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.     

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.     

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).     

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.     

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.     

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.     

Silicon condenser microphones with corrugated silicon oxide/nitride electret membranes

Corrugated electret membranes are used in a micromachined silicon microphone. The membranes consist of a permanently corona-charged double layer of silicon dioxide and silicon nitride, known to have excellent charge-storing properties. This electret can replace the external bias needed for condenser microphones. The well-known LOCOS technique—also combined with dry etching—is used for the first time to fabricate membranes with corrugation depths of several microns. The membrane thickness amounts to 600 nm.

The interferometrically measured center deflection is up to 40 nm/Pa for diaphragms with four corrugations of up to 3.3 μm depth and a size of A_M=1 mm². This high mechanical sensitivity limits the dynamic range to sound pressures below 50 Pa. The obtained mechanical sensitivities are in excellent agreement with the theory.

The most compliant corrugated diaphragms result in a microphone sensitivity of 2.9 mV/Pa, an equivalent noise level of 39 dB(A) and a total harmonic distortion below 1.7% at 28 Pa (123 dB SPL). The corrugation depth in the sensors has been only 1.3 μm. All sensors cover the whole audio and low ultrasonic range. The temperature coefficient is between 0.05 and 0.1 dB/K.     

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.     

3-D manipulation of millimeter- and micro-sized objects using an acoustically excited oscillating bubble

This communication describes novel 3-D manipulations of objects using an acoustically excited oscillating bubble deposited on a hydrophobic rod tip. The oscillating bubble captures various millimeter- and micron-sized neighboring objects including glass and polystyrene beads (~100 μm), fish egg, and live water flea (~1 mm). The captured objects are carried in a 3-D space by traversing the bubble tip, and released at desired positions by simply turning off the oscillation. Carrying performance is characterized along with high-speed imaging of oscillating bubbles by varying the frequency and amplitude of the acoustic excitation and the carrying speed. The higher the oscillation amplitude, the higher the carrying efficiency. The maximum carrying speed is measured at over 3 mm/s. This method is effective with a low-level acoustic excitation (bubble oscillation amplitude relative to the diameter ≤5%), possibly providing a cost-effective, soft-contact manipulating tool for handling biological objects.     

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.     

PECVD-SiOxNy films for large area self-sustained grids applications

In this work we study the structural properties and mechanical stress of silicon oxynitride (SiO_xN_y) films obtained by plasma enhanced chemical vapor deposition (PECVD) technique at low temperatures (320 °C) and report the feasibility of using this material for the fabrication of large area self-sustained grids. The films were obtained at different deposition conditions, varying the gas flow ratio between the precursor gases (N₂O and SiH₄) and maintaining all the other deposition parameters constant. The films were characterized by ellipsometry, by Fourier transform infrared (FT-IR) spectroscopy and by optically levered laser technique to measure the total mechanical stress. The results demonstrate that for appropriated deposition conditions, it is possible to obtain SiO_xN_y with very low mechanical stress, a necessary condition for the fabrication of mechanically stable thick films (up to 10 μm). Since this material (SiO_xN_y) is very resistant to KOH wet chemical etching it can be utilized to fabricate, by silicon substrate bulk micromachining, very large self-sustained grids and membranes, with areas up to 1 cm² and with thickness in the 2–6 μm range. These results allied with the compatibility of the PECVD SiO_xN_y films deposition with the standard silicon based microelectronic processing technology makes this material promising for micro electro mechanical system (MEMS) fabrication.     

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.     

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.     

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.     

Preconcentration and voltammetric analysis of mercury(II) at a carbon paste electrode modified with natural smectite-type clays grafted with organic chelating groups

This study is devoted to the evaluation of a carbon paste electrode modified by a natural 2:1 phyllosilicate clay functionalized with either amine or thiol groups as a sensor for mercury(II). Functionalization was achieved by grafting the pristine clay via its reaction with 3-aminopropyltriethoxysilane (APTES) or 3-mercaptopropyltrimethoxysilane (MPTMS), respectively. The electroanalytical procedure comprises two steps: the chemical accumulation of the analyte under open-circuit conditions followed by the electrochemical detection of the preconcentrated species using differential pulse anodic stripping voltammetry. The different parameters that govern the two steps (accumulation time, concentration of the analyte, composition of the detection medium, potential and duration of electrolysis) were studied in detail. After optimization, a linear response was obtained in the concentration range from 0.1 to 0.7 μM Hg(II). In these conditions, the detection limits of the method were found to be 8.7 × 10⁻⁸ and 6.8 × 10⁻⁸ M, respectively, for the amine- and thiol-functionalized clays, on the basis of a signal-to-noise ratio of 3. The effect of potential interference on the determination of Hg(II) by the carbon paste electrode modified with the thiol-functionalized clay was also studied and the applicability of the method to real sample analysis was evaluated.     

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.     

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.     

Computation of a high Reynolds number jet and its radiated noise using large eddy simulation based on explicit filtering

An isothermal circular jet with a Mach number of M = 0.9 and a Reynolds number of Re_D = 4 × 10⁵ is computed by compressible large eddy simulation (LES). The LES is carried out using an explicit filtering to damp the scales discretized by less than four grid points without affecting the resolved large scales. The jet features are thus found not to appreciably depend on the filtering procedure. The flow development is also shown from simulations on different grids to be independent of the location of the grid boundaries. The flow and the sound field obtained directly by LES are compared to measurements of the literature. The acoustic radiation especially displays spectra and azimuthal correlation functions which behave according to the observation angle as expected for a high Reynolds number. Furthermore the two components of jet noise usually associated to large structures and to fine-scale turbulence, respectively, are apparently found.     

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.