Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

The reaction of cis-[RuCl(2)(P-P)(N-N)] type complexes (P-P = 1,4-bis(diphenylphosphino)butane or (1,1`-diphenylphosphino)ferrocene; N-N = 2,2`-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P-P)(N-N)](+) species Upon characterization of the isolated compounds by elemental analysis, (31)P{(1)H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good pi acceptor, coordinates trans to the nitrogen atom. A (31)P{(1)H} NMR experiment following the reaction of the precursor cis-[RuCl(2)(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N-N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF(6) species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. (c) 2009 Elsevier Ltd. All rights reserved.

Orbitally driven east-west antiphasing of South American precipitation

The variations of tropical precipitation are antiphased between the hemispheres on orbital timescales. This antiphasing arises through the alternating strength of incoming solar radiation in the two hemispheres, which affects monsoon intensity and hence the position of the meridional atmospheric circulation of the Hadley cells(1-4). Here we compare an oxygen isotopic record recovered from a speleothem from northeast Brazil for the past 26,000 years with existing reconstructions of precipitation in tropical South America(5-8). During the Holocene, we identify a similar, but zonally oriented, antiphasing of precipitation within the same hemisphere: northeast Brazil experiences humid conditions during low summer insolation and aridity when summer insolation is high, whereas the rest of southern tropical South America shows opposite characteristics. Simulations with a general circulation model that incorporates isotopic variations support this pattern as well as the link to insolation-driven monsoon activity. Our results suggest that convective heating over tropical South America and associated adjustments in large-scale subsidence over northeast Brazil lead to a remote forcing of the South American monsoon, which determines most of the precipitation changes in the region on orbital timescales.

Automatic contour extraction from 2D neuron images

This work describes a novel methodology for automatic contour extraction from 2D images of 3D neurons (e.g. camera lucida images and other types of 2D microscopy). Most contour-based shape analysis methods cannot be used to characterize such cells because of overlaps between neuronal processes. The proposed framework is specifically aimed at the problem of contour following even in presence of multiple overlaps. First, the input image is preprocessed in order to obtain an 8-connected skeleton with one-pixel-wide branches, as well as a set of critical regions (i.e., bifurcations and crossings). Next, for each subtree, the tracking stage iteratively labels all valid pixel of branches, tip to a critical region, where it determines the suitable direction to proceed. Finally, the labeled skeleton segments are followed in order to yield the parametric contour of the neuronal shape under analysis. The reported system was successfully tested with respect to several images and the results from a set of three neuron images are presented here, each pertaining to a different class, i.e. alpha, delta and epsilon ganglion cells, containing a total of 34 crossings. The algorithms successfully got across all these overlaps. The method has also been found to exhibit robustness even for images with close parallel segments. The proposed method is robust and may be implemented in an efficient manner. The introduction of this approach should pave the way for more systematic application of contour-based shape analysis methods in neuronal morphology. (C) 2008 Elsevier B.V. All rights reserved.

Cellular automaton model for molecular traffic jams

We consider the time evolution of an exactly solvable cellular automaton with random initial conditions both in the large-scale hydrodynamic limit and on the microscopic level. This model is a version of the totally asymmetric simple exclusion process with sublattice parallel update and thus may serve as a model for studying traffic jams in systems of self-driven particles. We study the emergence of shocks from the microscopic dynamics of the model. In particular, we introduce shock measures whose time evolution we can compute explicitly, both in the thermodynamic limit and for open boundaries where a boundary-induced phase transition driven by the motion of a shock occurs. The motion of the shock, which results from the collective dynamics of the exclusion particles, is a random walk with an internal degree of freedom that determines the jump direction. This type of hopping dynamics is reminiscent of some transport phenomena in biological systems.

Decomposability problem on branched coverings

Given a branched covering of degree d between closed surfaces, it determines a collection of partitions of d, the branch data. In this work we show that any branch data are realized by an indecomposable primitive branched covering on a connected closed surface N with chi(N) <= 0. This shows that decomposable and indecomposable realizations may coexist. Moreover, we characterize the branch data of a decomposable primitive branched covering. Bibliography: 20 titles.

The role in the substrate specificity and catalysis of residues forming the substrate aglycone-binding site of a beta-glycosidase

The relative contributions to the specificity and catalysis of aglycone, of residues E190, E194, K201 and M453 that form the aglycone-binding site of a beta-glycosidase from Spodoptera frugiperda (EC 3.2.1.21), were investigated through site-directed mutagenesis and enzyme kinetic experiments. The results showed that E190 favors the binding of the initial portion of alkyl-type aglycones (up to the sixth methylene group) and also the first glucose unit of oligosaccharidic aglycones, whereas a balance between interactions with E194 and K201 determines the preference for glucose units versus alkyl moieties. E194 favors the binding of alkyl moieties, whereas K201 is more relevant for the binding of glucose units, in spite of its favorable interaction with alkyl moieties. The three residues E190, E194 and K201 reduce the affinity for phenyl moieties. In addition, M453 favors the binding of the second glucose unit of oligosaccharidic aglycones and also of the initial portion of alkyl-type aglycones. None of the residues investigated interacted with the terminal portion of alkyl-type aglycones. It was also demonstrated that E190, E194, K201 and M453 similarly contribute to stabilize ES double dagger. Their interactions with aglycone are individually weaker than those formed by residues interacting with glycone, but their joint catalytic effects are similar. Finally, these interactions with aglycone do not influence glycone binding.

FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

A Contour-based Separation of VerticallyAttached Traffic Signs

This report presents an algorithm for locating the cut points for and separatingvertically attached traffic signs in Sweden. This algorithm provides severaladvanced digital image processing features: binary image which representsvisual object and its complex rectangle background with number one and zerorespectively, improved cross correlation which shows the similarity of 2Dobjects and filters traffic sign candidates, simplified shape decompositionwhich smoothes contour of visual object iteratively in order to reduce whitenoises, flipping point detection which locates black noises candidates, chasmfilling algorithm which eliminates black noises, determines the final cut pointsand separates originally attached traffic signs into individual ones. At each step,the mediate results as well as the efficiency in practice would be presented toshow the advantages and disadvantages of the developed algorithm. Thisreport concentrates on contour-based recognition of Swedish traffic signs. Thegeneral shapes cover upward triangle, downward triangle, circle, rectangle andoctagon. At last, a demonstration program would be presented to show howthe algorithm works in real-time environment.

Rate Scheduling for HSDPA in UMTS

The introduction of a new technology High Speed Downlink Packet Access (HSDPA) in the Release 5 of the 3GPP specifications raises the question about its performance capabilities. HSDPA is a promising technology which gives theoretical rates up to 14.4 Mbits. The main objective of this thesis is to discuss the system level performance of HSDPAMainly the thesis exploration focuses on the Packet Scheduler because it is the central entity of the HSDPA design. Due to its function, the Packet Scheduler has a direct impact on the HSDPA system performance. Similarly, it also determines the end user performance, and more specifically the relative performance between the users in the cell.The thesis analyzes several Packet Scheduling algorithms that can optimize the trade-off between system capacity and end user performance for the traffic classes targeted in this thesis.The performance evaluation of the algorithms in the HSDPA system are carried out under computer aided simulations that are assessed under realistic conditions to predict the results as precise on the algorithms efficiency. The simulation of the HSDPA system and the algorithms are coded in C/C++ language

Baking Dalarna's biking cake : Collaboration as a means for destination competitiveness, a case study of “Biking Dalarna"

In the contemporary tourism industry, the competitive game is between destinations. Tourism operations struggle to remain competitive on the international market and their success depends to a large extent on other complementary and competing tourism organizations at the destination. It is the sum of the total tourism offerings at the destination which determines its attractiveness. This research explores tourism collaboration process as a means of generating destination competitiveness. The focus of the research is on the enhancing factors which contribute to the success of the collaboration and to the development of quality tourism products. The research studies the case of Biking Dalarna, a collaboration of different organizations at five biking destinations in Dalarna, Sweden. Its purpose is to develop biking tourism in the region and to make Dalarna into Sweden’s leading biking destination. It is a qualitative research; the empirical data was collected through in depth interviews with representatives of six Biking Dalarna member organizations. The qualitative data collected from the participants provides inside look into the members reflections and experience of collaborating. The findings of this research demonstrate how collaboration has improved the biking product in Dalarna and promoted solutions to development problems. The research finds the good relationship between the collaborating actors and the involvement and leadership of the regional tourism management organization as the most contributing factors to the success of Biking Dalarna. The research also suggests that a third desired outcome of collaboration, improved marketing attributes was yet to be achieved in the case of Biking Dalarna.

Gravitational self-localization for spherical masses

In this work, I consider the center-of-mass wave function for a homogenous sphere under the influence of the self-interaction due to Newtonian gravity. I solve for the ground state numerically and calculate the average radius as a measure of its size. For small masses, M≲10−17 kg, the radial size is independent of density, and the ground state extends beyond the extent of the sphere. For masses larger than this, the ground state is contained within the sphere and to a good approximation given by the solution for an effective radial harmonic-oscillator potential. This work thus determines the limits of applicability of the point-mass Newton Schrödinger equations for spherical masses. In addition, I calculate the fringe visibility for matter-wave interferometry and find that in the low-mass case, interferometry can in principle be performed, whereas for the latter case, it becomes impossible. Based on this, I discuss this transition as a possible boundary for the quantum-classical crossover, independent of the usually evoked environmental decoherence. The two regimes meet at sphere sizes R≈10−7 m, and the density of the material causes only minor variations in this value.

Le Statut comparé de l'autofiction chez Benjamin Constant et Amélie Nothomb : une histoire de genre?

Le genre autobiographique, malgré une popularité qui ne se dément pas depuis deux siècles, ne bénéficie pas d’une définition claire. Cet article se propose de montrer que cela est sans doute dû à l’hybridité intrinsèque de ce genre qui se traduit aussi par un pacte autobiographique complexe. Plus précisément, en s’appuyant sur les cas de Constant et de Nothomb, sera démontré que la lecture qui est faite des écrits intimes détermine bien souvent le genre. En ce qui concerne en particulier ces deux auteurs, leur personnalité changeante, contradictoire voire affabulatoire repousse le genre autobiographique dans ses limites, illustrent l’adage selon lequel le roman est plus vrai que la réalité vécue.  

Role of knowledge and ability in student nurses` clinical decision-making

Little is known about the acquisition of decision-making skills in nursing students as a function of experience and academic ability. Knowing how experience and academic skills interact may help inform clinical education programs and formulate ways of assessing students' progress. The aims of the present study were to develop a problem-solving task capable of measuring clinical decision-making skills in novice nurses at different levels of domain-specific knowledge; and to establish the relative impact on decision-making of domain-specific knowledge and general ability as determinants of the acquisition of decision-making skills. Three types of clinical problems of increasing complexity were developed. Sixty second-year and third-year student nurses with high and low academic scores were studied in terms of their ability to generate hypotheses for a hypothetical case, recognize disconfirming information and the need to access additional information, and diagnostic accuracy. The results showed that general academic ability and knowledge function partly independently in the acquisition of expertise in nursing. Academic ability affects decision-making in low complexity tasks, but as case complexity increases, domain-specific knowledge and experience determines decision-making skills. There are important differences in the way novices with different levels of knowledge and ability make clinical decisions and these can be studied by systematically increasing the complexity of the decision task. These results have implications for the way in which clinical education is structured and evaluated.

Feminists re-reading Bourdieu: old debates and new questions about gender habitus and gender change

There is a revival of interest in Bourdieu's work and this article examines dominant trends within feminist re-engagements. It considers the insights into gender identity afforded by ‘habitus’ and ‘social field’, distinguishing between analyses of 'gender habitus', and the potential of habitus and social field for feminist analysis of change. Feminist responses to Bourdieu continue to be divided on the extent to which social field structure determines habitus, and there is a tendency to represent the relationship as too seamless and coherent. Drawing on debates within recent feminist sociology, notably the work of Lois McNay and Lisa Adkins, this article argues instead for greater acknowledgement of the instability of gender norms and the contradictory effects of crossing different social fields. A feminist rethinking of the relationship between gender change, habitus and social field is suggested, which arises from a more contextual analysis of the varying degrees of correspondence between habitus and field. This addresses the co-existence of change and continuity in gender relations and identities, and aims to move such debates beyond questions of either freedom or reproduction.

Aggregate planning for seasonal demand : reconciling theory with practice

Purpose: The paper reports on the ramifications for production planning when monthly sales exhibit predictable seasonal highs and lows. The literature first acknowledged and dealt with the (aggregate planning) problem 50 years ago. Nevertheless, there is neither evidence that industry has adopted any of the mathematical techniques that were subsequently developed, nor a convincing explanation as to why not. Hence this research sets out to discover the methods manufacturers use to cope with seasonal demand, and how germane the published algorithms really are.

Design/methodology/approach: Forty-two case studies were compiled by interviewing senior managers and then conducting plant tours. No prior assumptions were made and the list of questions covered the gamut of production planning.

Findings: The main finding is that manufacturers select a straightforward production strategy, right from the outset, so the fundamental cost-balancing format is not relevant. The majority pick a “chase” strategy, since most organizations subscribe to a “just in time” ethos. Whenever a different strategy is preferred the rationale springs from skilled labour considerations or binding facilities constraints. The chosen strategy serves as a road map for resources acquisitions, and the master production schedule is constructed directly. So, the complex issue of how to disaggregate an optimal aggregate plan never even arises. Managers do not seek perfect solutions, but strive to eliminate, or contain, the most significant marginal costs. The nature of the business determines the most appropriate tactics to employ.

Originality/value: These findings break the mould as far as orthodox aggregate planning is concerned and show why theory is at odds with practice, whilst reaffirming the importance of concepts such as “flexibility”, “integration”, and “just-in-time production”.