A curvilinear approach to the kinetic analysis of linoleate peroxidation in aqueous liposomes by 2,2'azobis(2-amidoinopropane) dihydrochloride

Lipid peroxidation is a common feature of many chemical and biological processes, and is governed by a complex kinetic scheme. A fundamental stage in kinetic investigations of lipid peroxidation is the accurate determination of the rate of peroxidation, which in many instances is heavily reliant on the method of finite differences. Such numerical approximations of the first derivative are commonly employed in commercially available software, despite suffering from considerable inaccuracy due to rounding and truncation errors. As a simple solution to this, we applied three empirical sigmoid functions (viz. the Prout-Tompkins, Richards & Gompertz functions) to data obtained from the AAPH-mediated peroxidation of aqueous linoleate liposomes in the presence of increasing concentrations of Trolox, evaluating the curve fitting parameters using the widely available Microsoft Excel Solver add-in. We have demonstrated that the five-parameter Richards' function provides an excellent model for this peroxidation, and when applied to the determination of fundamental rate constants, produces results in keeping with those available in the literature. Overall, we present a series of equations, derived from the Richards' function, which enables direct evaluation of the kinetic measures of peroxidation. This procedure has applicability not only to investigations of lipid peroxidation, but to any system exhibiting sigmoid kinetics.

Analytical approximations to numerical solutions of theoretical emission measure distributions

Emission line fluxes from cool stars are widely used to establish an apparent emission measure distribution, EmdApp(Te), between temperatures characteristic of the low transition region and the low corona. The true emission measure distribution, EmdTrue(Te), is determined by the energy balance and geometry adopted and, with a numerical model, can be used to predict EmdApp(Te), to guide further modelling. The scaling laws that exist between coronal parameters arise from the dimensions of the terms in the energy balance equation. Here, analytical approximations to numerical solutions for EmdTrue(Te) are presented, which show how the constants in the coronal scaling laws are determined. The apparent emission measure distributions show a minimum value at some T0 and a maximum at the mean coronal temperature Tc (although in some stars, emission from active regions can contribute). It is shown that, for the energy balance and geometry adopted, the analytical values of the emission measure and electron pressure at T0 and Tc depend on only three parameters: the stellar surface gravity and the values of T0 and Tc. The results are tested against full numerical solutions for e Eri (K2 V) and are applied to Procyon (a CMi, F5 IV/V). The analytical approximations can be used to restrict the required range of full numerical solutions, to check the assumed geometry and to show where the adopted energy balance may not be appropriate. © 2011 The Authors Monthly Notices of the Royal Astronomical Society © 2011 RAS.

Numerical ‘health check’ for scientific codes: the CADNA approach

Scientific computation has unavoidable approximations built into its very fabric. One important source of error that is difficult to detect and control is round-off error propagation which originates from the use of finite precision arithmetic. We propose that there is a need to perform regular numerical `health checks' on scientific codes in order to detect the cancerous effect of round-off error propagation. This is particularly important in scientific codes that are built on legacy software. We advocate the use of the CADNA library as a suitable numerical screening tool. We present a case study to illustrate the practical use of CADNA in scientific codes that are of interest to the Computer Physics Communications readership. In doing so we hope to stimulate a greater awareness of round-off error propagation and present a practical means by which it can be analyzed and managed.

Macroscopic limit of time-dependent density-functional theory for adiabatic local approximations of the exchange-correlation kernel

Time-dependent density-functional theory is a rather accurate and efficient way to compute electronic excitations for finite systems. However, in the macroscopic limit (systems of increasing size), for the usual adiabatic random-phase, local-density, or generalized-gradient approximations, one recovers the Kohn-Sham independent-particle picture, and thus the incorrect band gap. To clarify this trend, we investigate the macroscopic limit of the exchange-correlation kernel in such approximations by means of an algebraical analysis complemented with numerical studies of a one-dimensional tight-binding model. We link the failure to shift the Kohn-Sham spectrum of these approximate kernels to the fact that the corresponding operators in the transition space act only on a finite subspace.