Amperometric biosensor for hypoxanthine based on immobilized xanthine oxidase on nanocrystal gold–carbon paste electrodes

The preparation and performance of a xanthine oxidase (XOD) biosensor, based on a carbon paste electrode (CPE) modified with electrodeposited gold nanoparticles (nAu), for the amperometric determination of hypoxanthine (Hx) is reported. Different XOD biosensor configurations were evaluated and compared with electrodes constructed by immobilizing XOD onto unmodified CPE and with biosensors prepared using glassy carbon electrodes and gold disk electrodes modified with electrodeposited gold. The XOD–nAu–CPE in which the enzyme was immobilized by cross-linking with glutaraldehyde (GA) and BSA exhibited the highest amperometric signal for Hx. Although Hx detection is usually carried out at potential values of around +600 mV versus Ag/AgCl, the GA–BSA–XOD–nAu–CPE allowed this detection to be carried out at 0.00 V, thus minimizing potential interferences from electrochemically oxidizable substances such as ascorbic acid. Experimental variables concerning the biosensor preparation were optimized. Calibration plots for Hx were constructed with the biosensor operating at +600 mV and at 0.00 V. The detection limit for Hx, 2.2 × 10⁻⁷ mol l⁻¹, obtained using the latter potential value is similar to the best detection limits reported in the literature with other biosensor designs working at much more extreme potentials. The usefulness of the biosensor for the analysis of real samples was demonstrated by determining Hx in sardines and chicken meat.     

Simultaneous determination of epinephrine and ascorbic acid at the electrochemical sensor of triazole SAM modified gold electrode

The electrochemical sensor of triazole (TA) self-assembled monolayer (SAM) modified gold electrode (TA SAM/Au) was fabricated. The electrochemical behaviors of epinephrine (EP) at TA SAM/Au have been studied. The TA SAM/Au shows an excellent electrocatalytic activity for the oxidation of EP and accelerates electron transfer rate. The diffusion coefficient is 1.135 × 10⁻⁶ cm² s⁻¹. Under the optimum experiment conditions (i.e. 0.1 mol L⁻¹, pH 4.4, sodium borate buffer, accumulation time: 180 s, accumulation potential: 0.6 V, scan rate: 0.1 Vs⁻¹), the cathodic peak current of EP versus its concentration has a good linear relation in the ranges of 1.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol L⁻¹ and 1.0 × 10⁻⁵ to 6.0 × 10⁻⁴ mol L⁻¹ by square wave adsorptive stripping voltammetry (SWASV), with the correlation coefficient of 0.9985 and 0.9996, respectively. Detection limit is down to 1.0 × 10⁻⁸ mol L⁻¹. The TA SAM/Au can be used for the determination of EP in practical injection. Meantime, the oxidative peak potentials of EP and ascorbic acid (AA) are well separated about 200 ± 10 mV at TA SAM/Au, the oxidation peak current increases approximately linearly with increasing concentration of both EP and AA in the concentration range of 2.0 × 10⁻⁵ to 1.6 × 10⁻⁴ mol L⁻¹. It can be used for simultaneous determination of EP and AA.     

Perchlorate-selective polymeric membrane electrode based on a cobaloxime as a suitable carrier

A cobaloxime ([chlorobis(dimethylglyoximeato)(triphenylphosphine)] cobalt (III), [Co(dmgH)₂pph₃Cl]) incorporated in a plasticized poly(vinyl chloride) membrane was used to develop a perchlorate-selective electrode. The influence of membrane composition on the electrode response was studied. The electrode exhibits a Nernstian response over the perchlorate concentration range 1.0 × 10⁻⁶ to 1 × 10⁻¹ mol l⁻¹ with a slope of −56.8 ± 0.7 mV per decade of concentration, a detection limit of 8.3 × 10⁻⁷, a wide working pH range (3–10) and a fast response time (<15 s). The electrode shows excellent selectivity towards perchlorate with respect to many common anions. The electrode was used to determine perchlorate in water and human urine.     

Flow-injection determination of iron(III) in soil by biamperometry using two independent redox couples

A flow-injection biamperometric method for the determination of iron(III) has been described. The detector consists of two chambers separated by a salt bridge, and one platinum wire working electrode is embedded in each chamber, respectively. When iron(III) solution and hydrogen peroxide solution simultaneously flow through two chambers, the reduction of iron(III) at one platinum electrode is associated with the oxidation of hydrogen peroxide at the other platinum electrode, forming such a system as similar to a reversible couple one. The biamperometric system can perform the determination of iron(III) without any external potential difference. The linear relationship is obtained from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol l⁻¹ with a detection limit of 6.0 × 10⁻⁷ mol l⁻¹. The proposed method exhibits the satisfactory reproducibility with a relative standard derivation (R.S.D.) of 1.4% for 17 successive determinations of 2.0 × 10⁻⁵ mol l⁻¹ iron(III) and is applied to the determination of iron(III) in soil.     

Using of hydrogen ion-selective poly(vinyl chloride) membrane electrode based on calix[4]arene as thiocyanate ion-selective electrode

A hydrogen ion-selective electrode (ISE) is prepared by using 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetracyanometoxy-calix[4]arene and an investigation about whether it could be used as a thiocyanate ion-selective electrode is made by using its characteristic of becoming thiocyanate sensitive in acidic regions. The electrode of the optimum characteristic has a composition of 1% ionophore, 66% 2-NPOE and 33% poly(vinyl chloride) (PVC). This electrode exhibits a linear response over the range 1.0 × 10⁻¹ to 3.0 × 10⁻⁵ M of thiocyanate with a slope of 52.0 ± 0.2 mV/pSCN. The effects of the pH and the membrane composition are also investigated. The lifetime of the electrode is at least 4 months and its response time is found to be 10–15 s. The selectivity coefficients of some anions are calculated by using mixed solution interference method. Application of the electrode to the potentiometric titration of thiocyanate ion with silver nitrate is reported. There is a good agreement between the results obtained by the proposed electrode and the Mohr method at 95% confidence level.     

Chromium(III)-selective sensor based on tri-o-thymotide in PVC matrix

Tri-o-thymotide (I) has been used as an electroactive material in PVC (poly(vinyl chloride)) matrix for fabrication of chromium(III)-selective sensor. The membrane containing tri-o-thymotide, sodium tetraphenyl borate (NaTPB), dibutyl phthalate (DBP) and PVC in the optimum ratio 5:1:75:100 (w/w) exhibits a working concentration range of 4.0 × 10⁻⁶ to 1.0 × 10⁻¹ M with a Nernstian slope of 20.0 ± 0.1 mV/decade of activity in the pH range of 2.8–5.1. The detection limit of this sensor is 2.0 × 10⁻⁷ M. The electrode exhibits a fast response time of 15 s, shows good selectivity towards Cr³⁺ over a number of mono-, bi- and trivalent cations and can also be used in partially non-aqueous medium (up to 15%, v/v) also. The assembly has been successfully used as an indicator electrode in the potentiometric titration of chromium(III) against EDTA and also to determine Cr(III) quantitatively in electroplating industry waste samples.     

Bi-enzymatic amperometric biosensor for oxalate

The development of a new amperometric biosensor for oxalate utilising two enzymes, oxalate oxidase (OXO) and horseradish peroxidase (HRP), incorporated into carbon paste electrode modified with silica gel coated with titanium oxide containing toluidine blue is described. OXO has been immobilised on silica gel modified with titanium oxide surface using glutaraldehyde for crosslinking. HRP has been immobilised with covalent binding with carbodiimide on graphite powder. The biosensor showed a good performance with a linear response range between 0.1 and 2.0 mmol l⁻¹ of oxalate, fit by the equation i=0.33(±0.04)+2.29(±0.04) [oxalate], where i is the current in μA and [oxalate] is the oxalate concentration in mmol l⁻¹ with a correlation coefficient of 0.998 for n=20. The biosensor could be used for 80 determinations when stored in a succinate buffer at pH 3.8 in a refrigerator. The response time was about 0.5 s. The detection limit, considering three times the noise, was 0.09 mmol l⁻¹ for oxalate. The time for oxalate determination in spinach samples decreased by 3 days when this biosensor was used, compared to the AOAC method.     

Tuning the push–pull configuration for efficient second-order nonlinear optical properties in some chalcone derivatives

Using the density functional theory methods, we effectively tune the second-order nonlinear optical (NLO) properties in some chalcone derivatives. Various unique push–pull configurations are used to efficiently enhance the intramolecular charge transfer process over the designed derivatives, which result in significantly larger amplitudes of the first hyperpolarizability as compared to their parent molecule. The ground state molecular geometries have been optimized using B3LYP/6-311G** level of theory. A variety of methods including B3LYP, CAM-B3LYP, PBE0, M06, BHandHLYP and MP2 are tested with 6-311G** basis set to calculate the first hyperpolarizability of parent system 1. The results of M06 are found closer to highly correlated MP2 method, which has been selected to calculate static and frequency dependent first hyperpolarizability amplitudes of all selected systems. At M06/6-311G** level of theory, the permanent electronic dipole moment (μ_tot), polarizability (α₀) and static first hyperpolarizability (β_tot) amplitudes for parent system 1 are found to be 5.139 Debye, 274 a. u. and 24.22 × 10⁻³⁰ esu, respectively. These amplitudes have been significantly enhanced in designed derivatives 2 and 3. More importantly, the (β_tot) amplitudes of systems 2 and 3 mount to 75.78 × 10⁻³⁰ and 128.51 × 10⁻³⁰ esu, respectively, which are about 3 times and 5 times larger than that of their parent system 1. Additionally, we have extended the structure-NLO property relationship to several newly synthesized chalcone derivatives. Interestingly, the amplitudes of dynamic frequency dependent hyperpolarizability μβ_ω (SHG) are also significantly larger having values of 366.72 × 10⁻⁴⁸, 856.32 × 10⁻⁴⁸ and 1913.46 × 10⁻⁴⁸ esu for systems 1–3, respectively, at 1400 nm of incident laser wavelength. The dispersion behavior over a wide range of change in wavelength has also been studied adopting a range of wavelength from 1907 to 544 nm. Thus, the present work realizes the potential of designed derivatives as efficient NLO-phores for modern NLO applications.     

Bounds for the Roots of Lacunary Polynomials

A polynomial P(X)  = X^d + a_d − 1X^d − 1 + ⋯ is called lacunary when a_d − 1 =  0. We give bounds for the roots of such polynomials with complex coefficients. These bounds are much smaller than for general polynomials.     

The possibility of using C20 fullerene and graphene as semiconductor segments for detection,and destruction of cyanogen-chloride chemical agent

Detection of hazardous chemical species by changing the electrical conductivity of a semiconductor matter is a proposed and applied way for decreasing their subsequent unpleasant effects. Recently, many examples of using inorganic or organic materials, polymeric, and also nano-sized species as sensors were reported in which, in some cases, those matters were strongly affective and suitable.In this project, we have made an assessment on whether the graphene segment or C₂₀ fullerene, able to sense the existence of cyanogen chloride NCCl? In order to gain trustable results, the possible reaction pathways along with the adsorption kinetics were investigated. Moreover, the electronic density of states DOS showed that C₂₀ fullerene senses the existence of cyanogen chloride agent with a clearer signal (ΔE_g = 0.0110 eV) compared to the graphene segment (ΔE_g = 0.0001 eV). Also the adsorption energy calculations showed that cyanogen chloride could be adsorbed by the fullerene in a multi-step process (E_ads1 = −0.852 kcal mol⁻¹; E_ads2 = −0.446 kcal mol⁻¹; E_ads3 = −2.330 kcal mol⁻¹).     

Highly fault-tolerant cycle embeddings of hypercubes

The hypercube Q_n is one of the most popular networks. In this paper, we first prove that the n-dimensional hypercube is 2n − 5 conditional fault-bipancyclic. That is, an injured hypercube with up to 2n − 5 faulty links has a cycle of length l for every even 4 ⩽ l ⩽ 2ⁿ when each node of the hypercube is incident with at least two healthy links. In addition, if a certain node is incident with less than two healthy links, we show that an injured hypercube contains cycles of all even lengths except hamiltonian cycles with up to 2n − 3 faulty links. Furthermore, the above two results are optimal. In conclusion, we find cycles of all possible lengths in injured hypercubes with up to 2n − 5 faulty links under all possible fault distributions.     

Evaluation of response characteristics of resistive oxygen sensors based on porous cerium oxide thick film using pressure modulation method

In order to reduce the response time of resistive oxygen sensors using porous cerium oxide thick film, it is important to ascertain the factors controlling response. Pressure modulation method (PMM) was used to find the rate-limiting step of sensor response. This useful method measures the amplitude of sensor output (H(f)) for the sine wave modulation of oxygen partial pressure at constant frequency (f). In PMM, “break” response time, which is minimum period in which the sensor responds precisely, can be measured. Three points were examined: (1) simulated calculations of PMM were carried out using a model of porous thick film in which spherical particles are connected in a three-dimensional network; (2) sensor response speed was experimentally measured using PMM; and (3) the diffusion coefficient and surface reaction coefficient were estimated by comparison between experiment and calculation. The plot of log f versus log H(f) in the high f region was found to have a slope of approximately −0.5 for both porous thick film and non-porous thin film, when the rate-limiting step was diffusion. Calculations showed the response time of porous thick film was 1/20 that of non-porous thin film when the grain diameter of the porous thick film was the same as the thickness of non-porous thin film. At 973 K, “break” response time (t_b) of the resistive oxygen sensor was found by experiment to be 109 ms. It was concluded that the response of the resistive oxygen sensor prepared in this study was strongly controlled by diffusion at 923–1023 K, since the experiment revealed that the slope of plot of log f versus log H(f) in the high f region was approximately −0.5. At 923–1023 K, the diffusion coefficient of oxygen vacancy in porous ceria (D_V) was expressed as follows: D_V (m²s⁻¹) = 5.78 × 10⁻⁴ exp(−1.94 eV/kT). At 1023 K, the surface reaction coefficient (K) was found to exceed 10⁻⁴ m/s.     

First-order piezoresistance coefficients in heavily doped p-type silicon crystals

The first-order piezoresistance coefficients π₁₁, π₁₂, π₄₄ were calculated for heavily doped p-type silicon crystals. The analytical calculation was carried out within the framework of the three-band model taking into account effect of anisotropy and influence of the spin-orbit split-off band (here the SO band) on shape of heavy and light hole bands as well as direct contribution of the SO band into magnitude of the piezoresistance coefficients. The letter is negligible for shear piezoresistance coefficient π₄₄ but for values of piezoresistance coefficients π₁₁ and π₁₂ its contribution reaches 30%. In correspondence with experimental data the calculated values of piezoresistance coefficients π₁₁ and π₁₂ have opposite signs for scattering by acoustic phonons or by ionized impurities.There is a good agreement between our numerical results (for scattering by ionized impurities) and experimental data for shear piezoresistance coefficient π₄₄ at temperatures 190–375 K. It has been obtained in wide range of impurity concentrations (5 × 10¹⁹–2 × 10²¹ cm⁻³).     

Design,simulation and validation of a novel uncooled infrared focal plane array

This paper describes a novel single-layer bi-material cantilever microstructure without silicon (Si) substrate for focal plane array (FPA) application in uncooled optomechanical infrared imaging system (UOIIS). The UOIIS, responding to the radiate infrared (IR) source with spectral range from 8 to 14 μm, may receive an IR image through visible optical readout method. The temperature distribution of the IR source could be obtained by measuring the thermal–mechanical rotation angle distribution of every pixel in the cantilever array, which is consisted of two materials with mismatching thermal expansion coefficients. In order to obtain a high detection to the IR object, gold (Au) film is coated alternately on silicon nitride (SiN_x) film in the flection beams of the cantilevers. And a thermal–mechanical model for such cantilever microstructure is proposed. The thermal and thermal–mechanical coupling field characteristics of the cantilever array structure are optimized through numerical analysis method and simulated by using the finite element simulation method. The thermal–mechanical rotation angle simulated and thermal–mechanical sensitivity tested in the experiment are 2.459 × 10⁻³ and 3.322 × 10⁻⁴ rad/K, respectively, generally in good agreement with what the thermal–mechanical model and numerical analysis forecast, which offers an effective reference for FPA structure parameters design in UOIIS.     

Theoretical studies on kinetics,mechanism and thermochemistry of gas-phase reactions of HFE-449mec-f with OH radicals and Cl atom

A theoretical study on the mechanism and kinetics of the gas phase reactions of CF₃CHFCF₂OCH₂CF₃ (HFE-449mec-f) with the OH radicals and Cl atom have been performed using meta-hybrid modern density functional M06-2X using 6-31+G(d,p) basis set. Two conformers have been identified for CF₃CHFCF₂OCH₂CF₃ and the most stable one is considered for detailed study. Reaction profiles for OH-initiated hydrogen abstraction are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels. Our calculations reveal that hydrogen abstraction from the CH₂ group is thermodynamically and kinetically more facile than that from the CHF group. Using group-balanced isodesmic reactions, the standard enthalpies of formation for HFE-449mecf and radicals generated by hydrogen abstraction, are also reported. The calculated bond dissociation energies for CH bonds are in good agreement with experimental results. The rate constants of the two reactions are determined for the first time in a wide temperature range of 250–450 K. The calculated rate constant values are found to be 9.10 × 10⁻¹⁵ and 4.77 × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹ for reactions with OH radicals and Cl atom, respectively. At 298 K, the total calculated rate coefficient for reactions with OH radical is in good agreement with the experimental results. The atmospheric life time of HFE-449mec-f is estimated to be 0.287 years.     

On reliability of the folded hypercubes

In this paper, we explore the 2-extra connectivity and 2-extra-edge-connectivity of the folded hypercube FQ_n. We show that κ₂(FQ_n) = 3n − 2 for n ⩾ 8; and λ₂(FQ_n) = 3n − 1 for n ⩾ 5. That is, for n ⩾ 8 (resp. n ⩾ 5), at least 3n − 2 vertices (resp. 3n − 1 edges) of FQ_n are removed to get a disconnected graph that contains no isolated vertices (resp. edges). When the folded hypercube is used to model the topological structure of a large-scale parallel processing system, these results can provide more accurate measurements for reliability and fault tolerance of the system.     

Remote sensing of canopy light use efficiency in temperate and boreal forests of North America using MODIS imagery

Light use efficiency (LUE) is an important variable characterizing plant eco-physiological functions and refers to the efficiency at which absorbed solar radiation is converted into photosynthates. The estimation of LUE at regional to global scales would be a significant advantage for global carbon cycle research. Traditional methods for canopy level LUE determination require meteorological inputs which cannot be easily obtained by remote sensing. Here we propose a new algorithm that incorporates the enhanced vegetation index (EVI) and a modified form of land surface temperature (T_m) for the estimation of monthly forest LUE based on Moderate Resolution Imaging Spectroradiometer (MODIS) imagery. Results demonstrate that a model based on EVI × T_m parameterized from ten forest sites can provide reasonable estimates of monthly LUE for temperate and boreal forest ecosystems in North America with an R² of 0.51 (p < 0.001) for the overall dataset. The regression coefficients (a, b) of the LUE–EVI × T_m correlation for these ten sites have been found to be closely correlated with the average EVI (EVI_ave, R² = 0.68, p = 0.003) and the minimum land surface temperature (LST_min, R² = 0.81, p = 0.009), providing a possible approach for model calibration. The calibrated model shows comparably good estimates of LUE for another ten independent forest ecosystems with an overall root mean square error (RMSE) of 0.055 g C per mol photosynthetically active radiation. These results are especially important for the evergreen species due to their limited variability in canopy greenness. The usefulness of this new LUE algorithm is further validated for the estimation of gross primary production (GPP) at these sites with an RMSE of 37.6 g C m^? 2 month^? 1 for all observations, which reflects a 28% improvement over the standard MODIS GPP products. These analyses should be helpful in the further development of ecosystem remote sensing methods and improving our understanding of the responses of various ecosystems to climate change.     

Development of an optical fibre reflectance sensor for copper (II) detection based on immobilised salicylic acid

Immobilized salicylic acid onto XAD-2 (styrene–divinylbenzene cross-linked copolymer) has been attempted in this study as a reagent phase for the development of an optical fibre copper (II) sensor. The measurements were carried out at a given wavelength of 690.27 nm since it yielded the largest divergence different in reflectance spectra before and after reaction with the analyte element. The optimum response was obtained at pH 5.0. The linear dynamic range of Cu(II) was found within the concentration range of 1.0–2.0 mmol L⁻¹ with its LOD of 0.5 mmol L⁻¹. The sensor response from different probes (n = 9) gave an R.S.D. of 8.4% at 0.55 mmol L⁻¹ Cu(II). The effect of interfered ions at 1:1 molar ratio of Cu(II):foreign ion was also studied in this work.     

Fabrication and characterization of Pb-free transparent dielectric layer for plasma display panel

Glasses within the Bi₂O₃–B₂O₃–BaO–ZnO system were examined as potential replacements for PbO-based glass frits with low firing temperatures. These frits are used in the transparent dielectric layer of plasma display panels (PDP). The glass transition temperature (T_g) of the prepared glasses varied between 450 and 460 °C. These glasses display dynamic dielectric properties, high transparency and thermal expansion as well as matching well with substrate glass. The thermal coefficient of expansion (TCE) was with the desired range of 81–86×10⁻⁷/K. Moreover, when the screen printed film was heat-treated at 570 °C for 30 min, optical transmittance (83%), root-mean square (rms) roughness (177.6 Å), dielectric constant (10.25) and withstand voltage (4.15 kV) satisfied the requirements necessary for transparent dielectric layers to be used in PDP applications.     

Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM]+[FeCl4]− ionic liquid in desulfurization: A novel charge transfer mechanism

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM]⁺[FeCl₄]⁻ have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH) < dibenzothiophene (DBT) ≈ benzothiophene (BT). Alkylation of TH or BT (e.g. 3-methylthiophene, and 3-methylbenzothiophene) leads to a stronger interaction with ionic liquid, but steric hindrance effects of some alkylic derivatives (e.g. 2,7-dimethylbenzothiophene) lead to a weaker interaction with ionic liquid. The mechanism of extractive desulfurization is attributed to the charge transfer effect. During extractive desulfurization, electrons on aromatic sulfur compounds transfer into the Lewis part of ionic liquid, namely, [FeCl₄]⁻. Furthermore, it is better to consider the Lewis acidity of Fe-containing ionic liquid by the whole unit (such as [FeCl₄]⁻ and aromatic sulfur compounds (X)) rather than only Fe or S atom.