Strategies for the development of a voltammetric sensor for the determination of hydrogen peroxide at high concentrations

Different strategies are presented for the development of a voltammetric sensor for in-line measurement and monitoring of H₂O₂ in high concentrations (up to 30 g/l) as used in textile bleaching systems. When using macroelectrodes, signal saturation is observed even at medium concentrations. Some improvement can be achieved by hydrodynamic electrodes like ring-disk electrodes. Satisfactory results up to the desired level in practical solutions (possessing only limited conductivity) are obtained with Pt-microelectrodes.     

Studies of the kinetics of the reduction of chromate by glutathione and related thiols

The reduction of chromate by glutathione, its mono- and diethyl esters, -cysteine, 2-mercapto-propionic acid and mercapto-succinic acid has been studied. The empirical rate law k_obs = ab[Thiol]²/(1 + b[Thiol]) is obeyed by all of these thiols, at neutral pH. No evidence could be obtained for a first-order pathway in glutathione under these conditions. These observations are used to comment on the stability of intermediates potentially important in explaining chromate toxicity.     

Theory of main chain nematic polymers with spacers of varying degree of flexibility

Main chain liquid crystal polymers are modelled as either worms or jointed rods. In reality they are composed of mesogenic units (rods) linked by spacers with varying degrees of flexibility. We present a molecular model to describe non-homogeneous nematic polymers. The model takes account of molecular parameters, such as the lengths of the mesogenic group and the spacer units, and the interactions between them. The spacers are found to have an order differing from the mesogenic units. If the spacer is not very long and thus in effect is inflexible, one end of the spacer can retain to some extent the orientation of the other end, allowing orientational correlation between spacers mediated by the intermediate mesogenic unit. This is important in giving the chain a global rod-like behaviour as the nematic field becomes strong or the temperature low. The nematic order of the two components (mesogens and spacers), the nematic-isotropic transition as well as the latent entropy are examined. Furthermore, the anisotropic conformations of the polymers are investigated, which show either rod-like or random walk behaviour. Comparison of our results with experiment is found to be satisfactory.     

A note on an SOR-like method for augmented systems

Golub et al. (2001, BIT, 41, 71–85) gave a generalizedsuccessive over-relaxation method for the augmented systems.In this paper, the connection between the SOR-like method andthe preconditioned conjugate gradient (PCG) method for the augmentedsystems is investigated. It is shown that the PCG method isat least as accurate (fast) as the SOR-like method. Numericalexamples demonstrate that the PCG method is much faster thanthe SOR-like method.     

Effect of track stiffness on vibration levels in railway tunnels

The paper discusses the difficulties in comparing and drawing conclusions from vibration measurements made in different railway tunnels. A number of new measurements are presented, which have been made and analyzed on a consistent basis. The track stiffness has been determined for each of the measurements. Graphs are presented which indicate the level of rail and tunnel floor vibration likely to occur for different track stiffnesses. The variance in the measurement results also indicates the potential error in using the data to predict vibration levels in new situations.     

Kinetics of phenyl radical reactions with propane,n‐butane,n‐hexane,and n‐octane: Reactivity of C6H5 toward the secondary C?H bond of alkanes

The kinetics of C₆H₅ reactions with n‐C_nH_2n+2 (n = 3, 4, 6, 8) have been studied by the pulsed laser photolysis/mass spectrometric method using C₆H₅COCH₃ as the phenyl precursor at temperatures between 494 and 1051 K. The rate constants were determined by kinetic modeling of the absolute yields of C₆H₆ at each temperature. Another major product C₆H₅CH₃ formed by the recombination of C₆H₅ and CH₃ could also be quantitatively modeled using the known rate constant for the reaction. A weighted least‐squares analysis of the four sets of data gave k (C₃H₈) = (1.96 ± 0.15) × 10¹¹ exp[?(1938 ± 56)/T], and k (n‐C₄H₁₀) = (2.65 ± 0.23) × 10¹¹ exp[?(1950 ± 55)/T] k (n‐C₆H₁₄) = (4.56 ± 0.21) × 10¹¹ exp[?(1735 ± 55)/T], and k (n?C₈H₁₈) = (4.31 ± 0.39) × 10¹¹ exp[?(1415 ± 65)T] cm³ mol^?1 s^?1 for the temperature range studied. For the butane and hexane reactions, we have also applied the CRDS technique to extend our temperature range down to 297 K; the results obtained by the decay of C₆H₅ with CRDS agree fully with those determined by absolute product yield measurements with PLP/MS. Weighted least‐squares analyses of these two sets of data gave rise to k (n?C₄H₁₀) = (2.70 ± 0.15) × 10¹¹ exp[?(1880 ± 127)/T] and k (n?C₆H₁₄) = (4.81 ± 0.30) × 10¹¹ exp[?(1780 ± 133)/T] cm³ mol^?1 s^?1 for the temperature range 297‐‐1046 K. From the absolute rate constants for the two larger molecular reactions (C₆H₅ + n‐C₆H₁₄ and n‐C₈H₁₈), we derived the rate constant for H‐abstraction from a secondary C? H bond, k_s?CH = (4.19 ± 0.24) × 10¹⁰ exp[?(1770 ± 48)/T] cm³ mol^?1 s^?1. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 49–56, 2004     

Analysis of transient wave scattering from an inclusion with an unilateral smoothly contact interface by BEM

Summary A 2D time-domain Boundary Element Method (BEM) is applied to solve the problem of transient scattering of plane waves by an inclusion with a unilateral smooth contact interface. The incident wave is assumed strong enough so that localized separations take place along the interface. The present problem is indeed a nonlinear boundary value problem since the mixed boundary conditions involve unknown intervals (separation and contact regions). In order to determine the unknown intervals, an iterative technique is developed. As an example, we consider the scattering of plane waves by the cross section of a circular cylinder embedded in an infinite solid. Numerical results for the near field solutions are presented. The distortion of the response waves and the variation of the interface states are discussed. The financial support by the China National Natural Science Foundation under Grant No. 19872001 and No. 59878004 is gratefully acknowledged. The second author is also grateful to the support of the National Science Fund for Distinguished Young Scholars under Grant No. 10025211.     

Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007