Simultaneous determination of lead and cadmium at a glassy carbon electrode modified with Langmuir–Blodgett film of p-tert-butylthiacalix[4]arene

A glassy carbon electrode (GCE) modified with a Langmuir–Blodgett (LB) film of p-tert-butylthiacalix[4]arene (TCA) has been investigated as a disposable sensor for measuring the trace levels of lead and cadmium. The possibility of determining lead and cadmium at trace levels was examined with differential pulse stripping voltammetry in the measurement step. The electrochemical response was characterized with respect to supporting electrolyte, pH of solution, accumulation time, accumulation potential, layers of the LB films, and possible interferences. Calibration plots were found to be linear in the range 2 × 10⁻⁷ to 5 × 10⁻⁵ mol l⁻¹ (Cd²⁺) and 1 × 10⁻⁷ to 2.5 × 10⁻⁵ mol l⁻¹ (Pb²⁺); the detection limits were 2 × 10⁻⁸ mol l⁻¹ (Cd²⁺) and 8 × 10⁻⁹ mol l⁻¹ (Pb²⁺). Possible recognition mechanism was also discussed. From the analysis of real samples (river, lake and tap water) it can be concluded that the method is sensitive and reproducible in determining of these elements and can be used in the analysis of natural water samples.     

A selective modified bentonite–porphyrin carbon paste electrode for determination of Mn(II) by using anodic stripping voltammetry

A novel voltammetric sensor based on chemically modified bentonite–porphyrin carbon paste electrode (MBPCE) has been introduced for the determination of trace amount of Mn(II) in wheat flour, wheat rice and vegetables. In this method Mn(II) gives well-defined voltammetric peak at the pH range of 3.5–7.5. For the preliminary screening purpose, the catalyst was prepared by modification of bentonite with porphyrin and characterized by thermogravimetric method (TG) and UV–vis spectroscopy. The detection limit (three times signal-to-noise) with 4 min accumulation is 1.07 × 10⁻⁷ mol L⁻¹ Mn(II). The peak currents increases linearly with Mn(II) concentration over the range of 6.0 × 10⁻⁷ to 5.0 × 10⁻⁴ mol L⁻¹ (r² = 0.9959). Statistical treatment of the results gave a relative standard deviation lower than 2.30%. The chemical and instrumental parameters have been optimized and the results showed that 1000-fold excess of the additive ions had not interferences on the determination of Mn(II).     

Perchlorate selective membrane electrodes based on synthesized platinum(II) complexes for low-level concentration measurements

Three synthesized platinum(II) complexes, [PtR₂(NN)] (R = Me, p-MeC₆H₄ and p-MeOC₆H₄; NN = 2,2′-bipyridyl), were studied to characterize their ability as an anion carrier in a PVC membrane electrode. The polymeric membrane electrodes (PME) and also coated glassy carbon electrodes (CGCE) prepared with [Pt(p-MeOC₆H₄)₂(NN)] showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to ClO₄⁻ ions over a wide concentration range from 5 × 10⁻⁷ to 4.0 × 10⁻¹ M for PME and 1.5 × 10⁻⁷ to 2.7 × 10⁻¹ M for CGCE with low detection limits (4.0 × 10⁻⁷ M for PME and 1.0 × 10⁻⁷ M for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward ClO₄⁻ relative to a variety of other common anions. The potentiometric response of the electrodes is independent of the pH of the test solution in the pH range 2.5–9.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water, urine samples and also samples containing interfering anions. The interaction of the ionophore with perchlorate ions was shown by UV–vis spectroscopy.     

Adsorptive voltammetry of Hg(II) ions at a glassy carbon electrode coated with electropolymerized methyl-red film

The glassy carbon electrode coated with electropolymerized methyl-red film, 1.2 × 10⁻⁶ m in thickness, (PMRE) showed high sensitivity towards Hg(II) ions. PMREs were adopted to accumulate and detect Hg(II) ions in a pH 2.56 Britton–Robinson buffer solution. Cyclic voltammogram of the accumulated Hg species on PMREs exhibited an anodic wave at 0.64 V and a cathodic wave at 0.13 V, due to the oxidation of accumulated Hg species on PMREs and the reduction of Hg(II) ions in the solution, respectively. For this heterogeneous adsorption of Hg(II) ions onto PMREs, the maximum surface concentration, adsorption equilibrium, and Gibbs energy change were evaluated to be 5.12 × 10⁻⁶ mol m⁻², 3.7 × 10⁵ l mol⁻¹, and −30.1 kJ mol⁻¹, respectively. The anodic peak current at 0.64 V was linear with the concentration of Hg(II) ions in the range of 1.1 × 10⁻¹⁰ to 1.1 × 10⁻⁷ M with a detection limit of 4.4 × 10⁻¹¹ M. The proposed method was utilized successfully for the detection of Hg(II) ions in the lake water.     

A novel potentiometric membrane sensor for determination of Co based on 5-amino-3-methylisothiazole

A new poly(vinylchloride) (PVC) membrane electrode for trace level determination of Co²⁺ ions has been developed based on 5-amino-3-methylisothiazole as an ionophore, o-nitrophenyloctylether as a plasticizer and oleic acid (OA) as a good lipophilic additive. The electrode exhibits a Nernstian slope of 29.5 ± 0.2 mV/decade in a linear range of 1.0 × 10⁻¹ to 6.3 × 10⁻⁷ M for Co²⁺ ions. The detection limit of this electrode is 3.9 × 10⁻⁷ M. It has a fast response time of 12 s and can be used for a period of 4 months without any divergence in potentials. The proposed electrode reveals a good selectivity for Co (II) over a wide variety of other tested cations and could be used in the pH range 3.3–9.0. The electrode was successfully applied as an indicator electrode for the potentiometric titration of cobalt ions with EDTA as well as for the direct determination of Co (II) in real samples.     

Nano levels detection of beryllium by a novel beryllium PVC-based membrane sensor based on 2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetra oxacyclododecine-12-carbaldehyde-12-(2,4-dinitrophenyl)hy

A novel poly(vinyl chloride)-based 2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetra oxacyclododecine-12-carbaldehyde-12-(2,4-dinitrophenyl)hy (PBC) with sodium tetraphenyl borate (NaTPB) as an anion excluder, benzyl acetate (BA), acetophenon (AP) and o-nitrophenyloctyl ether (NPOE) as plasticizing solvent mediators was prepared and investigated as a beryllium selective sensor. The best performance was observed with the membrane having the PVC–NaTPB–NPOE–PBC composition 30%:3%:62%:5%, which worked well over a very wide concentration range (1.0×10⁻⁷ M to 1.0×10⁻¹ M). The sensor exhibits a Nernstian slope of 29.9 mV per decade of Be²⁺ activity. The detection limit of the sensor is 7.0×10⁻⁸ M (630 ppt). The proposed electrode shows excellent discriminating ability toward Be²⁺ ion with regard to alkali, alkaline earth, transition and heavy metal ions. It was successfully applied to the determination of beryllium in a mineral sample.     

Perchlorate-selective membrane sensors based on two nickel-hexaazamacrocycle complexes

The perchlorate salts of nickel(II) complexes of 1,3,5,8,10,13-hexaazacyclotetradecane (1) and 1,8-tert-butyl-1,3,5,8,10,13-hexaazacyclotetradecane (2) were used in construction of PVC based membrane electrodes. These sensors show very good selectivity for ClO₄⁻ ions over a wide variety of anions. These electrodes exhibit Nernstian behavior with the slopes of 59.5 and 59.3 mV per decade for (1) and (2), respectively. The working concentration ranges of the sensors are 1.0 × 10⁻¹–9.0 × 10⁻⁷ M (1) and 1.0 × 10⁻¹–5.0 × 10⁻⁷ M (2) with the detection limits of 6.0 × 10⁻⁷ and 2.0 × 10⁻⁷ M, respectively. The response time of the both sensors is very fast, and can be used for 2 (I) and 12 (II) weeks in a pH range of 3.0–11.0. These electrodes were applied to the determination of perchlorate ions in wastewater and cattle urine samples.     

Fluorescence quenching of benzo[k]fluoranthene in poly(vinyl alcohol) film: a possible optical sensor for nitro aromatic compounds

Benzo[k]fluoranthene (BkF) is a condensed multi-ring compounds with high fluorescence quantum yield and Stokes’ shift. Nitro aromatic compounds (NACs) are known to be good electron acceptors and quenchers. The fluorescence quenching of benzo[k]fluoranthene in poly(vinyl alcohol) film by different NACs, e.g. nitrobenzene, m-dinitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrobromobenzene, o-nitroaniline, p-nitrophenol, etc. has been studied. The BkF film shows a strong quenching in the NACs concentration range from 1×10⁻⁴ to 1×10⁻³ M. The Stern–Volmer plots for NACs are found to be non-linear, but regular in this concentration range, which can be used for estimation of these compounds. The typical response time of the sensing film is found to be 2–10 s. The sensor film also shows minimal interference from different organic molecules and has good reversibility and reproducibility. The sensor gives a sensitivity of 1×10⁻⁵ M for p-nitrophenol.     

Fabrication of a highly selective Eu(III) membrane sensor based on a new S–N hexadentates Schiff''s base

A novel potentiometric membrane Eu (III) ion sensor is described based on a new S–N hexadentates Schiff's base, bis(thiophenol)butane2,3-dihydrazone (SNSB). The sensor exhibited a Nernstian response over a concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻² M, with a detection limit of 5.0 × 10⁻⁶ M. The best performance was achieved with a membrane composition of 30% PVC, 63% o-nitrophenyloctyl ether (NPOE), 5% SNSB, and 5% (0.010 mmol) potassium tetrakis(p-chlorophenyl) borate (KTpClPB). It was found that in the pH range of 3.0–8.5, the potential response of the sensor was not affected by the pH. Furthermore, the electrode presented satisfactory reproducibility, very fast response time (<5 s), and relatively good discriminating ability for Eu(III) ions with respect to many common cations and lanthanide ions, including sodium, potassium, magnesium, calcium, copper, nickel, cobalt, zinc, lead, lanthanum, cerium, gadolinium, samarium, ytterbium, presidium, terbium, neodymium, holmium, erbium, thulium, lutetium, dysprosium, iron and chromium metal ions. The sensor was applied to the determination of fluoride ions in two mouth wash preparations and binary mixtures.     

An organically modified sol–gel membrane for detection of lead ion by using 2-hydroxy-1-naphthaldehydene-8-aminoquinoline as fluorescence probe

A fluorescent reagent, 2-hydroxy-1-naphthaldehydene-8-aminoquinoline (HNAAQ) was synthesized, and an organically modified sol–gel membrane for detection of lead ion by using HNAAQ as fluorescence probe was fabricated. Under the optimum conditions, by a coplanar effect and the degree of molecular conjugation due to the complexation of Pb²⁺ with HNAAQ the relative fluorescence intensity I₁₀₀/I₀ of the sensing membrane is linearly increased over the Pb²⁺ concentration range of 1.9 × 10⁻⁷ to 1.9 × 10⁻⁴ mol/L with the detection limit of 8.3 × 10⁻⁸ mol/L. The preparation of this organically modified sol–gel membrane and its characteristics were investigated in detail.     

Development of a highly sensitive and selective optical chemical sensor for batch and flow-through determination of mercury ion

A very sensitive, highly selective and reversible optical chemical sensor (optode) for mercury ion is described. The sensor is based on the interaction of Hg²⁺ with 2-mercapto-2-thiazoline (MTZ) in plasticized PVC membrane incorporating a proton-selective chromoionophore (ETH5294) and lipophilic anionic sites (sodium tetraphenylborate, NaTPB). The membranes were cast onto glass substrates and used for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The sensor could be used in the range 2.0 × 10⁻¹⁰ to 1.5 × 10⁻⁵ M (0.04 ng mL⁻¹ to 3 μg mL⁻¹) Hg²⁺ with a detection limit of 5.0 × 10⁻¹¹ M and a response time of <40 s. It can be easily and completely regenerated by dilute nitric acid solution. The sensor has been incorporated into a home-made flow-through cell for determination of mercury ion in flowing streams with improved sensitivity, precision and detection limit. The sensor showed excellent selectivity for Hg²⁺ with respect to several common alkali, alkaline earth and transition metal ions. The results obtained for the determination of mercury ion in river water samples using the proposed optode was found to be comparable with the well-established cold-vapor atomic absorption method.     

Construction of a highly selective PVC-based membrane sensor for Ce(III) ions

A highly Ce(III) ion-selective poly vinyl chloride (PVC) membrane sensor based on N′-[(2-hydroxyphenyl)methylidene]-2-furohydrazide (NHMF) as an excellent sensing material is successfully developed. The electrode shows a good selectivity for Ce(III) ions with respect to most common cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor exhibits a wide linear response with a slope of 19.4 ± 0.3 mV/decade over the concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻¹ M, and a detection limit of 7.6 × 10⁻⁶ M of Ce(III) ions. The sensor response is independent of pH in the range of 3.5–10.0. The proposed electrode was applied as an indicator electrode in potentiometric titration of Ce(III) ions with EDTA and C₂O₄². It was also successfully applied in the determination of cerium ions in aqueous samples.     

Electrogenerated chemiluminescence sensor for itopride with Ru(bpy)3-doped silica nanoparticles/chitosan composite films modified electrode

A electrogenerated chemiluminescence (ECL) sensor for itopride was developed based on tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺)-doped silica (RuDS) nanoparticles/biopolymer chitosan composites membrane modified glassy carbon electrode (GCE). The RuDS nanoparticles (52 ± 5 nm) were prepared by a modified Stőber synthesis method and were characterized by electrochemical, fluorometric and transmission electron microscopy technology. The Ru(bpy)₃²⁺ encapsulation interior of the silica nanoparticle maintains its electrochemical activities and also reduces Ru(bpy)₃²⁺ leaching from the silica matrix when immersed in water due to the electrostatic interaction. The ECL analytical performances of this ECL sensor for itopride based on its enhancement ECL emission of Ru(bpy)₃²⁺ were investigated in details. Under the optimum condition, the enhanced ECL intensity was linear with the itopride concentration in the range of 1 × 10⁻⁸ to 2 × 10⁻⁵ g/mL (R = 0.9978). The detection limit was 3 × 10⁻⁹ g/mL, and the relative standard deviation was 2.3% for 8 × 10⁻⁸ g/mL itopride (n = 11). The method was successfully applied to the determination of itopride in pharmaceutical and human serum samples with satisfactory results. The as-prepared ECL sensor for the determination of itopride displayed good sensitivity and stability.     

Electrocatalytic oxidation of methanol and other short chain aliphatic alcohols on glassy carbon electrodes modified with conductive films derived from Ni-(N,N′-bis(2,5-dihydroxybenzylidene)-1,2-diaminobenzene)

Complexes of nickel(II) with the ligand N,N′-bis(2,5-dihydroxybenzylidene)-1,2-diaminobenzene (Ni^II-DHS) can be electropolymerized onto glassy carbon surfaces in alkaline solution to give electroactive films strongly adhered on the electrode surface. In alkaline solution, these poly-[Ni^II-DHS]/GC films present the typical voltammetric response of a surface-immobilized redox couple, as can be anticipated for the Ni²⁺/Ni³⁺ transitions into the film. In addition, the films exhibit a potent and persistent electrocatalytic activity towards the oxidation of methanol. The electrocatalytic currents are, at least, 80 times higher than those obtained for the oxidation of methanol at electrodes modified with nickel hydroxide films in alkaline solutions. In addition, the current is proportional to the concentration of methanol from 0.050 to 0.30 μM. The detection limit and the sensitivity were found to be 26 ± 2 nM and 7.4 × 10⁻² ± 6 × 10⁻³ A cm² mol⁻¹ M⁻¹, respectively. Electrodes modified with poly-[Ni^II-DHS]/GC films show a moderate electrocatalytic activity towards the oxidation of other aliphatic short chain alcohols, such as: ethanol, 1-propanol, 2-propanol and n-butanol. In all cases the catalytic currents present linear dependences with the concentration of alcohol in alkaline solution. The analytical properties of these potential alcohol sensors have also been studied.     

Sensitive PAT gene sequence detection by nano-SiO2/p-aminothiophenol self-assembled films DNA electrochemical biosensor based on impedance measurement

Nano-SiO₂/p-aminothiophenol (PATP) film was fabricated by self-assembly and electrodeposition methods. The immobilization and hybridization of DNA on the nano-SiO₂/PATP film were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). EIS was applied to label-free detection of the target DNA according to the increase of the electron transfer resistance (R_et) of the electrode surface after the hybridization of the probe DNA with the target DNA. This DNA electrochemical biosensor showed its own performance of simplicity, good stability, fine selectivity and high sensitivity, and was successfully applied to the detection of the PAT gene sequences by a label-free EIS method. The dynamic detection range was from 1.0 × 10⁻¹¹ to 1.0 × 10⁻⁶ mol/L 20-base sequence of the PAT gene, with the detection limit of 1.5 × 10⁻¹² mol/L. This DNA sensor has a good ability of recognizing single- or double-base mismatched DNA sequence with the complementary DNA sequence.     

DNA hybridization measurement by self-sensing piezoresistive microcantilevers in CMOS biosensor

Understanding the mechanism of how biological reactions produce mechanical loadings is fundamental to biomedical developments. A CMOS biosensor chip is developed to measure in situ the induced surface stress change by DNA hybridization. For 20-mer thiol-modified single stranded DNA (ssDNA), the mechanism of ssDNA attached to gold surface via a sulfur–gold linkage can be investigated by using the Langmuir adsorption model. Experimental results indicate that the immobilization response is less than 1 s, the total number of ssDNA molecules on the cantilever is about 3 × 10¹¹, and the induced surface stress is 0.15 N/m. The surface stress sensitivity of the sensor is about 3.5 × 10⁻⁵ m/N. The estimated adsorption rate of the ssDNA is 0.005 s⁻¹. The biosensor is capable of discriminating complimentary molecular targets and thus may provide a powerful platform for high throughput real-time analysis of DNA.     

Fabrication of a highly selective and sensitive Gd(III)-PVC membrane sensor based on N-(2-pyridyl)-N′-(4-nitrophenyl)thiourea

In this work we report the development of a highly selective and sensitive Gd(III) membrane based on N-(2-pyridyl)-N′-(4-nitrophenyl)thiourea (PyTu4NO₂) as an excellent neutral ion carrier. The Gd(III) sensor exhibits a Nernstian slope of 19.95 ± 0.3 mV per decade over the concentration range of 3.0 × 10⁻⁷ to 1.0 × 10⁻¹ M, and a detection limit of 3.0 × 10⁻⁷ M of Gd(III) ions. The potentiometric response of the sensor is independent of the solution pH in the range of 4.0–9.0. It manifests advantages of low detection limit, fast response time (10 s), and most significantly, very good selectivity with respect to a number of lanthanide ions (La, Ce, Sm, and Eu ions). It can be used at least for a period of 8 weeks without any significant divergences in its potential response. To assess its analytical applicability the proposed Gd(III) sensor was successfully applied as an indicator electrode in the titration of Gd(III) ion solutions with EDTA and for the determination of the fluoride ion in two mouth wash preparations. It was also used for the direct monitoring of Gd(III) ions in binary mixtures.     

A hydrogen peroxide biosensor based on direct electrochemistry of hemoglobin in Hb–Ag sol films

Hemoglobin (Hb) was used as a template to fabricate hemoglobin–silver (Hb–Ag) sol in which the hemoglobin showed direct electrochemistry on a glass carbon (GC) electrode. Ultraviolet–visible (UV–vis) spectra and reflectance absorption infrared (RAIR) spectra suggested that hemoglobin in Hb–Ag sol retained its native secondary structure. Scanning electron microscopy (SEM) demonstrated that the morphology of the Hb film was much different from the Hb–Ag sol film. The Hb–Ag film proved to exhibit a good electrocatalytic activity for the reduction of hydrogen peroxide. Based on this, a novel amperometric hydrogen peroxide biosensor was developed, which showed a sensitive response to the reduction of H₂O₂ without any electron mediator. Under optimum conditions, the biosensor responded linearly to H₂O₂ in the concentration range of 1 × 10⁻⁶ to 2.5 × 10⁻² M with detection limit of 1 × 10⁻⁷ M at 3σ. Moreover, the studied biosensor exhibited high sensibility, good reproducibility, and long-term stability.     

Direct electrochemistry and electrocatalysis of myoglobin immobilized in zirconium phosphate nanosheets film

Myoglobin (Mb) is incorporated on a novel matrix—zirconium phosphate nanosheets (ZrPNS) and immobilized at a glassy carbon electrode surface. UV–vis spectra and electrochemical measurements show that the matrix is well biocompatible and can retain the bioactivity of immobilized Mb. The direct electron transfer between Mb and electrode exhibits a couple of well-defined redox peaks. The cathodic and anodic peaks are located at −0.340 and −0.280 V vs. Ag/AgCl, respectively. The ZrPNS can improve the electron transfer between Mb and electrode with an electron transfer constant of 5.6 s⁻¹. Meanwhile, the catalytic ability of the protein toward the reduction of H₂O₂, O₂, NaNO₂, trichloroacetic acid (TCA) is also studied and a third-generation biosensor is subsequently fabricated. The linear range of biosensor to H₂O₂ is from 8 × 10⁻⁷ to 1.28 × 10⁻⁵ M with the limit detection of 1.4 × 10⁻⁷ M. The small apparent Michaelis–Menten constant (34 μM) suggests that Mb/ZrPNS film performs good affinity with H₂O₂. The biosensor also exhibits acceptable stability and reproducibility. This work paves a way to develop other biologic active materials in this kind of nanosheets for constructing novel biosensors.     

Organic field-effect transistors based on Langmuir–Blodgett films of substituted phthalocyanines

Three substituted phthalocyanines (Pcs), two asymmetrical and one symmetrical, named amino-tri-tert-butyl-phthalocyanine (AmBuPc), 1,8-naphthalimide-tri-tert-butyl-phthalocyanine (NaBuPc), and tetra-iso-propoxy-phthalocyaninato copper(II) (i-Pro-CuPc), were used as semiconductor layers in organic field-effect transistors (OFETs) based on their Langmuir–Blodgett (LB) films. These substituted Pcs possess good solubility in common organic solvents. From the long-wavelength absorption edge of their UV–VIS absorption spectra and their electrochemical data, the highest occupied molecular orbital and the lowest unoccupied molecular orbital were determined and the energy band diagram of their OFETs was deduced. The narrower energy gaps of them indicated stronger electron donor–acceptor ability than other symmetrical Pcs because of the substituents at the peripheral ring. The results of their OFETs demonstrated that the LB films of these substituted Pcs can be used as semiconducting layers of OFETs functioned as p-channel accumulation devices. From the electrical characteristics of their OFETs, the channel carrier mobilities of AmBuPc, NaBuPc and i-Pro-CuPc were calculated to be about 2.84×10⁻⁵, 4.42×10⁻⁴ and 3.25×10⁻⁴ cm² V⁻¹ s⁻¹, respectively.