A complete atomistic model of molten polyethylene from neutron scattering data: a new methodology for polymer structure

A new approach to the study of the local organization in amorphous polymer materials is presented. The method couples neutron diffraction experiments that explore the structure on the spatial scale 1–20 Å with the reverse Monte Carlo fitting procedure to predict structures that accurately represent the experimental scattering results over the whole momentum transfer range explored. Molecular mechanics and molecular dynamics techniques are also used to produce atomistic models independently from any experimental input, thereby providing a test of the viability of the reverse Monte Carlo method in generating realistic models for amorphous polymeric systems. An analysis of the obtained models in terms of single chain properties and of orientational correlations between chain segments is presented. We show the viability of the method with data from molten polyethylene. The analysis derives a model with average C-C and C-H bond lengths of 1.55 Å and 1.1 Å respectively, average backbone valence angle of 112, a torsional angle distribution characterized by a fraction of trans conformers of 0.67 and, finally, a weak interchain orientational correlation at around 4 Å.

A detailed single chain model for molten poly(tetrafluoroethylene) from a novel structure refinement technique on neutron scattering data

We present a new methodology that couples neutron diffraction experiments over a wide Q range with single chain modelling in order to explore, in a quantitative manner, the intrachain organization of non-crystalline polymers. The technique is based on the assignment of parameters describing the chemical, geometric and conformational characteristics of the polymeric chain, and on the variation of these parameters to minimize the difference between the predicted and experimental diffraction patterns. The method is successfully applied to the study of molten poly(tetrafluoroethylene) at two different temperatures, and provides unambiguous information on the configuration of the chain and its degree of flexibility. From analysis of the experimental data a model is derived with CC and CF bond lengths of 1.58 and 1.36 Å, respectively, a backbone valence angle of 110° and a torsional angle distribution which is characterized by four isometric states, namely a split trans state at ± 18°, giving rise to a helical chain conformation, and two gauche states at ± 112°. The probability of trans conformers is 0.86 at T = 350°C, which decreases slightly to 0.84 at T = 400°C. Correspondingly, the chain segments are characterized by long all-trans sequences with random changes in sign, rather anisotropic in nature, which give rise to a rather stiff chain. We compare the results of this quantitative analysis of the experimental scattering data with the theoretical predictions of both force fields and molecular orbital conformation energy calculations.

Analyzing the performance of non-listed real estate funds: an panel data analysis

The rapid growth of non-listed real estate funds over the last several years has contributed towards establishing this sector as a major investment vehicle for gaining exposure to commercial real estate. Academic research has not kept up with this development, however, as there are still only a few published studies on non-listed real estate funds. This paper aims to identify the factors driving the total return over a seven-year period. Influential factors tested in our analysis include the weighted underlying direct property returns in each country and sector as well as fund size, investment style gearing and the distribution yield. Furthermore, we analyze the interaction of non-listed real estate funds with the performance of the overall economy and that of competing asset classes and found that lagged GDP growth and stock market returns as well as contemporaneous government bond rates are significant and positive predictors of annual fund performance.

Predicting the arrival of high-speed solar wind streams at Earth using the STEREO Heliospheric Imagers

High-speed solar wind streams modify the Earth's geomagnetic environment, perturbing the ionosphere, modulating the flux of cosmic rays into the Earth atmosphere, and triggering substorms. Such activity can affect modern technological systems. To investigate the potential for predicting the arrival of such streams at Earth, images taken by the Heliospheric Imager (HI) on the STEREO-A spacecraft have been used to identify the onsets of high-speed solar wind streams from observations of regions of increased plasma concentrations associated with corotating interaction regions, or CIRs. In order to confirm that these transients were indeed associated with CIRs and to study their average properties, arrival times predicted from the HI images were used in a superposed epoch analysis to confirm their identity in near-Earth solar wind data obtained by the Advanced Composition Explorer (ACE) spacecraft and to observe their influence on a number of salient geophysical parameters. The results are almost identical to those of a parallel superposed epoch analysis that used the onset times of the high-speed streams derived from east/west deflections in the ACE measurements of solar wind speed to predict the arrival of such streams at Earth, assuming they corotated with the Sun with a period of 27 days. Repeating the superposed epoch analysis using restricted data sets demonstrates that this technique can provide a timely prediction of the arrival of CIRs at least 1 day ahead of their arrival at Earth and that such advanced warning can be provided from a spacecraft placed 40° ahead of Earth in its orbit.

The role of the international cocoa germplasm database and the international cocoa quarantine centre in information management and distribution of cocoa genetic resources

A range of physiological parameters (canopy light transmission, canopy shape, leaf size, flowering and flushing intensity) were measured from the International Clone Trial, typically over the course of two years. Data were collected from six locations, these being: Brazil, Ecuador, Trinidad, Venezuela, Côte d’Ivoire and Ghana. Canopy shape varied significantly between clones, although it showed little variation between locations. Genotypic variation in leaf size was differentially affected by the growth location; such differences appeared to underlie a genotype by environment interaction in relation to canopy light transmission. Flushing data were recorded at monthly intervals over the course of a year. Within each location, a significant interaction was observed between genotype and time of year, suggesting that some genotypes respond to a greater extent than others to environmental stimuli. A similar interaction was observed for flowering data, where significant correlations were found between flowering intensity and temperature in Brazil and flowering intensity and rainfall in Côte d’Ivoire. The results demonstrate the need for local evaluation of cocoa clones and also suggest that the management practices for particular planting material may need to be fine-tuned to the location in which they are cultivated.

Reconstruction of gusty wind speed time series from autonomous data logger records

The collection of wind speed time series by means of digital data loggers occurs in many domains, including civil engineering, environmental sciences and wind turbine technology. Since averaging intervals are often significantly larger than typical system time scales, the information lost has to be recovered in order to reconstruct the true dynamics of the system. In the present work we present a simple algorithm capable of generating a real-time wind speed time series from data logger records containing the average, maximum, and minimum values of the wind speed in a fixed interval, as well as the standard deviation. The signal is generated from a generalized random Fourier series. The spectrum can be matched to any desired theoretical or measured frequency distribution. Extreme values are specified through a postprocessing step based on the concept of constrained simulation. Applications of the algorithm to 10-min wind speed records logged at a test site at 60 m height above the ground show that the recorded 10-min values can be reproduced by the simulated time series to a high degree of accuracy.

Surrounding buildings and wind pressure distribution on a high-rise building

The effect of the surrounding lower buildings on the wind pressure distribution on a high-rise building is investigated by computational fluid dynamics (CFD). When B/H=0.1, it is found that the wind pressure on the windward side was reduced especially on the lower part, but for different layers of surrounding buildings, there was no great difference, which agrees with our previous wind tunnel experiment data. Then we changed the aspect ratio from 0.1 to 2, to represent different airflow regimes: skimming flow (SF), and wake interference (WI). It shows that the average Cp increases when B/H increases. For different air flow regimes, it is found that insignificant difference exists when the number of the building layers is more than 2. From the engineering point of view, it is sufficient to only include the first layer for natural ventilation design by using CFD simulation or wind tunnel experiment.

From ensemble forecasts to predictive distribution functions

The translation of an ensemble of model runs into a probability distribution is a common task in model-based prediction. Common methods for such ensemble interpretations proceed as if verification and ensemble were draws from the same underlying distribution, an assumption not viable for most, if any, real world ensembles. An alternative is to consider an ensemble as merely a source of information rather than the possible scenarios of reality. This approach, which looks for maps between ensembles and probabilistic distributions, is investigated and extended. Common methods are revisited, and an improvement to standard kernel dressing, called ‘affine kernel dressing’ (AKD), is introduced. AKD assumes an affine mapping between ensemble and verification, typically not acting on individual ensemble members but on the entire ensemble as a whole, the parameters of this mapping are determined in parallel with the other dressing parameters, including a weight assigned to the unconditioned (climatological) distribution. These amendments to standard kernel dressing, albeit simple, can improve performance significantly and are shown to be appropriate for both overdispersive and underdispersive ensembles, unlike standard kernel dressing which exacerbates over dispersion. Studies are presented using operational numerical weather predictions for two locations and data from the Lorenz63 system, demonstrating both effectiveness given operational constraints and statistical significance given a large sample.

Describing seasonal variability in the distribution of daily effective temperatures for 1985-2009 compared to 1904-1984 for De Bilt, Holland

This paper proposes a method for describing the distribution of observed temperatures on any day of the year such that the distribution and summary statistics of interest derived from the distribution vary smoothly through the year. The method removes the noise inherent in calculating summary statistics directly from the data thus easing comparisons of distributions and summary statistics between different periods. The method is demonstrated using daily effective temperatures (DET) derived from observations of temperature and wind speed at De Bilt, Holland. Distributions and summary statistics are obtained from 1985 to 2009 and compared to the period 1904–1984. A two-stage process first obtains parameters of a theoretical probability distribution, in this case the generalized extreme value (GEV) distribution, which describes the distribution of DET on any day of the year. Second, linear models describe seasonal variation in the parameters. Model predictions provide parameters of the GEV distribution, and therefore summary statistics, that vary smoothly through the year. There is evidence of an increasing mean temperature, a decrease in the variability in temperatures mainly in the winter and more positive skew, more warm days, in the summer. In the winter, the 2% point, the value below which 2% of observations are expected to fall, has risen by 1.2 °C, in the summer the 98% point has risen by 0.8 °C. Medians have risen by 1.1 and 0.9 °C in winter and summer, respectively. The method can be used to describe distributions of future climate projections and other climate variables. Further extensions to the methodology are suggested.

Connecting mean field models of neural activity to EEG and fMRI data

Progress in functional neuroimaging of the brain increasingly relies on the integration of data from complementary imaging modalities in order to improve spatiotemporal resolution and interpretability. However, the usefulness of merely statistical combinations is limited, since neural signal sources differ between modalities and are related non-trivially. We demonstrate here that a mean field model of brain activity can simultaneously predict EEG and fMRI BOLD with proper signal generation and expression. Simulations are shown using a realistic head model based on structural MRI, which includes both dense short-range background connectivity and long-range specific connectivity between brain regions. The distribution of modeled neural masses is comparable to the spatial resolution of fMRI BOLD, and the temporal resolution of the modeled dynamics, importantly including activity conduction, matches the fastest known EEG phenomena. The creation of a cortical mean field model with anatomically sound geometry, extensive connectivity, and proper signal expression is an important first step towards the model-based integration of multimodal neuroimages.

A method for under-sampled ecological network data analysis: plant-pollination as case study

In this paper, we develop a method, termed the Interaction Distribution (ID) method, for analysis of quantitative ecological network data. In many cases, quantitative network data sets are under-sampled, i.e. many interactions are poorly sampled or remain unobserved. Hence, the output of statistical analyses may fail to differentiate between patterns that are statistical artefacts and those which are real characteristics of ecological networks. The ID method can support assessment and inference of under-sampled ecological network data. In the current paper, we illustrate and discuss the ID method based on the properties of plant-animal pollination data sets of flower visitation frequencies. However, the ID method may be applied to other types of ecological networks. The method can supplement existing network analyses based on two definitions of the underlying probabilities for each combination of pollinator and plant species: (1), pi,j: the probability for a visit made by the i’th pollinator species to take place on the j’th plant species; (2), qi,j: the probability for a visit received by the j’th plant species to be made by the i’th pollinator. The method applies the Dirichlet distribution to estimate these two probabilities, based on a given empirical data set. The estimated mean values for pi,j and qi,j reflect the relative differences between recorded numbers of visits for different pollinator and plant species, and the estimated uncertainty of pi,j and qi,j decreases with higher numbers of recorded visits.

Distribution of calcium (Ca) and magnesium (Mg) in the leaves of Brassica rapa under varying exogenous Ca and Mg supply

Background and Aims Leafy vegetable Brassica crops are an important source of dietary calcium (Ca) and magnesium (Mg) and represent potential targets for increasing leaf Ca and Mg concentrations through agronomy or breeding. Although the internal distribution of Ca and Mg within leaves affects the accumulation of these elements, such data are not available for Brassica. The aim of this study was to characterize the internal distribution of Ca and Mg in the leaves of a vegetable Brassica and to determine the effects of altered exogenous Ca and Mg supply on this distribution. Methods Brassica rapa ssp. trilocularis ‘R-o-18’ was grown at four different Ca:Mg treatments for 21 d in a controlled environment. Concentrations of Ca and Mg were determined in fully expanded leaves using inductively coupled plasma-mass spectrometry (ICP-MS). Internal distributions of Ca and Mg were determined in transverse leaf sections at the base and apex of leaves using energy-dispersive X-ray spectroscopy (EDS) with cryo-scanning electron microscopy (cryo-SEM). Key Results Leaf Ca and Mg concentrations were greatest in palisade and spongy mesophyll cells, respectively, although this was dependent on exogenous supply. Calcium accumulation in palisade mesophyll cells was enhanced slightly under high Mg supply; in contrast, Mg accumulation in spongy mesophyll cells was not affected by Ca supply. Conclusions The results are consistent with Arabidopsis thaliana and other Brassicaceae, providing phenotypic evidence that conserved mechanisms regulate leaf Ca and Mg distribution at a cellular scale. The future study of Arabidopsis gene orthologues in mutants of this reference B. rapa genotype will improve our understanding of Ca and Mg homeostasis in plants and may provide a model-to-crop translation pathway for targeted breeding.

The distribution of interplanetary dust between 0.96 and 1.04 au as inferred from impacts on the STEREO spacecraft observed by the heliospheric imagers

The distribution of dust in the ecliptic plane between 0.96 and 1.04 au has been inferred from impacts on the two Solar Terrestrial Relations Observatory (STEREO) spacecraft through observation of secondary particle trails and unexpected off-points in the heliospheric imager (HI) cameras. This study made use of analysis carried out by members of a distributed web-based citizen science project Solar Stormwatch. A comparison between observations of the brightest particle trails and a survey of fainter trails shows consistent distributions. While there is no obvious correlation between this distribution and the occurrence of individual meteor streams at Earth, there are some broad longitudinal features in these distributions that are also observed in sources of the sporadic meteor population. The different position of the HI instrument on the two STEREO spacecraft leads to each sampling different populations of dust particles. The asymmetry in the number of trails seen by each spacecraft and the fact that there are many more unexpected off-points in the HI-B than in HI-A indicates that the majority of impacts are coming from the apex direction. For impacts causing off-points in the HI-B camera, these dust particles are estimated to have masses in excess of 10−17 kg with radii exceeding 0.1 μm. For off-points observed in the HI-A images, which can only have been caused by particles travelling from the anti-apex direction, the distribution is consistent with that of secondary ‘storm’ trails observed by HI-B, providing evidence that these trails also result from impacts with primary particles from an anti-apex source. Investigating the mass distribution for the off-points of both HI-A and HI-B, it is apparent that the differential mass index of particles from the apex direction (causing off-points in HI-B) is consistently above 2. This indicates that the majority of the mass is within the smaller particles of this population. In contrast, the differential mass index of particles from the anti-apex direction (causing off-points in HI-A) is consistently below 2, indicating that the majority of the mass is to be found in larger particles of this distribution.

Building the niche through time: using 13,000 years of data to predict the effects of climate change on three tree species in Europe

Aim  Species distribution models (SDMs) based on current species ranges underestimate the potential distribution when projected in time and/or space. A multi-temporal model calibration approach has been suggested as an alternative, and we evaluate this using 13,000 years of data. Location  Europe. Methods  We used fossil-based records of presence for Picea abies, Abies alba and Fagus sylvatica and six climatic variables for the period 13,000 to 1000 yr bp. To measure the contribution of each 1000-year time step to the total niche of each species (the niche measured by pooling all the data), we employed a principal components analysis (PCA) calibrated with data over the entire range of possible climates. Then we projected both the total niche and the partial niches from single time frames into the PCA space, and tested if the partial niches were more similar to the total niche than random. Using an ensemble forecasting approach, we calibrated SDMs for each time frame and for the pooled database. We projected each model to current climate and evaluated the results against current pollen data. We also projected all models into the future. Results  Niche similarity between the partial and the total-SDMs was almost always statistically significant and increased through time. SDMs calibrated from single time frames gave different results when projected to current climate, providing evidence of a change in the species realized niches through time. Moreover, they predicted limited climate suitability when compared with the total-SDMs. The same results were obtained when projected to future climates. Main conclusions  The realized climatic niche of species differed for current and future climates when SDMs were calibrated considering different past climates. Building the niche as an ensemble through time represents a way forward to a better understanding of a species' range and its ecology in a changing climate.

An environmental uncertainty-based diagnostic reference tool for evaluating the performance of supply chain value streams

This research has responded to the need for diagnostic reference tools explicitly linking the influence of environmental uncertainty and performance within the supply chain. Uncertainty is a key factor influencing performance and an important measure of the operating environment. We develop and demonstrate a novel reference methodology based on data envelopment analysis (DEA) for examining the performance of value streams within the supply chain with specific reference to the level of environmental uncertainty they face. In this paper, using real industrial data, 20 product supply value streams within the European automotive industry sector are evaluated. Two are found to be efficient. The peer reference groups for the underperforming value streams are identified and numerical improvement targets are derived. The paper demonstrates how DEA can be used to guide supply chain improvement efforts through role-model identification and target setting, in a way that recognises the multiple dimensions/outcomes of the supply chain process and the influence of its environmental conditions. We have facilitated the contextualisation of environmental uncertainty and its incorporation into a specific diagnostic reference tool.