinol (TAR). The methodology involves controlled preconcentration at pH 5, during which antimony(III) – TAR complex is adsorbed onto a hanging mercury drop electrode followed by measuring the cathodic peak current (I_p,c) at ?0.39 V versus Ag/AgCl electrode. The plot of I_p,c versus antimony(III) concentration was linear in the range 1.35×10^?9–9.53×10^?8 mol L^?1.The LOD and LOQ for Sb(III) were found 4.06×10^?10 and 1.35×10^?9 mol L^?1, respectively. Antimony(V) species after reduction to antimony(III) with Na₂SO₃ were also determined. Analysis of antimony in environment water samples was applied satisfactorily.     

DNA Binding Studies and Cytotoxicity of Ethylenediamine 8‐Hydroxyquinolinato Palladium(II) Chloride

Interaction between ethylenediamine 8‐hydroxyquinolinato palladium(II) chloride and calf thymus DNA (CT‐DNA) in aqueous solution were studied by UV‐Visible absorption, fluorescence spectroscopic techniques and gel chromatography at temperatures of 300 K and 310 K. The complex bound strongly and intercalatively to the CT‐DNA. The results of the cytotoxicity assay of the Pd(II) complex on the leukemia cell line, K562 indicated lower cytotoxicity than cisplatin. The Pd(II) complex is considered an agent with potential antitumor activity. The calculation of several binding and thermodynamic parameters of the inclusion Pd(II) complex with CT‐DNA may provide deeper insights into the mechanism of action of these types of complexes with nucleic acids.     

XPS analysis of glassy carbon electrodes chemically modified with 8‐hydroxyquinoline‐5‐sulphonic acid

Glassy carbon (GC) modified electrodes were obtained by cycling the potential in an 8‐hydroxyquinoline‐5‐sulphonic acid (HQSA) solution. These electrodes were successfully tested as sensors of some species of alimentary and pharmaceutical interest, showing improved performances with respect to those of unmodified GC electrodes and of GC electrodes cycled under the same experimental conditions but in the absence of HQSA. As a matter of fact, in the wide potential range explored for modifying the electrodes, even in the absence of HQSA, complex redox processes leading to the production of several functional groups take place at the surface of glassy carbon itself. An XPS investigation was consequently performed to better understand the effective nature of active species present on the surface of HQSA modified electrodes. The spectroscopic experiments involved acquiring survey and detailed scans of an HQSA powder standard sample and of GC electrodes cycled both in the presence and in the absence of HQSA. The experimental value of the binding energy of the S2p_3/2 level of HQSA‐modified electrodes was found equal to that of the HQSA standard powder, thus confirming that HQSA molecules are adsorbed on the surface of the GC/HQSA electrodes and that they maintain their chemical structure and properties. Copyright © 2011 John Wiley & Sons, Ltd.     

Novel,Sensitive Voltammetric Methods for Titanium Determination Using Chromotropic Acid and Azo‐Compounds as Complexing Agents

Voltammetric behavior of titanium(IV) complexes with chromotropic acid, its azo‐derivatives: 2‐(4‐sulfophenylazo)‐1,8‐dihydroxy‐3,6‐naphthalenedisulfonic acid (SPANDS), chromotrope 2B, sulfonazo III and other azo‐compounds: calmagite, tropeoline O and kalces was investigated at a hanging mercury drop electrode. These complexes strongly adsorb onto the electrode, thus can be determined by an adsorptive stripping voltammetry (optimal pH about 6). At pH about 3 reduction current enhancement for Ti‐kalces complex was observed in the presence of chlorate ions. It is a rare example of a catalytic process with azo‐compound as a complexing agent. Signal for Fe‐calmagite complex reduction was also observed. Influence of foreign ions and the optimal conditions for titanium determination are described in detail. Additionally, a connection between obtained results and a structure of titanium complexes is discussed.     

A New Voltammetric Sensor for Hydrazine Based on Michael Addition Reaction Using 1‐Amino‐2‐naphtol‐4‐sulfonic Acid

In this paper, voltammetric determination of hydrazine was investigated by 1‐amino‐2‐naphtol‐4‐sulfonic acid (ANSA) at the surface of carbon paste electrode (CPE) using cyclic voltammetry (CV) and double potential step chronoamperometry. Results showed that in pH 7.00, hydrazine participates in Michael addition reaction with ANSA and the anodic peak potential of hydrazine shifted to 726 mV less positive than CPE in absence of ANSA, this value is unique compared with other research works. Also, the value of rate constant for the oxidation of hydrazine was calculated 8.3 × 10⁴ cm³ mol^‐1 s^‐1 and the diffusion coefficient of ANSA at the surface of CPE was determined 7.3 × 10^‐7 cm² s^‐1. A linear correlation between Ip and hydrazine concentration in the ranges, from 5 × 10^‐5 mol/L to 2.5 × 10^‐2 mol/L with CV method was obtained and the detection limit was found as 4.3 × 10^‐5 mol/L.     

Synthesis and structural characterization of new 2-bromo-1,3-bis(triazol-1-ylmethyl)benzene ligands. Study of their behavior as complexing agents for determination of nickel(II) by adsorptive stripping voltammetry

Reaction of 2-bromo-1,3-bis(bromomethyl)benzene (1) with 1,2,3-triazole and benzotriazole yields 2-bromo-1,3-bis(triazol-1-ylmethyl)benzene (2) and 2-bromo-1,3-bis(benzotriazol-1-ylmethyl)benzene (3), isolated as white solids, air stable at room temperature, and characterized by elemental analysis, mass spectra, IR, and NMR (¹H, ¹³C) spectroscopy. The molecular structure of 3 was determined by single-crystal X-ray diffraction. These ligands were evaluated for determination of ultra-trace concentrations of nickel by adsorptive stripping voltammetry. The method is based on adsorptive accumulation of the Ni(II)-L complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species by voltammetric scan using square wave modulation. However, only with 2 was a signal observed at ?0.81?V. Under the best experimental conditions (pH 5.5; ligand concentration 0.30?μmol?L^?1; adsorptive potential (E _ads) ?0.70?V and adsorptive time (t _ads) 80 s), the peak current is proportional to the Ni(II) concentration to 15.0?μg?L^?1, with a 3 detection limit of 0.2?μg?L^?1. The proposed method was validated by determining Ni(II) in certified reference waste water (SPS–WW1) with satisfactory results.     

Simultaneous Electrochemical Detection of Co(II) and Cu(II) by 1‐Diazo‐2‐Naphthol‐4‐Sulfonic Acid/MWCNTs Modified Electrode

This work describes a simple preparation of 1‐diazo‐2‐naphthol‐4‐sulfonic acid (1,2,4‐acid) and multiwalled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE) for the simultaneous detection of Co(II) and Cu(II). MWCNTs, with their good conductivity and large surface area, were drop‐casted onto the surface of the GCE prior to the electrodeposition of 1,2,4‐acid, a metal chelating agent. Co(II) and Cu(II) were simultaneously measured by differential pulse anodic stripping voltammetry (DPASV) in a batch system. Under optimum conditions, the linear range of Co(II) was between 0.10 and 2.5 μg mL⁻¹ with an LOD of 80 ng mL⁻¹. Two linear ranges were obtained for Cu(II), 0.0050 to 0.030 μg mL⁻¹ and 0.040 to 0.25 μg mL⁻¹,with an LOD of 2.4 ng mL⁻¹. The method offered a high operational stability for up to 52 measurements (RSD=3.4 % for Co(II) and 2.6 % for Cu(II)) and good reproducibility (RSD=1.2 % for Co(II) and 1.7 % for Cu(II)). In the simultaneous detection of Co(II) and Cu(II), there was no effect from common interferences found in wastewater. The method was successfully applied in real water samples with good recoveries (88.2±0.8 to 102.0±0.8 % for Co(II) and 96.5±0.4 to 103.8±0.9 % for Cu(II)) and the results were in good agreement with those obtained from inductively coupled plasma optical emission spectrometry (ICP‐OES) (P >0.05).     

Silica‐bonded S‐sulfonic Acid as a Recyclable Catalyst for Synthesis of 2,3‐Dihydroquinazolin‐4(1H)‐ones

2,3‐Dihydroquinazolin‐4(1H)‐one derivatives were synthesized via a one‐pot, three component reaction of isatoic anhydride and an aromatic aldehyde with ammonium acetate or primary amine catalyzed by silica‐bonded S‐sulfonic acid in ethanol at 80°C. The reaction work‐up is simple and the catalyst is easily separated from the products by filtration. The heterogeneous catalyst was recycled for ten runs upon the condensation reaction of isatoic anhydride and 4‐chlorobenzaldehyde with ammonium acetate without losing its catalytic activity.     

绝热量热和热分析研究8－羟基喹啉的热力学性质

采用绝热量热和热分析技术研究了8-羟基喹啉的热力学性质。用精密绝热量热仪测定了8-羟基喹啉在78 K ~370 K 温区的低温热容。根据实验测定的热容数据计算出了热容拟合方程及热力学函数,得到该物质的熔点、摩尔熔化焓和摩尔熔化熵分别是(345.74±0.15) K、(13.93±0.11) kJ· mol-1 和 (40.26±0.33) J·K-1·mol-1。 根据热力学函数关系式计算了其在78 K ~370 K 温区每隔5 K 的热力学函数 和 。通过部分熔化实验计算出该样品及其绝对纯物质的熔化温度分别是 345.601 K和345.761 K。根据Van’t Hoff方程计算出该样品纯度的摩尔分数为 0.9978。用DSC技术进一步考察了该物质的热稳定性。