Synthesis,characterization of nanosized CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and its electrocatalytic activity for enhanced sensing application

Nanosized cobalt aluminate (CoAl₂O₄) was prepared by thermolysis of heteronuclear coordination compound, namely [Al₂Co(C₂O₄)₄(OH₂)₆]. The synthesized precursor was characterized by chemical analysis, vibrational spectra and thermal analysis. The cobalt aluminate obtained after a heating treatment of the precursor at 700 °C was characterized by IR, XRD, TEM coupled with SAED measurements. Two types of carbon-based electrodes, glassy carbon and boron-doped diamond electrodes were decorated with the obtained cobalt aluminate in order to enhance the electroanalytical performance for the tetracycline (TC) detection in the aqueous solutions. Cyclic voltammetry technique was used to determine the effect of the nanosized CoAl₂O₄ on the electrochemical oxidation of TC and as consequence, for TC detection at both carbon-based electrodes. The obtained cobalt aluminate exhibited the electrocatalytic activity toward TC detection in direct relation with the type of the carbon substrate, which allowed enhancing the electroanalytical parameters of TC detection in the aqueous solution.     

Ultrahigh-throughput screening system for directed glucose oxidase evolution in yeast cells

A compartmentalized tyramide labeling system (CoaTi) employing flow cytometry for sorting of yeast cells was developed as ultrahigh-throughput screening for Glucose oxidase (GOx) from Aspergillus niger. CoaTi combines in vitro compartmentalization technology with the CARD reporter system which uses fluorescein tyramide labels for detection of peroxidase activity. Physical connection between cells and fluorescein tyramide radicals was achieved by compartmentalization of yeast cells inside microdroplets of single water-in-oil emulsions. After reaction cells were recovered from single emulsions and sorted by flow cytometry, an error prone PCR mutant library of Glucose oxidase (GOx) containing 10(7) cells and ~10(5) of different GOx variants was screened. Mutagenic conditions of GOx mutant library were selected to generate <1 % of active GOx population in order to explore influence of high mutation frequency on GOx activity. GOx variant Mut12 that contains 5 mutations (N2Y, K13E, T30V, I94V, K152R) showed a 1.2 times decreased K(m) (22.0 vs 18.1 mM) and a 2.7 fold increased k(cat) (150 s(-1) vs 54.8 s(-1)) compared to wt GOx. Compared to the employed parent B11 GOx (16 mM, 80 s(-1)) it has a slightly increased K(m) and 1.8 times increased k(cat).     

Heterogeneous reactivity of chlorine atoms with sodium chloride and synthetic sea salt particles

The uptake of chlorine atoms on sodium chloride (NaCl) and synthetic sea salt (SSS) particles was studied using a discharge flow reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor using two different methods: either by depositing size-selected particles on halocarbon wax or by spray depositing thin films using a constant output atomizer. The observed uptake coefficients of Cl˙ on NaCl particles are γ(NaCl)(Cl) ≈ 2 × 10(-2) for size-selected particles or γ(NaCl)(Cl) ≈ 5 × 10(-2) for thin films and for SSS particles γ(SSS)(Cl) ≈ 4 × 10(-3). Heterogeneous recombination of Cl atoms to Cl(2) molecules was observed for the two solid surfaces. The study was performed over the temperature range 258 to 353 K. The temperature dependence of the uptake was observed and the heat of adsorption of Cl˙ on NaCl particles was estimated at Q(ads) = 63 kJ mol(-1) assuming an Eley-Rideal mechanism. The role of surface adsorbed water has also been shown. The atmospheric implications of these findings are discussed briefly.     

A pulse sequence for averaging the strong homonuclear scalar coupling in AB spin systems

A pulse sequence is proposed for the suppression of the strong homonuclear scalar coupling in the case of AB spin systems. The theoretical treatment is presented in terms of the average Hamiltonian theory in the case of aperiodic perturbations. The zero-order and the first-order correction terms in the full average Hamiltonian are calculated. It is shown that the chemical shift interaction for one of the spins is completely refocused and the conditions in which the interactions bilinear in spin operators are efficiently suppressed are analyzed.     

Unbounded divergence of simple quadrature formulas

Given a sequence of real or complex coefficients c_i and a sequence of distinct nodes t_i in a compact interval T, we prove the divergence and the unbounded divergence on superdense sets in the space C(T) of the simple quadrature formulas ∝_Tx(t)du(t) = Q_n(x) + R_n(x) and ∝_Tw(t)x(t)dt = Q_n(x) + R_n(x), where Q_n(x)=∑_i=1^m_n c_ix(t_i), ε C(T).The divergence (not certainly unbounded) for at most one continuous function of the first simple quadrature formula, with m_n = n and u(t) = t, was established by P. J. Davis in 1953.     

Effect of the interface on separation in multicapillary gas chromatography-based hyphenated techniques for speciation analysis of organometallic compounds

This paper reports the effect of transfer line (TL) internal diameter (i.d.) on gas chromatographic separation characteristics such as efficiency and speed, when a multicapillary (MC) column is used for speciation analysis of mercury. Five different TL consisting of fused-silica capillaries with 0.15, 0.20, 0.25, 0.32, and 0.53 mm i.d. are compared. The separation efficiency and total chromatographic run time are critically affected by the i.d. of the TL. Narrow capillaries (i.d.0.20 mm) produce minimum peak dispersion whereas wide capillaries result in narrow peaks and shorter chromatographic analysis times. A thermodynamic approach is proposed to describe the motion of the analytes through the separation column and TL. The model provides good agreement with the experimental data for high pressures (35 psig) and wide TL (0.25 mm i.d.).Dedicated to the memory of Wilhelm Fresenius     

A Priori Feedback Estimates for Multiscale Reaction-Diffusion Systems

We study the approximation of a multiscale reaction–diffusion system posed on both macroscopic and microscopic space scales. The coupling between the scales is done through micro–macro flux conditions. Our target system has a typical structure for reaction–diffusion flow problems in media with distributed microstructures (also called, double porosity materials). Besides ensuring basic estimates for the convergence of two-scale semi-discrete Galerkin approximations, we provide a set of a priori feedback estimates and a local feedback error estimator that help in designing a distributed-high-errors strategy to allow for a computationally e?cient zooming in and out from microscopic structures. The error control on the feedback estimates relies on two-scale-energy, regularity, and interpolation estimates as well as on a fine bookeeping of the sources responsible with the propagation of the (multiscale) approximation errors. The working technique based on a priori feedback estimates is in principle applicable to a large class of systems of PDEs with dual structure admitting strong solutions.     

Bivariate Bernoulli Weighted Sums and Distribution of Single-Period Tontine Benefits

This paper studies the distribution of particular weighted sums of Bernoulli random variables. The computing methods are applied to derive the probability distribution of the random amount of survivor credits to be shared among surviving participants in single-period tontine schemes. The effectiveness of this new arrangement can then be evaluated beyond the classical analysis based on crude approximations for the two first moments, only.     

Efficient solver for swirling flow problems in ducts with variable radius

The paper presents preliminary results of a work in progress addressing the hydrodynamic stability of swirling flows problems in ducts with variable radius which imply mathematical modeling, dynamic and stability investigations. The proposed quasi-analytical method aims to obtain the velocity profiles with a low order approximation method of which the computation costs were neglijable and regain the central stagnation zone developed in the fluid. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)