Molecular Parameterisation and the Theoretical Calculation of Electrode Potentials

The difference in reduction potentials between ortho and para-benzoquinones has been calculated. The employs gas phase ab initio and semi-empirical computations in combination with free energy perturbation theory applied to gas and solution phase Monte Carlo simulations. The effects on calculated results of altering solute electrostatic parameterisation in solution phase simulations is examined. Atom centred charges derived from the molecular electrostatic potentials, MEPs, from optimised ab initio wavefunctions and charges generated by consideration of hydrogen bonded complexes are considered. Parameterisation of hydroxyl torsions in hydroquinone molecules is treated in a physically realistic manner. The coupled torsional system of the ortho-hydrobenzoquinone molecule is described by a potential energy surface calculated using gas phase AM1 semi-empirical computations rather than the simple torsional energy functions frequently employed in such calculations. Calculated differences in electrode potentials show that the electrostatic interactions of quinone and hydroquinone molecules in aqueous solution are not well described by atom centred charges derived from ab initio calculated MEPs. Moreover, results in good agreement with the experimental reduction potential difference can be obtained by employing high level ab initio calculations and solution phase electrostatic parameters developed by consideration of hydrogen bonded complexes.     

Competing Risks and Time‐Dependent Covariates

Time‐dependent covariates are frequently encountered in regression analysis for event history data and competing risks. They are often essential predictors, which cannot be substituted by time‐fixed covariates. This study briefly recalls the different types of time‐dependent covariates, as classified by Kalbfleisch and Prentice [The Statistical Analysis of Failure Time Data, Wiley, New York, 2002] with the intent of clarifying their role and emphasizing the limitations in standard survival models and in the competing risks setting. If random (internal) time‐dependent covariates are to be included in the modeling process, then it is still possible to estimate cause‐specific hazards but prediction of the cumulative incidences and survival probabilities based on these is no longer feasible. This article aims at providing some possible strategies for dealing with these prediction problems. In a multi‐state framework, a first approach uses internal covariates to define additional (intermediate) transient states in the competing risks model. Another approach is to apply the landmark analysis as described by van Houwelingen [Scandinavian Journal of Statistics 2007, 34 , 70–85] in order to study cumulative incidences at different subintervals of the entire study period. The final strategy is to extend the competing risks model by considering all the possible combinations between internal covariate levels and cause‐specific events as final states. In all of those proposals, it is possible to estimate the changes/differences of the cumulative risks associated with simple internal covariates. An illustrative example based on bone marrow transplant data is presented in order to compare the different methods.     

The impact of Rhinanthus minor in newly established meadows on a productive site

Question: What is the impact of the presence of Rhinanthus minor on forb abundance in newly established swards? Location: Wetherby, West Yorkshire, UK (53°55’N, 1°22’W). Method: A standard meadow mix containing six forbs and six grasses was sown on an ex‐arable field and immediately over‐sown using a randomised plot design with three densities of Rhinanthus minor (0, 600, and 1000 seeds per m²). Above‐ground biomass was analysed over a period of three years, while detailed assessments of sward composition were performed during the first two years. Results: Values of grass biomass were reduced in the presence of Rhinanthus, especially at the higher sowing density. The ratio of grass: forb biomass was also lower in association with Rhinanthus, but only at the higher sowing density. The presence of Rhinanthus had no effect on species number or diversity, which decreased between years regardless of treatment. Conclusions: Although not tested in a multi‐site experiment, the benefit of introducing Rhinanthus into newly established swards to promote forb abundance was determined. The efficacy of Rhinanthus presence is likely to depend on whether species not susceptible to the effects of parasitism are present.     

Why we should conserve ‘limiting factors’, at least sometimes!

Körner's recent paper provided an excellent initial discussion of the term ‘limitation’ in ecology. I accept most of his arguments but would argue that there are some circumstances in applied ecology where the concept of limitation can be useful; these are (1) where there is a deficiency of a factor that prevents growth, and (2) where there is a need to manage an ecosystem so that a limitation is enforced.     

Species introduction through seeds from an old,species‐rich hay meadow: Effects of management

Abstract. A local seed mixture from plants growing in a species‐rich, traditionally managed hay meadow site at Varaldsoy, Hardanger, western Norway, where many endangered hay meadow species of the region are growing, was sown in a newly harrowed experimental field 1 km from the source meadow in order to increase the habitat area for the endangered species. Of 25 endangered species recorded in the source meadow, only one (Holcus lanatus) was present in the target meadow. After sowing, 16 of the endangered species in addition to Holcus lanatus were recorded in the new site. Six species were only present in sown plots and seven others were more frequent there, while three species might have arrived by chance or originated from the seed bank. Replacing the traditional management regime, including one late cut and grazing in spring and in autumn, with three cutting times and the creation of gaps in the sward, resulted in a higher number of endangered species in plots which were only cut, possibly because the grazing was too intensive in the small enclosures.     

内蒙古库布齐沙地四种啮齿动物非颤拌性产热的季节变化

为了解非颤抖性产热在内陆荒漠小型哺乳动物适应性热能调节中的作用,1997年对库布齐荒漠沙地环境4种啮齿动物：三趾跳鼠（Dipus sagitta)、子午沙鼠（Meriones meridianus)、小毛足鼠（Phodopus roborovskii)和黑线仓鼠（Cricetulus barabensis)的非颤抖性产热季节变化进行了测定。4种动物的非颤抖性产热在秋季低温刺激下明显高于夏季,而且小毛足鼠和黑线仓鼠在秋季的最大非颤抖性产热分别高于春季14％和35％。典型荒漠种小毛足鼠的季节变化最明显,夏季最低。结果表明,生活在内陆干旱地区的动物生长期进化过程中,发展了良好的非颤抖性产热体温调节机制适应环境温度的季节变化。