Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

User-intimate requirements hierarchy resolution framework (UI-REF)

Abstract. This paper presents the User-Intimate Requirements Hierarchy Resolution Framework (UI-REF) based on earlier work (Badii 1997-2008) to optimise the requirements engineering process particularly to support userintimate interactive systems co-design. The stages of the UI- EF framework for requirements resolution-and-prioritisation are described. UI-REF has been established to ensure that the most-deeply-valued needs of the majority of stakeholders are elicited and ranked, and the root rationale for requirements evolution is trace-able and contextualised so as to help resolve stakeholder conflicts. UI-REF supports the dynamically evolving requirements of the users in the context of digital economy as under-pinned by online service provisioning. Requirements prioritisation in UI-REF is fully resolved while a promotion path for lower priority requirements is delineated so as to ensure that as the requirements evolve so will their resolution and prioritisation.

Investigating global tropical cyclone activity with a hierarchy of AGCMs: the role of model resolution

The ability to run General Circulation Models (GCMs) at ever-higher horizontal resolutions has meant that tropical cyclone simulations are increasingly credible. A hierarchy of atmosphere-only GCMs, based on the Hadley Centre Global Environmental Model (HadGEM1), with horizontal resolution increasing from approximately 270km to 60km (at 50N), is used to systematically investigate the impact of spatial resolution on the simulation of global tropical cyclone activity, independent of model formulation. Tropical cyclones are extracted from ensemble simulations and reanalyses of comparable resolutions using a feature-tracking algorithm. Resolution is critical for simulating storm intensity and convergence to observed storm intensities is not achieved with the model hierarchy. Resolution is less critical for simulating the annual number of tropical cyclones and their geographical distribution, which are well captured at resolutions of 135km or higher, particularly for Northern Hemisphere basins. Simulating the interannual variability of storm occurrence requires resolutions of 100km or higher; however, the level of skill is basin dependent. Higher resolution GCMs are increasingly able to capture the interannual variability of the large-scale environmental conditions that contribute to tropical cyclogenesis. Different environmental factors contribute to the interannual variability of tropical cyclones in the different basins: in the North Atlantic basin the vertical wind shear, potential intensity and low-level absolute vorticity are dominant, while in the North Pacific basins mid-level relative humidity and low-level absolute vorticity are dominant. Model resolution is crucial for a realistic simulation of tropical cyclone behaviour, and high-resolution GCMs are found to be valuable tools for investigating the global location and frequency of tropical cyclones.

The basic ingredients of the North Atlantic storm track. Part I: land-sea contrast and orography

Understanding and predicting changes in storm tracks over longer time scales is a challenging problem, particularly in the North Atlantic. This is due in part to the complex range of forcings (land–sea contrast, orography, sea surface temperatures, etc.) that combine to produce the structure of the storm track. The impact of land–sea contrast and midlatitude orography on the North Atlantic storm track is investigated through a hierarchy of GCM simulations using idealized and “semirealistic” boundary conditions in a high-resolution version of the Hadley Centre atmosphere model (HadAM3). This framework captures the large-scale essence of features such as the North and South American continents, Eurasia, and the Rocky Mountains, enabling the results to be applied more directly to realistic modeling situations than was possible with previous idealized studies. The physical processes by which the forcing mechanisms impact the large-scale flow and the midlatitude storm tracks are discussed. The characteristics of the North American continent are found to be very important in generating the structure of the North Atlantic storm track. In particular, the southwest–northeast tilt in the upper tropospheric jet produced by southward deflection of the westerly flow incident on the Rocky Mountains leads to enhanced storm development along an axis close to that of the continent’s eastern coastline. The approximately triangular shape of North America also enables a cold pool of air to develop in the northeast, intensifying the surface temperature contrast across the eastern coastline, consistent with further enhancements of baroclinicity and storm growth along the same axis.

Where do winds drive the Antarctic Circumpolar Current?

The strength of the Antarctic Circumpolar Current (ACC) is believed to depend on the westerly wind stress blowing over the Southern Ocean, although the exact relationship between winds and circumpolar transport is yet to be determined. Here we show, based on theoretical arguments and a hierarchy of numerical modeling experiments, that the global pycnocline depth and the baroclinic ACC transport are set by an integral measure of the wind stress over the path of the ACC, taking into account its northward deflection. Our results assume that the mesoscale eddy diffusivity is independent of the mean flow; while the relationship between wind stress and ACC transport will be more complicated in an eddy-saturated regime, our conclusion that the ACC is driven by winds over the circumpolar streamlines is likely to be robust.

Data assimilation for marine monitoring and prediction: The MERCATOR operational assimilation systems and the MERSEA developments

During the past 15 years, a number of initiatives have been undertaken at national level to develop ocean forecasting systems operating at regional and/or global scales. The co-ordination between these efforts has been organized internationally through the Global Ocean Data Assimilation Experiment (GODAE). The French MERCATOR project is one of the leading participants in GODAE. The MERCATOR systems routinely assimilate a variety of observations such as multi-satellite altimeter data, sea-surface temperature and in situ temperature and salinity profiles, focusing on high-resolution scales of the ocean dynamics. The assimilation strategy in MERCATOR is based on a hierarchy of methods of increasing sophistication including optimal interpolation, Kalman filtering and variational methods, which are progressively deployed through the Syst`eme d’Assimilation MERCATOR (SAM) series. SAM-1 is based on a reduced-order optimal interpolation which can be operated using ‘altimetry-only’ or ‘multi-data’ set-ups; it relies on the concept of separability, assuming that the correlations can be separated into a product of horizontal and vertical contributions. The second release, SAM-2, is being developed to include new features from the singular evolutive extended Kalman (SEEK) filter, such as three-dimensional, multivariate error modes and adaptivity schemes. The third one, SAM-3, considers variational methods such as the incremental four-dimensional variational algorithm. Most operational forecasting systems evaluated during GODAE are based on least-squares statistical estimation assuming Gaussian errors. In the framework of the EU MERSEA (Marine EnviRonment and Security for the European Area) project, research is being conducted to prepare the next-generation operational ocean monitoring and forecasting systems. The research effort will explore nonlinear assimilation formulations to overcome limitations of the current systems. This paper provides an overview of the developments conducted in MERSEA with the SEEK filter, the Ensemble Kalman filter and the sequential importance re-sampling filter.

Mathematical modelling of decision making processes in construction projects

Many different individuals, who have their own expertise and criteria for decision making, are involved in making decisions on construction projects. Decision-making processes are thus significantly affected by communication, in which a dynamic performance of human intentions leads to unpredictable outcomes. In order to theorise the decision making processes including communication, it is argued here that the decision making processes resemble evolutionary dynamics in terms of both selection and mutation, which can be expressed by the replicator-mutator equation. To support this argument, a mathematical model of decision making has been made from an analogy with evolutionary dynamics, in which there are three variables: initial support rate, business hierarchy, and power of persuasion. On the other hand, a survey of patterns in decision making in construction projects has also been performed through self-administered mail questionnaire to construction practitioners. Consequently, comparison between the numerical analysis of mathematical model and the statistical analysis of empirical data has shown a significant potential of the replicator-mutator equation as a tool to study dynamic properties of intentions in communication.

Phylogeny and the hierarchical organization of plant diversity

R. H. Whittaker's idea that plant diversity can be divided into a hierarchy of spatial components from alpha at the within-habitat scale through beta for the turnover of species between habitats to gamma along regional gradients implies the underlying existence of alpha, beta, and gamma niches. We explore the hypothesis that the evolution of a, (3, and gamma niches is also hierarchical, with traits that define the a niche being labile, while those defining a and 7 niches are conservative. At the a level we find support for the hypothesis in the lack of close significant phylogenetic relationship between meadow species that have similar a niches. In a second test, a niche overlap based on a variety of traits is compared between congeners and noncongeners in several communities; here, too, there is no evidence of a correlation between a niche and phylogeny. To test whether beta and gamma niches evolve conservatively, we reconstructed the evolution of relevant traits on evolutionary trees for 14 different clades. Tests against null models revealed a number of instances, including some in island radiations, in which habitat (beta niche) and elevational maximum (an aspect of the gamma niche) showed evolutionary conservatism.

Towards a definition of a crop wild relative

Crop wild relatives are an important socio-economic resource that is currently being eroded or even extinguished through careless human activities. If the Conference of the Parties (COP) to the CBD 2010 Biodiversity Target of achieving a significant reduction in the current rate of loss is to be achieved, we must first define what crop wild relatives are and how their conservation might be prioritised. A definition of a crop wild relative is proposed and illustrated in the light of previous Gene Pool concept theory. Where crossing and genetic diversity information is unavailable, the Taxon Group concept is introduced to assist recognition of the degree of crop wild relative relatedness by using the existing taxonomic hierarchy.