Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.     

Solid Phase Extraction and Determination of Ultra Trace Amounts of Copper using Activated Carbon Modified by N,N′‐Bis(Salicylidene)‐1,2‐Phenylenediamine

Abstract

N,N′‐bis(salicylidene)‐1,2‐phenylenediamine(salophen) modified activated carbon was prepared and used as an effective sorbent for solid phase extraction of Cu(II) ions from aqueous solutions. The salophen modified activated carbon showed a high sorption affinity for Cu(II). In this method a column mode was used for preconcentration of copper(II) in the pH range 3.5–6.5. The retained copper was eluted with 0.1 mol l^?1 EDTA and determined by atomic absorption spectrometry. The calibration graph was linear over the copper concentration in the range 0.05–1.5 µg ml ^?1. Five replicate determination of 0.4 µg ml^?1 of copper(II) gave a mean absorbance of 0.385 with a relative standard deviation of 1.35%. The detection limit was 0.0133 µg ml^?1. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for determination of copper in various real samples.     

Nanostructured manganese oxide–chitosan-based cholesterol sensor

Manganese oxide nano-rod (nano-MnO₂) was prepared by simple oxidation method. To fabricate nanocomposite film (nano-MnO₂/CT) onto glassy carbon electrode (GCE), nano-MnO₂ was homogeneously dispersed in chitosan (CT). Cholesterol oxidase (ChOx) was immobilized onto nano-MnO₂/CT by physisorption. Modified electrode was characterized by Fourier transform infrared, X-ray diffraction, cyclic voltammetry, scanning electron microscopy, transmission electron microscopy, and electrochemical impedance spectroscopy techniques. Prepared ChOx/nano-MnO₂/CT/GCE bioelectrode exhibited 0.03–11.66 mM linearity and 2.07 × 10^?3 mM limit of detection for cholesterol. Biosensing characteristics of modified bioelectrode were superior than other electrodes modified with metal oxide nanoparticles, reported in the literature.     

Construction and Performance Characteristics of Modified Screen Printed and Modified Carbon Paste Sensors for Selective Determination of Cu(II) Ion in Different Polluted Water Samples

Four new ion-selective electrodes (ISEs), based on N,N′-bis(salicylaldehyde)-p-phenylene diamine (SPD) as ionophore, are constructed for the determination of copper(II) ion. The modified carbon paste (MCPEs; electrodes I and II) and modified screen-printed sensors (MSPEs; electrodes III and IV) exhibit good potentiometric response for Cu(II) over a wide concentration range of 1.0 × 10^?6 – 1.0 × 10^?2 mol L^?1 for electrodes (I and II) and 4.8 × 10^?7–1.0 × 10^?2 mol L^?1 for electrodes (III and IV) with a detection limit of 1.0 × 10^?6 mol L^?1 for electrodes (I and II) and 4.8 × 10^?7 mol L^?1 for electrodes (III and IV), respectively. The slopes of the calibration graphs are 29.62 ± 0.9 and 30.12 ± 0.7 mV decade^?1 for electrode (I) (tricresylphosphate (TCP) plasticizer) and electrode (II) (o-nitrophenyloctylether o-NPOE plasticizer), respectively. Also, the MSPEs showed good potentiometric slopes of 29.91 ± 0.5 and 30.70 ± 0.3 mV decade^?1 for electrode (III) (TCP plasticizer) and electrode (IV) (o-NPOE plasticizer), respectively. The electrodes showed stable and reproducible potentials over a period of 60, 88, 120, and 145 days at the pH range from 3 to 7 for electrodes (II), (III), and (IV) and pH range from 3 to 6 for electrode (I). This method was successfully applied for potentiometric determination of Cu(II) in tap water, river, and formation water samples in addition to pharmaceutical preparation. The results obtained agree with those obtained with the atomic absorption spectrometry (AAS).     

Electrochemical determination of malachite green at graphene quantum dots–gold nanoparticles multilayers–modified glassy carbon electrode

A graphene quantum dots–gold nanoparticles–modified glassy carbon electrode was used to investigate the electrochemical behaviors of malachite green (MG). Cyclic voltammetry curves of MG at the modified electrode exhibited a pair of quasi-reversible adsorption-controlled redox peaks at 0.502 V (E _pa) and 0.446 V (E _pc) in a 0.05 mol L^?1 H₂SO₄ solution. Under the optimal conditions, by using differential pulse voltammetry as the detection method, a linear relationship was obtained between the oxidation peak current and the MG concentration in the range of 4.0 × 10^?7 to 1.0 × 10^?5 mol L^?1 with the detection limit as 1.0 × 10^?7 mol L^?1 (signal-to-noise ratio of 3). The modified electrode was applied in the determination of MG in fish samples, and the results were satisfactory with recoveries from 96.25 to 98.00 %. Furthermore, the modified electrode showed very good reproducibility and stability.     

Voltammetric determination of alkannin using an Au nanoparticles–poly(diallyldimethylammonium chloride)-functionalized graphene nanocomposite film

An electrochemical sensor based on Au nanoparticles (AuNPs)–poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene (AuNPs–PDDA-G) nanocomposite was fabricated for the sensitive detection of alkannin. The nanocomposite was characterized by X-ray diffraction, ultraviolet/visible spectra, scanning electron microscopy, and transmission electron microscopy. Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behaviors of alkannin on the AuNPs–PDDA-G nanocomposite film-modified glassy carbon electrode. This electrochemical sensor displayed satisfactory analytical performance for alkannin detection over a range from 5.0 nmol L^?1 to 3.0 μmol L^?1 with a detection limit of 1.4 nmol L^?1 (S/N = 3). Moreover, the sensor also exhibited good reproducibility and stability, and could be used for the detection of alkannin in real samples with satisfactory results.     

Zinc ion-imprinted polymer based on silica particles modified carbon paste electrodes for highly selective electrochemical determination of zinc ions

ABSTRACT

In this study, Zn(II) ion-imprinted polymer was prepared on the surface of vinyl silica particles and applied for detection of Zn(II) ions using differential pulse voltametry. The ion- imprinted polymer particles were prepared by free radical polymerization. The prepared particles were characterized by different morphological and elemental techniques. The ion-imprinted particles were used to fabricate the carbon paste electrode as a zinc ions sensor. The modified zinc sensor showed linear response in the concentration range 6.12 × 10^?9 to 4.59 × 10^?8 mol L^?1. The limit of detection and limit of quantification of the electrode were 1.351 × 10^?8 and 4.094 × 10^?8 mol L^?1, respectively.     

Electropolymerized Poly(3,4-ethylendioxythiophene)/Graphene Composite Film and its Application in Quantum Dots Electrochemiluminescence Immunoassay

Poly(3,4-ethylendioxythiophene) (PEDOT) films have been electrochemically polymerized on graphene (GR) modified glassy carbon electrode (GCE) simply by a one-step cyclic voltammetry (CV) method in an aqueous media in the absence of any surfactant. The PEDOT/GR composite films were characterized by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). This composite film provided an excellent platform for immobilization of antibody with good bioactivity, and conductivity through Au nanoparticles (AuNPs) as a linker. With a sandwich-type immunoassay format, the analyte and then the CdTe quantum dots coated carbon nanosphere (CNS@CdTe)-labeled antibody were successively bound to the immunosensor. The dual-amplification strategy greatly enhanced the sensitivity for point-of-care testing (POCT) of prostate-specific antigen (PSA). Under optimal conditions, the proposed method could detect PSA with a linear range of 0.001–10 ng mL^?1 and a detection limit down to 0.8 pg mL^?1. The assay results of PSA in clinical serum samples from the Tumor Hospital were in acceptable agreement with the reference values from enzyme-linked immunosorbent assay. The proposed ECL immunosensor exhibited high sensitivity and stability, and could be applied in POCT of other tumor markers for remote regions and developing countries.     

Vibrating screen printed electrode of gold nanoparticle-modified carbon nanotubes for the determination of arsenic(III)

A linear sweep anodic stripping voltammetric method using a carbon nanotube–gold nanoparticle-modified vibrating screen printed electrode for the determination of arsenic(III) is reported. The experiments were conducted with a 0.1 mol L^?1 solution of H₂SO₄ in order to estimate the electrode area related to gold oxide formation. The results showed a clear reduction peak at approximately +0.85 V corresponding to the reduction of the gold surface oxide with a superficial area of 0.089 cm². A vibrating motor was attached to the screen printed electrode to create a portable and autonomous system with enhanced mass transfer. The repeatability of the measurements was 2.4 % (n = 10) at the level of 0.5 mg L^?1 of arsenic(III) under the best instrumental operating conditions. The peak current was linearly dependent on the arsenic(III) concentration, thus allowing the construction of a linear analytical curve in the range from 10 to 550 μg L^?1 with the equation: ?I_p (μA) = 0.05 + 134.59 [As(III) (μg L^?1)], R² = 0.99. The obtained detection and quantification limits were 0.5 (3 SD) and 1.5 (10 SD) μg L^?1, respectively, using 120 s as the deposition time. It was shown that Cu(II) does not interfere in the detection of As(III) using the proposed method.     

Molecularly imprinted electrochemical sensor for the determination of ampicillin based on a gold nanoparticle and multiwalled carbon nanotube‐coated pt electrode

A novel molecularly imprinted electrochemical sensor was developed for the sensitive and selective determination of ampicillin (AMP). The sensor was prepared on a platinum electrode modified with multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (AuNPs), and a thin film of molecularly imprinted polymers (MIPs). MWCNTs and AuNPs were introduced to enhance the sensor's electronic transmission and sensitivity. The molecularly imprinted polymer (MIP) was synthesized using AMP as the template molecule, methacrylic acid as functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as cross‐linker. The performance of the proposed imprinted sensor was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The results showed that the imprinted film displayed a fast and sensitive response to AMP. Under optimal conditions, response peak current had a linear relationship with the concentration of AMP in the range of 1.0 × 10^?8 mol/L to 5.0 × 10^?6 mol/L and a detection limit of 1.0 × 10^?9 mol/L (S/N = 3). This imprinted sensor was used to detect AMP in food samples with recoveries of 91.4–105%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40613.     

Gold nanoparticle/carbon nanotube hybrids as an enhanced material for sensitive amperometric determination of tryptophan

In this work, a highly sensitive electrochemical sensor for the determination of tryptophan (Trp) was fabricate by electrodeposition of gold nanoparticles (AuNPs) onto carbon nanotube (CNT) films pre-cast on a glassy carbon electrode (GCE), forming an AuNP-CNT composite-modified GCE (AuNP-CNT/GCE). Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used for the surface analysis of the electrode. The results indicate that the hybrid nanomaterials induced a substantial decrease in the overpotential of the Trp oxidation reaction and exhibited a remarkable synergistic effect on the electrocatalytic activity toward the oxidation of Trp. In phosphate buffer solution (pH 7.4), the modified electrode showed excellent analytical performance for the amperometric determination of Trp. The peak currents possess a linear relationship with the concentration of Trp in the range of 30 nM to 2.5 μM, and the detection limit is 10 nM (S/N = 3). In addition, the modified electrode was used to determine Trp concentration in pharmaceutical samples with satisfactory results.     

Solvent Impregnated Resins containing Quinizarin: Preparation and Application to Batch‐mode Separation of Cd(II), Cu(II), Ni(II), and Zn(II) in Aqueous Media Prior to the Determination by Flame Atomic Absorption Spectrometry

Abstract

Preparation of a high stable solvent impregnated resins (SIR) containing 1,4‐dihydroxyanthraquinone (quinizarin, QNZ) was proposed using Amberlite XAD‐16 beads. The SIR was applied for the separation of Cd(II), Cu(II), Ni(II), and Zn(II) in aqueous media prior to the determination by flame atomic absorption spectrometry (FAAS). The optimum conditions for batch mode extraction of the above metal ions were investigated and it was found that the sorption of these metal ions from a 1000‐ml aliquots of the solution on 1.5 g of the SIR can be carried out quantitatively at pH of 9.5 and an ionic strength of 0.01 mol dm^?3. The sorbed metal ions were subsequently eluted with 10 ml 2 mol dm^?3 HCl and the eluent was subjected to FAAS. Beer's law was obeyed in the range of 9×10^?9 ?1×10^?7 mol dm^?3 for Cd(II) and Zn(II), and 9×10^?8 ?1×10^?6 mol dm^?3 for Cu(II) and Ni(II) contents. Significant interference was not observed due to the various ions, which could be found in natural water samples. The practical applicability of the method was confirmed using a synthetic certificated reference material (CRM) and spiked natural water samples.     

Removal of Cu(II), Fe(III), and Cr(III) from Aqueous Solution by Aniline Grafted Silica Gel

Abstract

The aniline moiety was covalently grafted onto silica gel surface. The modified silica gel with aniline groups (SiAn) was used for removal of Cu(II), Fe(III), and Cr(III) ions from aqueous solution and industrial effluents using a batch adsorption procedure. The maximum adsorption of the transition metal ions took place at pH 4.5. The adsorption kinetics for all the adsorbates fitted better the pseudo second‐order kinetic model, obtaining the following adsorption rate constants (k₂): 1.233 · 10^?2, 1.902 · 10^?2, and 8.320 · 10^?3 g · mg^?1 min^?1 for Cr(III), Cu(II), and Fe(III), respectively. The adsorption of these transition metal ions were fitted to Langmuir, Freundlich, Sips, and Redlich‐Peterson isotherm models; however, the best isotherm model fitting which presented a lower difference of the q (amount adsorbed per gram of adsorbent) calculated by the model from the experimentally measured, was achieved by using the Sips model for all adsorbates chosen. The SiAn adsorbent was also employed for the removal of the transition metal ions Cr(III) (95%), Cu(II) (95%), and Fe(III) (94%) from industrial effluents, using the batch adsorption procedure.     

EDTA modified glassy carbon electrode: Preparation and characterization

EDTA-phenoxyamide modified glassy carbon electrode (EDTA-GC) was prepared at a glassy carbon electrode by surface synthesis. In the first step, nitrophenyl was grafted to the glassy carbon (GC) surface via the electrochemical reduction of its tetraflouroborate diazonium salt. In the second step, nitrophenyl-modified electrode (NP-GC) was subjected to the cathodic potential scan to reduce the nitro to amine group. p-Aminophenyl modified glassy carbon electrode (AP-GC) was dipped into a EDTA solution containing 1-ethyl-3(3-(dimethlyamino)propyl)-carbodiimide (EDC) as an activating agent. Thus formed ((2-anilino-2-oxoethyl){2-[bis(carboxymethyl)amino]-ethyl}amino)acetic acid modified GC electrode was denoted as EDTA-GC and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry and X-ray photoelectron spectroscopy (XPS). Complexation of the EDTA-GC surface with Pb²⁺ ions was investigated if this electrode could be used as a metal sensor.     

Electrochemical modification of glassy carbon electrode by poly-4-nitroaniline and its application for determination of copper(II)

Electrochemical modification of glassy carbon (GC) electrode by poly-4-nitroaniline (P4NA), electrochemical reduction of P4NA and applicability of electrode modified in this way for determination of copper(II) (Cu(II)) is reported in this study. Electrochemical surface modification was performed by cyclic voltammetry in the potential range between +0.9 V and +1.4 V vs. Ag/Ag⁺ (in 10 mM AgNO₃) at the scan rate of 100 mV/s by 100 cycles in non-aqueous media. In order to provide electrochemical reduction of nitro groups on the P4NA-modified GC electrode surface (P4NA/GC), the cyclic voltammograms inducing/evidencing the reduction of nitro groups were performed in the potential range between −0.1 V and −0.8 V vs. Ag/AgCl/(sat.KCl) at the scan rate of 100 mV/s. The reduced P4NA/GC surfaces (Reduced-P4NA/GC) were treated with aqueous solution of nitrilotriacetic acid. The sensitivity of GC electrode modified in described way towards Cu(II) was investigated in Britton-Robinson buffer solution, pH 5.0. The potentiometric generic pulse technique was applied as innovative electrochemical method for detection of analytical signal. It was shown that GC electrodes modified in here described way will be suitable for the determination of Cu(II) in technological waste water and/or some other solutions containing Cu(II) ions.     

Electrocatalysis of gold nanoparticles/layered double hydroxides nanocomposites toward methanol electro-oxidation in alkaline medium

A nanocomposite based on layered double hydroxides (LDHs) and gold nanoparticles (AuNPs) was prepared via hydrothermal treatment followed by a reduction procedure. The AuNPs were obtained in Mg-Al LDHs, and they maintained good stability. The electrocatalytic activities of AuNPs/LDH-modified glassy carbon electrodes for methanol oxidation in alkaline medium were investigated in detail. Under the same conditions, the modified electrode exhibited higher electrocatalytic activity than both the pure AuNPs-modified electrode and LDH-modified electrode. The role of the AuNPs and LDHs in this composite system was explored by cyclic voltammetry and chronoamperometry, respectively. Further studies demonstrated that the promoting effect of LDHs could be due to its strong adsorption and partly to the discharge of OH⁻ during methanol oxidation. This work indicates that LDHs is expected to be a good supporting material in the development of methanol anode catalysts.     

Poly(crystal violet)/graphene-modified electrode for the simultaneous determination of trace lead and cadmium ions in water samples

A novel poly(crystal violet)/graphene-modified glassy carbon electrode (PCV/Gr/GCE) was fabricated for the simultaneous determination of Pb²⁺ and Cd²⁺. The electrochemical behavior of both species at the PCV/Gr/GCE was investigated employing cyclic voltammetry. In acetate buffer, the modified electrode showed an excellent electrocatalytical effect on the oxidation of both species and was further used for their determination. Under optimized analytical conditions, the oxidation peak currents of Pb²⁺ and Cd²⁺ obtained by differential pulse voltammetry in pH 4.6 acetate buffer showed a linear relationship with their concentrations in the ranges of 2.00 × 10^?8–1.95 × 10^?5 mol L^?1 and 4.00 × 10^?8–5.58 × 10^?5 mol L^?1, respectively. The developed method has excellent sensitivity, selectivity, reproducibility and has been successfully applied to the determination of Pb²⁺ and Cd²⁺ in water samples.     

Simultaneous determination of catechol and hydroquinone based on poly(sulfosalicylic acid)/functionalized graphene modified electrode

A glassy carbon electrode (GCE) modified with poly(sulfosalicylic acid) (PSA) and poly(diallyldimethylammonium chloride)-graphene (PDDA-GN) was prepared by a simple self-assembly method. The formation of films was ascribed to the electrostatic force between negatively charged PSA and positively charged PDDA-GN as well as the π–π stacking interaction between PSA and PDDA-GN. The as prepared films were characterized by scanning electron microscopy (SEM), Raman spectroscopy and electrochemical methods. Under the optimized condition, the modified GCE showed two well-defined redox waves for catechol (CT) and hydroquinone (HQ) in cyclic voltammetry (CV) with a peak potential separation of 111 mV, which ensured the anti-interference ability of the electrochemical sensor and made simultaneous determination of dihydroxybenzene isomers possible in real samples. The corresponding oxidation currents increased remarkably compared with those obtained at the bare GCE, PSA/GCE and PDDA-GN/GCE, respectively. Differential pulse voltammetry (DPV) was used for the simultaneous determination of CT and HQ. The anodic peak current of CT was linear in the concentration from 1 × 10^?6 to 4 × 10^?4 M in the presence of 3 × 10^?5 M HQ, and the detection limit was 2.2 × 10^?7 M (S/N = 3). At the same time, the anodic peak current of HQ was linear in the concentration from 2 × 10^?6 to 4 × 10^?4 M in the presence of 2 × 10^?5 M CT, and the detection limit was 3.9 × 10^?7 M (S/N = 3). The proposed method was applied to simultaneous determination of CT and HQ in tap water with satisfactory results. These results indicated that PSA/PDDA-GN is a promising modified material with great potential in electrocatalysis and electrochemical sensing.     

Amperometric biosensor for nitrite and hydrogen peroxide based on hemoglobin immobilized on gold nanoparticles/polythionine/platinum nanoparticles modified glassy carbon electrode

BACKGROUND: This paper describes a convenient and effective strategy to construct a highly sensitive amperometric biosensor for nitrite (NO₂^?) and hydrogen peroxide (H₂O₂). First, Pt nanoparticles (PtNPs) were electrodeposited on a glassy carbon electrode (GCE) surface, which promoted electron transfer and enhanced the loading of poly‐thionine (PTH). Subsequently, thionine (TH) was electropolymerized on the PtNPs/GCE, and gold nanoparticles (AuNPs) were assembled onto the PTH film to improve the absorption capacity of hemoglobin (Hb) and further facilitate electron transfer. Finally, Hb was immobilized onto the electrode through the AuNPs. RESULTS: Cyclic voltammetry (CV) and scanning electron microscopy (SEM) were used to characterize the fabrication process of the sensing surface. Under optimum conditions, the biosensors can be used for the determination of NO₂^? in the concentration range 70 nmol L^?1 to 1.2 mmo L^?1 and of H₂O₂ in the range 4.9 µmol L^?1 to 6.8 mmol L^?1. The detection limits (S/N = 3) were 20 nmol L^?1 and 1.4 µmol L^?1, respectively. CONCLUSION: The biosensor exhibits good analytical performance, acceptable stability and good selectivity. Copyright © 2011 Society of Chemical Industry     

A simple and sensitive electroanalytical determination of anxiolytic buspirone hydrochloride drug based on multiwalled carbon nanotubes modified electrode

In the present study, a simple and sensitive buspirone hydrochloride (BPH) sensor was developed based on multiwalled carbon nanotubes (MWCNT) modified electrode. The modified electrode was characterized using transmission electron microscopy and electrochemical impedance spectroscopy. The MWCNT modified electrode showed an enhanced oxidation peak current response toward BPH than unmodified electrode. The oxidation peak potential of BPH at modified electrode was 0.85, which was quite lower than that of bare electrode (0.88 V). The BPH was successfully determined at modified electrode using different electrochemical methods, such as cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometry. The good sensitivity and linear range response of BPH were obtained using amperometry when compared with other methods employed in this study (CV and DPV). The modified electrode displayed the electro-oxidation of BPH in the linear response from 0.5 to 99.5 μM with the sensitivity of 16.49 μA μM^?1 cm^?2. The limit of detection was calculated as 0.22 μM. In addition, the modified electrode exhibited a good repeatability and repeatability with acceptable stability.