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.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate

Raman spectroscopy has exhibited the C–H stretch (A₁ mode) frequency ν₁ of hydrated methanes at 2915 cm⁻¹ for the 5¹² cage and 2905 cm⁻¹ for the 5¹²6² cage. These values are lower than the frequency of 2916.5 cm⁻¹ in gaseous methane. In this paper, we theoretically examine the Raman spectra observed in methane hydrate by normal mode analysis using the independent molecule model. By a breakdown of the symmetry, the four frequencies in modes A₁, E, T₂ and T₂ observed in gaseous methane are separated into nine frequencies in the hydrate. It is necessary to consider the anharmonic potential energy within methane and hydrogen bonding between methane hydrogen and water oxygen in order to get a result in qualitative agreement with experiment. The frequency in the 5¹²6² cage is shifted downward in comparison to the one in 5¹², and the frequencies in the both cages are also shifted downward compared with the frequencies in gas. Calculations are also reported for the isotopic methane (CD₄, ¹³CH₄) hydrates.     

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.     

Integrated optical pH sensor using replicated chirped grating coupler sensor chips

Integrated optical sensor chips suitable for high-resolution pH measurements are presented. The pH-sensitive swelling of a polymer membrane is detected by refractometry using a compact multi-channel sensor module. The signal transduction is achieved by means of chirped grating couplers which allow simple yet high functionality sensor modules to be built. The experiments have been performed with high sensitivity replicated polycarbonate TiO₂ waveguide sensor chips coated with an ultrathin photopatterned hydrogel membrane having functional groups which reversibly change from the neutral state to a charged state upon acidification. A resolution δpH <±1.1×10⁻⁴ in terms of the pH (at pH 7.5) has been obtained in a dual-channel module with size 10×10×10 cm³.     

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.     

Trace detection of nitroaromatic compounds with layer-by-layer assembled {SBA/PSS}n/PDDA modified electrode

The {SBA/PSS}_n/PDDA films modified electrode was prepared by layer-by-layer (LBL) assembly with mesoporous SiO₂ (SBA), poly(sodium 4-styrene-sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDDA) in this paper. SBA is a large pore-size mesoporous material with highly ordered hexagonally arranged mesochannels and high thermal stability etc. The electrochemical characteristics of the {SBA/PSS}_n/PDDA films have been studied by electrochemical impedance spectroscopy in 0.1 M KCl solution containing 5.0 mM Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ at the formal potential of 0.230 V. The ultratrace nitroaromatic compounds (NACs) such as TNT, TNB, DNT and DNB were determined by differential pulse voltammetry (DPV) measurement. The sensitivities for NACs determination with {SBA/PSS}_n/PDDA modified electrode were dependent on the number of layers, pH and ionic strength of electrolyte, based on which a set of optimized conditions for film fabrication was inferred. The current responses were linear with NACs ranging from 10⁻⁹ to 10⁻⁷ mol/l. The results showed that the {SBA/PSS}_n/PDDA modified electrode established a new way for fast, simple and sensitive analysis of NACs.     

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.     

LTCC compatible PLZT thick-films for piezoelectric devices

The production of PLZT thick-films for piezoelectric devices prepared from perovskite-type (Pb, La)(Zr, Ti)O₃ powders is described. The powder manufacture, paste preparation and thick-film production compatible with the low temperature co-fired ceramics (LTCC) process are detailed. The maximum firing temperature of applied technology is 850 °C. Measurements of the dielectric and piezoelectric properties of the produced films are carried out. The low dielectric loss (0.022) and high d₃₃ and d₃₁ piezoelectric coefficients (85.7×10⁻¹² and −34.6×10⁻¹² m/V, respectively) of the material, together with a relatively low sintering temperature, make it suitable for various applications, e.g. ultrasonics.     

Biinfinite words with maximal recurrent unbordered factors

A finite non-empty word z is said to be a border of a finite non-empty word w if w=uz=zv for some non-empty words u and v. A finite non-empty word is said to be bordered if it admits a border, and it is said to be unbordered otherwise. In this paper, we give two characterizations of the biinfinite words of the form ^ωuvu^ω, where u and v are finite words, in terms of its unbordered factors.

The main result of the paper states that the words of the form ^ωuvu^ω are precisely the biinfinite words w=a₋₂a₋₁a₀a₁a₂ for which there exists a pair (l₀,r₀) of integers with l₀<r₀ such that, for every integers ll₀ and rr₀, the factor a_la_l0a_r0a_r is a bordered word.

The words of the form ^ωuvu^ω are also characterized as being those biinfinite words w that admit a left recurrent unbordered factor (i.e., an unbordered factor of w that has an infinite number of occurrences “to the left” in w) of maximal length that is also a right recurrent unbordered factor of maximal length. This last result is a biinfinite analogue of a result known for infinite words.     

Metallic thin-film thermocouple for thermoelectric microgenerators

A new metallic thin-film thermocouple orientated towards thermoelectric microgenerators has been developed. It consists of a 3 μm thick NiCr/SiO₂/Sb multilayer structure sputter deposited onto a thermally oxidized silicon substrate. A relative Seebeck coefficient of _ab = 76 μV K⁻¹ and an optimal figure of merit of z_ab = 0.08 × 10⁻³ K⁻¹ have been measured for this material combination. Both parameters are very close to the theoretical values.     

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.     

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.     

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.     

Thin-film thermocouples of Ge doped with Au and B

High thermoelectric power (S300 μV K⁻¹;ρ10⁻⁴ Ω m) has been achieved for germanium layers doped with gold deposited by evaporation. The relative simplicity and good reproducibility of the method seems to be promising for thermopiles in some types of microsensors.     

Fabrication of improved piezoresistive silicon cantilever probes for the atomic force microscope

This paper describes an improved design for a monolithic silicon atomic force microscope (AFM) probe using piezoresistive sensing. The probe is V shaped, with a sharp tip at the free end and two piezoresistors at the root, and is fabricated using silicon-on-insulator (SOI) starting material. The maximum sensitivity of the AFM probe is measured to be 4.0(± 0.1) × 10⁻⁷ Å⁻¹, which is larger than that of the previous parallel-arm piezoresistive AFM probe. The measured results are in reasonable agreement with the values predicted by theory. The minimum detectable force and minimum detectable deflection of the AFM probes are predicted to be 1.0 × 10⁻¹⁰ N and 0.29 Å_r.m.s., respectively, using a Wheatstone bridge arrangement biased at a voltage of ± 5 V and bandwidth of 10 Hz–1 kHz.     

Manganese(II)-selective PVC membrane electrode based on a pentaazamacrocyclic manganese complex

Manganese(II) complex of 14,16-dimethyl-1,4,7,10,13-pentaazacyclohexadeca-13,16-diene [Me₂(16)dieneN₅] (I) was synthesized and used in the fabrication of Mn²⁺-selective ISE membrane in PVC matrix. The membrane having Mn(II) macrocyclic complex as electroactive material along with sodium tetraphenylborate (NaTPB) as anion discriminator and dioctylphthalate (DOP) as plasticizer in poly(vinylchloride) (PVC) matrix was prepared for the determination of Mn²⁺. The best performance was observed by the membrane having Mn(II) complex–PVC–NaTPB–DOP in the ratio 1:5:1:3. The sensor worked well over a concentration range of 1.25 × 10⁻⁵ to 1.0 × 10⁻¹ M between pH 3.0 and 8.0 and had a fast response time of 20 s with a lifetime of 4 months. Their performance in partially non-aqueous medium was found satisfactory up to 30% (v/v) alcoholic content. Electrodes exhibited excellent selectivity for Mn²⁺ ion over other mono-, di-, trivalent cations. It can also be used as indicator electrode in the potentiometric titration of Mn²⁺ against EDTA.     

Thermal expansion of Chromium (Cr) to melting temperature

In situ x-ray data on molar volumes of chromium have been collected over the temperature range from 300 K to melting. The sample was heated to melting by passing an electrical current through the sample (the technique of electrical resistance wire heating). The sample consists of a tungsten wire as a heater and a mixture of Cr and W powder, which is placed in a hole of 250 μm diameter. Tungsten was used as an internal standard for temperature determination. In order to prevent the specimen from oxidation, the experiments were carried out in an argon flow. Unit cell parameters of Cr at different temperatures were calculated using (110), (200), (211), and (220) reflections. Precision of determination of lattice parameter is 10⁻⁴ A at 300 K and 5 10⁻⁴ A at 2000 K. Thermal expansion of Cr increases rapidly at temperatures higher than 1200 K. The linear thermal expansion () of chromium between 300 and 2130 K is given by: = 1.220(5) 10⁻⁵ − 1.150(6) 10⁻⁸ T + 1.132(8) 10⁻⁶ T² − 0.507(7)/T² (T, K). In our experiments, Cr melted between 2120 and 2150 K.     

Development of a bienzyme system based on sugar–lectin biospecific interactions for amperometric determination of phenols and aromatic amines

Bienzyme electrode with horseradish peroxidase (HRP) and glucose oxidase (GOD) multilayers was constructed based on sugar–lectin biospecific interactions for amperometric determination of phenolic compounds and aromatic amines. Atomic force microscopy (AFM) was applied to monitor the uniform layer-by-layer assembly of concanavalin A (Con A) and HRP or GOD on polyelectrolyte precursor film-modified Au electrode. Substituted phenolic compounds and aromatic amines could be determined with in situ generation of H₂O₂ by GOD-catalyzed oxidation of glucose. The parameters of the biosensor including the number of assembled HRP and GOD layer, and the concentrations of glucose were optimized. The linear range for the determination of catechol and p-phenyldiamine was 6.0–60.0 μmol L⁻¹ and 7.6–68.4 μmol L⁻¹ with detection limit of 0.9 μmol L⁻¹ and 0.4 μmol L⁻¹, respectively. The biosensor possessed high sensitivity and fast response for phenolic compounds and 95% of the maximum response could be reached in about 3 s. Glucose, ascorbic acid, tartaric acid, citric acid and starch exhibited no interference for the detection. The biosensor presented high stability due to the design for in situ generation of H₂O₂ with bienzyme system.     

A simple approximation for the Erlang loss function

In this paper we present a simple non-iterative computational procedure for approximating the Erlang loss function B(N, ). It is applicable to the practical range 10⁻⁵<B(N, )<10⁻¹ and gives results that are within 10% of the exact values. The formula can be computed on a pocket calculator in constant time and could be used to approximately compute B(N, ) for systems of practically any size.     

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.