Computational Approach to the Study of Thermal Spin Crossover Phenomena

The key parameters associated to the thermally induced spin crossover process have been calculated for a series of Fe(II) complexes with mono-, bi-, and tridentate ligands. Combination of density functional theory calculations for the geometries and for normal vibrational modes, and highly correlated wave function methods for the energies, allows us to accurately compute the entropy variation associated to the spin transition and the zero-point corrected energy difference between the low- and high-spin states. From these values, the transition temperature, T 1/2, is estimated for different compounds.

Pauson-Khand Adducts of N-Boc-propargylamine: A New Approach to 4,5-Disubstituted Cyclopentenones

A new approach to the synthesis of 4,5-disubstituted cyclopentenones is described. The strategy is based on the Pauson-Khand (PK) reaction of norbornadiene and N-Boc-propargylamine as alkyne with a masked leaving group, which can be eliminated at will. This approach to the synthesis of 4,5-disubstituted cyclopentenones overcomes the problem of using the alkylation to introduce the alpha-side-chain. As an example, prostane 13-epi-12-oxo-phytodienoic acid (13-epi-12-oxo-PDA) methyl ester was synthesized.

Technical Note: Dissolved organic matter fluorescence a finite mixture approach to deconvolve excitation-emission matrices

The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves individual EEMs is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimisation algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. The EEMs of a simple artificial mixture of fluorophores and DOM samples collected in a Mediterranean river are used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

Testing a new multigroup inference approach to reconstructing past environmental conditions

A new, quantitative, inference model for environmental reconstruction (transfer function), based for the first time on the simultaneous analysis of multigroup species, has been developed. Quantitative reconstructions based on palaeoecological transfer functions provide a powerful tool for addressing questions of environmental change in a wide range of environments, from oceans to mountain lakes, and over a range of timescales, from decades to millions of years. Much progress has been made in the development of inferences based on multiple proxies but usually these have been considered separately, and the different numeric reconstructions compared and reconciled post-hoc. This paper presents a new method to combine information from multiple biological groups at the reconstruction stage. The aim of the multigroup work was to test the potential of the new approach to making improved inferences of past environmental change by improving upon current reconstruction methodologies. The taxonomic groups analysed include diatoms, chironomids and chrysophyte cysts. We test the new methodology using two cold-environment training-sets, namely mountain lakes from the Pyrenees and the Alps. The use of multiple groups, as opposed to single groupings, was only found to increase the reconstruction skill slightly, as measured by the root mean square error of prediction (leave-one-out cross-validation), in the case of alkalinity, dissolved inorganic carbon and altitude (a surrogate for air-temperature), but not for pH or dissolved CO2. Reasons why the improvement was less than might have been anticipated are discussed. These can include the different life-forms, environmental responses and reaction times of the groups under study.

A territorial approach to R&D subsidies: Empirical evidence for Catalonian firms

Using a database of 2,263 responses to R&D public calls in Catalonia, during the period 2007–2010, this paper proceeds to analyse the potential interaction of the territorial and policy dimensions with the propensity to apply for, and be awarded, a public R&D subsidy. Controlling for characteristics at the firm and project level, we estimate models using a twostep procedure. In the first step, our results suggest that large firms which export and which belong to high-tech manufactures are more likely to participate in a public R&D call. Furthermore, both urban location and past experience of such calls have a positive effect. Our territorial proxy of information spillovers shows a positive sign, but this is only significant at intra-industry level. Membership of one of the sectors prioritized by the Catalan government, perhaps surprisingly, does not have a significant impact. In the second step, our results show that cooperative projects, SMEs or old firms shows a positive effect on the probability of obtaining a public subsidy. Finally, the cluster policy does not show a clear relationship with the public R&D call, suggesting that cluster policies and R&D subsidies follow different goals. Our results are in line with previous results in the literature, but they highlight the unequal territorial distribution of the firms which apply and the fact that policymakers should interlink the decision criteria for their public call with other policies.

Approach to the Lower Pliocene marine-continental correlation from southern Spain. The micrommamal site of Alhaurín el Grande-1 (Málaga Basin, Betic Cordillera, Spain)

A new micromammal site at Alhaurín el Grande (Málaga, southern Spain) located above early Pliocene marine deposits allows an approach to the marine-continental correlation for this age. The early Pliocene marine filling throughout the Málaga Basin is developed in three transgressive-regressive sequences (Pl-1, Pl-2, and Pl-3 units) bounded by discontinuities. At the top of the intermediate sequence Pl-2, peaty sediments have yielded fossils of Rodentia, Lagomorpha, Insectivora, and Crocodylia. The presence of Cricetus barrieri Mein & Michaux, 1970 in combination with murids, both of primitive morphology, such as Apodemus gudrunae Van de Weerd, 1976, and more advanced forms (i.e. Occitanomys brailloni Michaux, 1969 and Stephanomys donnezani cordii Ruiz Bustos, 1986), points to an early Ruscinian age (MN 14 biozone). Based on the planktonic foraminifers, the biostratigraphic data indicate that marine sediments just below the micromammal beds belong to the MPl-2 biozone of the early Zanclean. Available paleomagnetic data from the marine sediments show that the micromammal bed must be located between the normal geomagnetic subchron C3n3n (4.89-4.80 Ma) and the subchron C3n2n (4.63-4.49 Ma), limiting the age of this site to the late part of the early Zanclean.

A relational approach to the geography of innovation: a typology of regions

The aim of this study was to devise a method for computing a composite indicator that measures the regional degree of exposure to external knowledge sources. On the basis of this indicator, we propose a typology of regions according to their potential capacity to access extra-local items of knowledge, which might help them to recombine complementary elements of such an asset to produce a higher number of new ideas. Building on various research streams that have been relatively independent to date, we summarize a non-exhaustive instrumental list of recent studies that motivates our approach and the construction of our complex indicator, which can be used to appraise the extent to which each region is in an optimal position to access external innovative resources.

A novel approach to analysing the regimes of temporary streams in relation to their controls on the composition and structure of aquatic biota

Temporary streams are those water courses that undergo the recurrent cessation of flow or the complete drying of their channel. The structure and composition of biological communities in temporary stream reaches are strongly dependent on the temporal changes of the aquatic habitats determined by the hydrological conditions. Therefore, the structural and functional characteristics of aquatic fauna to assess the ecological quality of a temporary stream reach cannot be used without taking into account the controls imposed by the hydrological regime. This paper develops methods for analysing temporary streams' aquatic regimes, based on the definition of six aquatic states that summarize the transient sets of mesohabitats occurring on a given reach at a particular moment, depending on the hydrological conditions: Hyperrheic, Eurheic, Oligorheic, Arheic, Hyporheic and Edaphic. When the hydrological conditions lead to a change in the aquatic state, the structure and composition of the aquatic community changes according to the new set of available habitats. We used the water discharge records from gauging stations or simulations with rainfall-runoff models to infer the temporal patterns of occurrence of these states in the Aquatic States Frequency Graph we developed. The visual analysis of this graph is complemented by the development of two metrics which describe the permanence of flow and the seasonal predictability of zero flow periods. Finally, a classification of temporary streams in four aquatic regimes in terms of their influence over the development of aquatic life is updated from the existing classifications, with stream aquatic regimes defined as Permanent, Temporary-pools, Temporary-dry and Episodic. While aquatic regimes describe the long-term overall variability of the hydrological conditions of the river section and have been used for many years by hydrologists and ecologists, aquatic states describe the availability of mesohabitats in given periods that determine the presence of different biotic assemblages. This novel concept links hydrological and ecological conditions in a unique way. All these methods were implemented with data from eight temporary streams around the Mediterranean within the MIRAGE project. Their application was a precondition to assessing the ecological quality of these streams.

A hybrid approach to treebank construction

Este artículo describe investigación sobre los efectos de la desambiguación morfosintáctica usada como un preproceso de un analizador sint´actico profundo basado en HPSG, en el contexto del desarrollo de un treebank del español de código abierto, en el entorno de DELPH-IN. La anotación treebank se realiza manualmente tomando las decisiones apropiadas entre las opciones propuestas por el sistema y ordenadas por un módulo estadístico. Los experimentos presentados muestran que el uso de un etiquetador reduce la ambigüedad de las frases, y contribuye a limitar la cantidad de frases cuyo análisis sobrepasa a el límite de tiempo, y ayuda a al m´odulo estadístico a clasificar el árbol correcto entre los n mejores. Por un lado, nuestros resultados validan los beneficios ya reportados en la literatura de tal preproceso de análisis profundo con respecto a la velocidad, cobertura y precisión. Por otro lado, proponemos una estrategia basada en existentes herramientas de código abierto y recursos para desarrollar con alta consitencia treebanks de sintaxis profunda para idiomas con limitada disponibilidad de recursos lingüísticos.

A territorial approach to R&D subsidies: Empirical evidence for Catalonian firms

Using a database of 2,263 responses to R&D public calls in Catalonia, during the period 2007–2010, this paper proceeds to analyse the potential interaction of the territorial and policy dimensions with the propensity to apply for, and be awarded, a public R&D subsidy. Controlling for characteristics at the firm and project level, we estimate models using a two-step procedure. In the first step, our results suggest that large firms which export and which belong to high-tech manufactures are more likely to participate in a public R&D call. Furthermore, both urban location and past experience of such calls have a positive effect. Our territorial proxy of information spillovers shows a positive sign, but this is only significant at intra-industry level. Membership of one of the sectors prioritized by the Catalan government, perhaps surprisingly, does not have a significant impact. In the second step, our results show that cooperative projects, SMEs or old firms shows a positive effect on the probability of obtaining a public subsidy. Finally, the cluster policy does not show a clear relationship with the public R&D call, suggesting that cluster policies and R&D subsidies follow different goals. Our results are in line with previous results in the literature, but they highlight the unequal territorial distribution of the firms which apply and the fact that policymakers should interlink the decision criteria for their public call with other policies. Keywords: Evaluation, R&D policies, territorial approach, clusters JEL Classifications: L53, L25, O38

An Explanatory Approach to the Political Uses of ICT Initiatives for Participation : Institutions, Context, and Characteristics of the Actors

Political actors use ICTs in a different manner and in different degrees when it comes to achieving a closer relationship between the public and politicians. Usually, political parties develop ICT strategies only for electoral campaigning and therefore restrain ICT usages to providing information and establishing a few channels of communication. By contrast, local governments make much more use of ICT tools for participatory and deliberative purposes. These differences in usages have not been well explained in the literature because of a lack of a comprehensive explanatory model. This chapter seeks to build the basis for this model, that is, to establish which factors affect and condition different political uses of ICTs and which principles underlie that behaviour. We consider that political actors are intentional and their behaviour is mediated by the political institutions and the socioeconomic context of the country. Also, though, the actor¿s own characteristics, such as the type and size of the organization or the model of e-democracy that the actor upholds, can have an influence in launching ICT initiatives for approaching the public.

An ontology to automated learning scenarios? an approach to its knowledge domain

Automation or semi-automation of learning scenariospecifications is one of the least exploredsubjects in the e-learning research area. There isa need for a catalogue of learning scenarios and atechnique to facilitate automated retrieval of stored specifications. This requires constructing anontology with this goal and is justified inthis paper. This ontology must mainlysupport a specification technique for learning scenarios. This ontology should also be useful in the creation and validation of new scenarios as well as in the personalization of learning scenarios or their monitoring. Thus, after justifying the need for this ontology, a first approach of a possible knowledge domain is presented. An example of a concrete learning scenario illustrates some relevant concepts supported by this ontology in order to define the scenario in such a way that it could be easy to automate.

A new approach to segmentation based on fusing circumscribed contours, region growing and clustering

One of the major problems in machine vision is the segmentation of images of natural scenes. This paper presents a new proposal for the image segmentation problem which has been based on the integration of edge and region information. The main contours of the scene are detected and used to guide the posterior region growing process. The algorithm places a number of seeds at both sides of a contour allowing stating a set of concurrent growing processes. A previous analysis of the seeds permits to adjust the homogeneity criterion to the regions's characteristics. A new homogeneity criterion based on clustering analysis and convex hull construction is proposed