Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly

Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest.

Nocturnal ranging behaviour of urban hedgehogs, Erinaceus europaeus, in relation to risk and reward

Urban areas have both positive and negative influences on wildlife. For terrestrial mammals, one of the principle problems is the risk associated with moving through the environment whilst foraging. In this study, we examined nocturnal patterns of movement of urban-dwelling hedgehogs (Erinaceus europaeus) in relation to (i) the risks posed by predators and motor vehicles and (ii) nightly weather patterns. Hedgehogs preferentially utilised the gardens of semi-detached and terraced houses. However, females, but not males, avoided the larger back gardens of detached houses, which contain more of the habitat features selected by badgers. This difference in the avoidance of predation risk is probably associated with sex differences in breeding behaviour. Differences in nightly movement patterns were consistent with strategies associated with mating behaviour and the accumulation of fat reserves for hibernation. Hedgehogs also exhibited differences in behaviour associated with the risks posed by humans; they avoided actively foraging near roads and road verges, but did not avoid crossing roads per se. They were, however, significantly more active after midnight when there was a marked reduction in vehicle and foot traffic. In particular, responses to increased temperature, which is associated with increased abundance of invertebrate prey, were only observed after midnight. This variation in the timing of bouts of activity would reduce the risks associated with human activities. There were also profound differences in both area ranged and activity with chronological year which warrant further investigation.

Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of similar to 10(-11) cm(2) s(-1) for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.

Prospects and challenges for sustainable management of the mango stone weevil, Sternochetus mangiferae (F.) (Coleoptera: Curculionidae) in West Africa: a review

Commercial mango production in Ghana is a relatively young industry faced with several pest problems including the mango stone weevil, Sternochetus mangiferae (F.). There is an urgent need to control this and other pests to facilitate access to the international export market for fresh mango fruits. A literature survey identifies stone weevil control tactics in the areas of host plant resistance, administrative and legislative controls, use of pesticides, biological control, cultural control and quarantine and phytosanitary measures that have been developed in other mango-producing areas. We assess these pest management approaches for their relevance to Ghana and West Africa, with emphasis on the research required for their appropriate, effective and sustainable use in the systems of mango production of the West African sub-region. The importance of processing and value addition technologies, as a means of circumventing the quarantine hurdles of S. mangiferae, is highlighted.

Some physical drivers of changes in the winter storm tracks over the North Atlantic and Mediterranean during the Holocene

The winter climate of Europe and the Mediterranean is dominated by the weather systems of the mid-latitude storm tracks. The behaviour of the storm tracks is highly variable, particularly in the eastern North Atlantic, and has a profound impact on the hydroclimate of the Mediterranean region. A deeper understanding of the storm tracks and the factors that drive them is therefore crucial for interpreting past changes in Mediterranean climate and the civilizations it has supported over the last 12 000 years (broadly the Holocene period). This paper presents a discussion of how changes in climate forcing (e.g. orbital variations, greenhouse gases, ice sheet cover) may have impacted on the ‘basic ingredients’ controlling the mid-latitude storm tracks over the North Atlantic and the Mediterranean on intermillennial time scales. Idealized simulations using the HadAM3 atmospheric general circulation model (GCM) are used to explore the basic processes, while a series of timeslice simulations from a similar atmospheric GCM coupled to a thermodynamic slab ocean (HadSM3) are examined to identify the impact these drivers have on the storm track during the Holocene. The results suggest that the North Atlantic storm track has moved northward and strengthened with time since the Early to Mid-Holocene. In contrast, the Mediterranean storm track may have weakened over the same period. It is, however, emphasized that much remains still to be understood about the evolution of the North Atlantic and Mediterranean storm tracks during the Holocene period.

Effect of soil waterlogging on below-ground biomass allometric relations in Norway spruce

An increasing importance is assigned to the estimation and verification of carbon stocks in forests. Forestry practice has several long-established and reliable methods for the assessment of aboveground biomass; however we still miss accurate predictors of belowground biomass. A major windthrow event exposing the coarse root systems of Norway spruce trees allowed us to assess the effects of contrasting soil stone and water content on belowground allocation. Increasing stone content decreases root/shoot ratio, while soil waterlogging leads to an increase in this ratio. We constructed allometric relationships for belowground biomass prediction and were able to show that only soil waterlogging significantly impacts model parameters. We showed that diameter at breast height is a reliable predictor of belowground biomass and, once site-specific parameters have been developed, it is possible to accurately estimate belowground biomass in Norway spruce.

Analysis of disputed single-parent/child and sibling relationships using 16 STR loci

This study describes the validation of short tandem repeat (STR) systems for the resolution of cases of disputed parentage where only a single parent is available for testing or where the claimed relationship of both parents is in doubt and also cases where sibship must be tested. Three separate multiplex systems the Second Generation Multiplex, Powerplex 1.2 and FFFL have been employed, giving a total of 16 STR loci. Both empirical and theoretical approaches to the validation have been adopted. Appropriate equations have been derived to calculate likelihood ratios for different relationships, incorporating a correction for subpopulation effects. An F(ST) point estimate of 1% has been applied throughout. Empirically, 101 cases of alleged father, alleged mother and child where analysed using six SLP systems and also using the three multiplex STR systems. Of the 202 relationships tested, 197 were independently resolved by both systems, providing either clear evidence of non-parentage or strong support for the relationship.

Studying the effect of systemisation on design activity

It is considered that systemisation, the use of standard systems of components and design solutions, has an effect on the activities of the designer. This paper draws on many areas of knowledge; design movements, economic theory, quality evaluation and organisation theory to substantiate the view that systemisation will reduce the designer's discretion at the point of design. A methodology to test this hypothesis is described which will be of use to other researchers studying the social processes of construction organisations.

L1 transfer in the acquisition of manner and path in Spanish by native speakers of English

In this article the authors argue that L1 transfer from English is not only important in the early stages of L2 acquisition of Spanish, but remains influential in later stages if there is not enough positive evidence for the learners to progress in their development (Lefebvre, White, & Jourdan, 2006). The findings are based on analyses of path and manner of movement in stories told by British students of Spanish (N = 68) of three different proficiency levels. Verbs that conflate motion and path, on the one hand, are mastered early, possibly because the existence of Latinate path verbs, such as enter and ascend in English, facilitate their early acquisition by British learners of Spanish. Contrary to the findings of Cadierno (2004) and Cadierno and Ruiz (2006), the encoding of manner, in particular in boundary crossing contexts, seems to pose enormous difficulties, even among students who had been abroad on a placement in a Spanish-speaking country prior to the data collection. An analysis of the frequency of manner verbs in Spanish corpora shows that one of the key reasons why students struggle with manner is that manner verbs are so infrequent in Spanish. The authors claim that scarce positive evidence in the language exposed to and little or no negative evidence are responsible for the long-lasting effect of transfer on the expression of manner.

The use of cursor measures for motion-impaired computer users

“Point and click” interactions remain one of the key features of graphical user interfaces (GUIs). People with motion-impairments, however, can often have difficulty with accurate control of standard pointing devices. This paper discusses work that aims to reveal the nature of these difficulties through analyses that consider the cursor’s path of movement. A range of cursor measures was applied, and a number of them were found to be significant in capturing the differences between able-bodied users and motion-impaired users, as well as the differences between a haptic force feedback condition and a control condition. The cursor measures found in the literature, however, do not make up a comprehensive list, but provide a starting point for analysing cursor movements more completely. Six new cursor characteristics for motion-impaired users are introduced to capture aspects of cursor movement different from those already proposed.

PDM 2006: Proceedings of the International Workshop on Data Mining

Recently major processor manufacturers have announced a dramatic shift in their paradigm to increase computing power over the coming years. Instead of focusing on faster clock speeds and more powerful single core CPUs, the trend clearly goes towards multi core systems. This will also result in a paradigm shift for the development of algorithms for computationally expensive tasks, such as data mining applications. Obviously, work on parallel algorithms is not new per se but concentrated efforts in the many application domains are still missing. Multi-core systems, but also clusters of workstations and even large-scale distributed computing infrastructures provide new opportunities and pose new challenges for the design of parallel and distributed algorithms. Since data mining and machine learning systems rely on high performance computing systems, research on the corresponding algorithms must be on the forefront of parallel algorithm research in order to keep pushing data mining and machine learning applications to be more powerful and, especially for the former, interactive. To bring together researchers and practitioners working in this exciting field, a workshop on parallel data mining was organized as part of PKDD/ECML 2006 (Berlin, Germany). The six contributions selected for the program describe various aspects of data mining and machine learning approaches featuring low to high degrees of parallelism: The first contribution focuses the classic problem of distributed association rule mining and focuses on communication efficiency to improve the state of the art. After this a parallelization technique for speeding up decision tree construction by means of thread-level parallelism for shared memory systems is presented. The next paper discusses the design of a parallel approach for dis- tributed memory systems of the frequent subgraphs mining problem. This approach is based on a hierarchical communication topology to solve issues related to multi-domain computational envi- ronments. The forth paper describes the combined use and the customization of software packages to facilitate a top down parallelism in the tuning of Support Vector Machines (SVM) and the next contribution presents an interesting idea concerning parallel training of Conditional Random Fields (CRFs) and motivates their use in labeling sequential data. The last contribution finally focuses on very efficient feature selection. It describes a parallel algorithm for feature selection from random subsets. Selecting the papers included in this volume would not have been possible without the help of an international Program Committee that has provided detailed reviews for each paper. We would like to also thank Matthew Otey who helped with publicity for the workshop.

Duality, observability, and controllability for linear time-varying descriptor systems

A characterization of observability for linear time-varying descriptor systemsE(t)x(t)+F(t)x(t)=B(t)u(t), y(t)=C(t)x(t) was recently developed. NeitherE norC were required to have constant rank. This paper defines a dual system, and a type of controllability so that observability of the original system is equivalent to controllability of the dual system. Criteria for observability and controllability are given in terms of arrays of derivatives of the original coefficients. In addition, the duality results of this paper lead to an improvement on a previous fundamental structure result for solvable systems of the formE(t)x(t)+F(t)x(t)=f(tt).

The domestication of water: water management in the ancient world and its prehistoric origins in the Jordan Valley

The ancient civilizations were dependent upon sophisticated systems of water management. The hydraulic engineering works found in ancient Angkor (ninth to thirteenth century AD), the Aztec city of Tenochtitlan (thirteenth to fifteenth century AD), Byzantine Constantinople (fourth to sixth century AD) and Nabatean Petra (sixth century BC to AD 106) are particularly striking because each of these is in localities of the world that are once again facing a water crisis. Without water management, such ancient cities would never have emerged, nor would the urban communities and towns from which they developed. Indeed, the ‘domestication’ of water marked a key turning point in the cultural trajectory of each region of the world where state societies developed. This is illustrated by examining the prehistory of water management in the Jordan Valley, identifying the later Neolithic (approx. 8300–6500 years ago) as a key period when significant investment in water management occurred, laying the foundation for the development of the first urban communities of the Early Bronze Age.