Bulk-plasmon dispersion relations in metals

Using an extended-random-phase-approximation sum-rule technique, we have investigated the bulk-plasmon dispersion relation, incorporating in a simple way exchange and correlation effects within the jellium model. The results obtained are compared with recent experimental findings. The key role played by exchange and correlation effects in improving the agreement between theory and experiment is stressed. The static polarizability has also been calculated as a function of q. The formulas can be easily modified to incorporate band-structure effects (through an intraband electron effective mass) and core-polarization effects (through a static dielectric constant).

Cheminformatic studies of molecular properties and their influence on bioactivity in the context of drug discovery

Molecular shape has long been known to be an important property for the process of molecular recognition. Previous studies postulated the existence of a drug-like shape space that could be used to artificially bias the composition of screening libraries, with the aim to increase the chance of success in Hit Identification. In this work, it was analysed to which extend this assumption holds true. Normalized Principal Moments of Inertia Ratios (NPRs) have been used to describe the molecular shape of small molecules. It was investigated, whether active molecules of diverse targets are located in preferred subspaces of the NPR shape space. Results illustrated a significantly stronger clustering than could be expected by chance, with parts of the space unlikely to be occupied by active compounds. Furthermore, a strong enrichment of elongated, rather flat shapes could be observed, while globular compounds were highly underrepresented. This was confirmed for a wide range of small molecule datasets from different origins. Active compounds exhibited a high overlap in their shape distributions across different targets, making a purely shape­ based discrimination very difficult. An additional perspective was provided by comparing the shapes of protein binding pockets with those of their respective ligands. Although more globular than their ligands, it was observed that binding sites shapes exhibited a similarly skewed distribution in shape space: spherical shapes were highly underrepresented. This was different for unoccupied binding pockets of smaller size. These were on the contrary identified to possess a more globular shape. The relation between shape complementarity and exhibited bioactivity was analysed; a moderate correlation between bioactivity and parameters including pocket coverage, distance in shape space, and others could be identified, which reflects the importance of shape complementarity. However, this also suggests that other aspects are of relevance for molecular recognition. A subsequent analysis assessed if and how shape and volume information retrieved from pocket or respective reference ligands could be used as a pre-filter in a virtual screening approach. ln Lead Optimization compounds need to get optimized with respect to a variety of pararneters. Here, the availability of past success stories is very valuable, as they can guide medicinal chemists during their analogue synthesis plans. However, although of tremendous interest for the public domain, so far only large corporations had the ability to mine historical knowledge in their proprietary databases. With the aim to provide such information, the SwissBioisostere database was developed and released during this thesis. This database contains information on 21,293,355 performed substructural exchanges, corresponding to 5,586,462 unique replacements that have been measured in 35,039 assays against 1,948 molecular targets representing 30 target classes, and on their impact on bioactivity . A user-friendly interface was developed that provides facile access to these data and is accessible at http//www.swissbioisostere.ch. The ChEMBL database was used as primary data source of bioactivity information. Matched molecular pairs have been identified in the extracted and cleaned data. Success-based scores were developed and integrated into the database to allow re-ranking of proposed replacements by their past outcomes. It was analysed to which degree these scores correlate with chemical similarity of the underlying fragments. An unexpectedly weak relationship was detected and further investigated. Use cases of this database were envisioned, and functionalities implemented accordingly: replacement outcomes are aggregatable at the assay level, and it was shawn that an aggregation at the target or target class level could also be performed, but should be accompanied by a careful case-by-case assessment. It was furthermore observed that replacement success depends on the activity of the starting compound A within a matched molecular pair A-B. With increasing potency the probability to lose bioactivity through any substructural exchange was significantly higher than in low affine binders. A potential existence of a publication bias could be refuted. Furthermore, often performed medicinal chemistry strategies for structure-activity-relationship exploration were analysed using the acquired data. Finally, data originating from pharmaceutical companies were compared with those reported in the literature. It could be seen that industrial medicinal chemistry can access replacement information not available in the public domain. In contrast, a large amount of often-performed replacements within companies could also be identified in literature data. Preferences for particular replacements differed between these two sources. The value of combining different endpoints in an evaluation of molecular replacements was investigated. The performed studies highlighted furthermore that there seem to exist no universal substructural replacement that always retains bioactivity irrespective of the biological environment. A generalization of bioisosteric replacements seems therefore not possible. - La forme tridimensionnelle des molécules a depuis longtemps été reconnue comme une propriété importante pour le processus de reconnaissance moléculaire. Des études antérieures ont postulé que les médicaments occupent préférentiellement un sous-ensemble de l'espace des formes des molécules. Ce sous-ensemble pourrait être utilisé pour biaiser la composition de chimiothèques à cribler, dans le but d'augmenter les chances d'identifier des Hits. L'analyse et la validation de cette assertion fait l'objet de cette première partie. Les Ratios de Moments Principaux d'Inertie Normalisés (RPN) ont été utilisés pour décrire la forme tridimensionnelle de petites molécules de type médicament. Il a été étudié si les molécules actives sur des cibles différentes se co-localisaient dans des sous-espaces privilégiés de l'espace des formes. Les résultats montrent des regroupements de molécules incompatibles avec une répartition aléatoire, avec certaines parties de l'espace peu susceptibles d'être occupées par des composés actifs. Par ailleurs, un fort enrichissement en formes allongées et plutôt plates a pu être observé, tandis que les composés globulaires étaient fortement sous-représentés. Cela a été confirmé pour un large ensemble de compilations de molécules d'origines différentes. Les distributions de forme des molécules actives sur des cibles différentes se recoupent largement, rendant une discrimination fondée uniquement sur la forme très difficile. Une perspective supplémentaire a été ajoutée par la comparaison des formes des ligands avec celles de leurs sites de liaison (poches) dans leurs protéines respectives. Bien que plus globulaires que leurs ligands, il a été observé que les formes des poches présentent une distribution dans l'espace des formes avec le même type d'asymétrie que celle observée pour les ligands: les formes sphériques sont fortement sous­ représentées. Un résultat différent a été obtenu pour les poches de plus petite taille et cristallisées sans ligand: elles possédaient une forme plus globulaire. La relation entre complémentarité de forme et bioactivité a été également analysée; une corrélation modérée entre bioactivité et des paramètres tels que remplissage de poche, distance dans l'espace des formes, ainsi que d'autres, a pu être identifiée. Ceci reflète l'importance de la complémentarité des formes, mais aussi l'implication d'autres facteurs. Une analyse ultérieure a évalué si et comment la forme et le volume d'une poche ou de ses ligands de référence pouvaient être utilisés comme un pré-filtre dans une approche de criblage virtuel. Durant l'optimisation d'un Lead, de nombreux paramètres doivent être optimisés simultanément. Dans ce contexte, la disponibilité d'exemples d'optimisations réussies est précieuse, car ils peuvent orienter les chimistes médicinaux dans leurs plans de synthèse par analogie. Cependant, bien que d'un extrême intérêt pour les chercheurs dans le domaine public, seules les grandes sociétés pharmaceutiques avaient jusqu'à présent la capacité d'exploiter de telles connaissances au sein de leurs bases de données internes. Dans le but de remédier à cette limitation, la base de données SwissBioisostere a été élaborée et publiée dans le domaine public au cours de cette thèse. Cette base de données contient des informations sur 21 293 355 échanges sous-structuraux observés, correspondant à 5 586 462 remplacements uniques mesurés dans 35 039 tests contre 1948 cibles représentant 30 familles, ainsi que sur leur impact sur la bioactivité. Une interface a été développée pour permettre un accès facile à ces données, accessible à http:/ /www.swissbioisostere.ch. La base de données ChEMBL a été utilisée comme source de données de bioactivité. Une version modifiée de l'algorithme de Hussain et Rea a été implémentée pour identifier les Matched Molecular Pairs (MMP) dans les données préparées au préalable. Des scores de succès ont été développés et intégrés dans la base de données pour permettre un reclassement des remplacements proposés selon leurs résultats précédemment observés. La corrélation entre ces scores et la similarité chimique des fragments correspondants a été étudiée. Une corrélation plus faible qu'attendue a été détectée et analysée. Différents cas d'utilisation de cette base de données ont été envisagés, et les fonctionnalités correspondantes implémentées: l'agrégation des résultats de remplacement est effectuée au niveau de chaque test, et il a été montré qu'elle pourrait également être effectuée au niveau de la cible ou de la classe de cible, sous réserve d'une analyse au cas par cas. Il a en outre été constaté que le succès d'un remplacement dépend de l'activité du composé A au sein d'une paire A-B. Il a été montré que la probabilité de perdre la bioactivité à la suite d'un remplacement moléculaire quelconque est plus importante au sein des molécules les plus actives que chez les molécules de plus faible activité. L'existence potentielle d'un biais lié au processus de publication par articles a pu être réfutée. En outre, les stratégies fréquentes de chimie médicinale pour l'exploration des relations structure-activité ont été analysées à l'aide des données acquises. Enfin, les données provenant des compagnies pharmaceutiques ont été comparées à celles reportées dans la littérature. Il a pu être constaté que les chimistes médicinaux dans l'industrie peuvent accéder à des remplacements qui ne sont pas disponibles dans le domaine public. Par contre, un grand nombre de remplacements fréquemment observés dans les données de l'industrie ont également pu être identifiés dans les données de la littérature. Les préférences pour certains remplacements particuliers diffèrent entre ces deux sources. L'intérêt d'évaluer les remplacements moléculaires simultanément selon plusieurs paramètres (bioactivité et stabilité métabolique par ex.) a aussi été étudié. Les études réalisées ont souligné qu'il semble n'exister aucun remplacement sous-structural universel qui conserve toujours la bioactivité quel que soit le contexte biologique. Une généralisation des remplacements bioisostériques ne semble donc pas possible.

Multiscaling and information content of natural color images

Naive scale invariance is not a true property of natural images. Natural monochrome images possess a much richer geometrical structure, which is particularly well described in terms of multiscaling relations. This means that the pixels of a given image can be decomposed into sets, the fractal components of the image, with well-defined scaling exponents [Turiel and Parga, Neural Comput. 12, 763 (2000)]. Here it is shown that hyperspectral representations of natural scenes also exhibit multiscaling properties, observing the same kind of behavior. A precise measure of the informational relevance of the fractal components is also given, and it is shown that there are important differences between the intrinsically redundant red-green-blue system and the decorrelated one defined in Ruderman, Cronin, and Chiao [J. Opt. Soc. Am. A 15, 2036 (1998)].

Electronic structure and magnetic interactions of the spin-chain compounds Ca2CuO3 and Sr2CuO3

The results are presented of a combined periodic and cluster model approach to the electronic structure and magnetic interactions in the spin-chain compounds Ca2CuO3 and Sr2CuO3. An extended t-J model is presented that includes in-chain and interchain hopping and magnetic interaction processes with parameters extracted from ab initio calculations. For both compounds, the in-chain magnetic interaction is found to be around -240 meV, larger than in any of the other cuprates reported in the literature. The interchain magnetic coupling is found to be weakly antiferromagnetic, -1 meV. The effective in-chain hopping parameters are estimated to be ~650 meV for both compounds, whereas the value of the interchain hopping parameter is 30 meV for Sr2CuO3 and 40 meV for Ca2CuO3, in line with the larger interchain distance in the former compound. These effective parameters are shown to be consistent with expressions recently suggested for the Néel temperature and the magnetic moments, and with relations that emerge from the t-J model Hamiltonian. Next, we investigate the physical nature of the band gap. Periodic calculations indicate that an interpretation in terms of a charge-transfer insulator is the most appropriate one, in contrast to the suggestion of a covalent correlated insulator recently reported in the literature.

Chemodiversity and molecular plasticity: recognition processes as explored by property spaces.

In the last few years, a need to account for molecular flexibility in drug-design methodologies has emerged, even if the dynamic behavior of molecular properties is seldom made explicit. For a flexible molecule, it is indeed possible to compute different values for a given conformation-dependent property and the ensemble of such values defines a property space that can be used to describe its molecular variability; a most representative case is the lipophilicity space. In this review, a number of applications of lipophilicity space and other property spaces are presented, showing that this concept can be fruitfully exploited: to investigate the constraints exerted by media of different levels of structural organization, to examine processes of molecular recognition and binding at an atomic level, to derive informative descriptors to be included in quantitative structure--activity relationships and to analyze protein simulations extracting the relevant information. Much molecular information is neglected in the descriptors used by medicinal chemists, while the concept of property space can fill this gap by accounting for the often-disregarded dynamic behavior of both small ligands and biomacromolecules. Property space also introduces some innovative concepts such as molecular sensitivity and plasticity, which appear best suited to explore the ability of a molecule to adapt itself to the environment variously modulating its property and conformational profiles. Globally, such concepts can enhance our understanding of biological phenomena providing fruitful descriptors in drug-design and pharmaceutical sciences.

Occurrence and structure of extrafloral nectariesin Pterodon pubescens Benth. and Pterodon polygalaeflorus Benth.

Extrafloral nectaries (EFNs) are structurally variable and widely spread among the angiosperms. The occurrence of EFNs in leaves of Pterodon polygalaeflorus Benth. and Pterodon pubescens Benth. (Fabaceae: Papilionoideae) were detected in adult specimens, at the time of production of new buds and flowers. The goals of the present study are to register the occurrence of the EFNs in P. pubescens and P. polygalaeflorus, and provide comparative data on the anatomical structures. The EFNs occur in the rachis and are located under the insertion of each petiolule. Each nectary consists of a small elevation whose apical portion is deeply invaginated, resulting in a depression (secretory pole), a common characteristic of both species. Unicellular, nonglandular trichomes occur along the rachis, being less numerous in P. polygalaeflorus while in P. pubescens they cover the EFNs. The secretory tissue consists of parenchyma cells with dense cytoplasm compactly arranged. The nectar reaches the surface of the EFNs by rupturing the thin cuticle which covers the secretory pole, since both species lack stomata or any other interruption at the epidermis. The basic difference between the two species, in relation to the EFNs, is the density of the pubescence, which is always greater in P. pubescens. Structural and dimensional modifications may be observed, even between basal and apical nectaries in the same rachis, so it does not constitute a taxonomical tool.

Formation of virus-like clusters is an intrinsic property of the tumor necrosis factor family member BAFF (B cell activating factor).

The oligomeric state of BAFF (B cell activing factor), a tumor necrosis factor (TNF) family cytokine that plays a critical role in B cell development and survival, has been the subject of recent debate. Myc-tagged BAFF starting at residue Gln136 was previously reported to crystallize as trimers at pH 4.5, whereas a histidine-tagged construct of BAFF, starting at residue Ala134, formed a virus-like cluster containing 60 monomers when crystallized at pH 9.0. The formation of the BAFF 60-mer was pH dependent, requiring pH >or= 7.0. More recently, 60-mer formation was suggested to be artificially induced by the histidine tag, and it was proposed that BAFF, like all other TNF family members, is trimeric. We report here that a construct of BAFF with no amino-terminal tag (Ala134-BAFF) can form a 60-mer in solution. Using size exclusion chromatography and static light scattering to monitor trimer to 60-mer ratios in BAFF preparations, we find that 60-mer formation is pH-dependent and requires histidine 218 within the DE loop of BAFF. Biacore measurements established that the affinity of Ala134-BAFF for the BAFF receptor BAFFR/BR3 is similar to that of myc-Gln136-BAFF, which is exclusively trimeric in solution. However, Ala134-BAFF is more efficacious than myc-Gln136-BAFF in inducing B cell proliferation in vitro. We additionally show that BAFF that is processed and secreted by 293T cells transfected with full-length BAFF, or by a histiocytic lymphoma cell line (U937) that expresses BAFF endogenously, forms a pH-dependent 60-mer in solution. Our results indicate that the formation of the 60-mer in solution by the BAFF extracellular domain is an intrinsic property of the protein, and therefore that this more active form of BAFF may be physiologically relevant.

Predicting the physicochemical profile of diastereoisomeric histidine-containing dipeptides by property space analysis.

OBJECTIVES: This study aimed at measuring the lipophilicity and ionization constants of diastereoisomeric dipeptides, interpreting them in terms of conformational behavior, and developing statistical models to predict them. METHODS: A series of 20 dipeptides of general structure NH(2) -L-X-(L or D)-His-OMe was designed and synthetized. Their experimental ionization constants (pK(1) , pK(2) and pK(3) ) and lipophilicity parameters (log P(N) and log D(7.4) ) were measured by potentiometry. Molecular modeling in three media (vacuum, water, and chloroform) was used to explore and sample their conformational space, and for each stored conformer to calculate their radius of gyration, virtual log P (preferably written as log P(MLP) , meaning obtained by the molecular lipophilicity potential (MLP) method) and polar surface area (PSA). Means and ranges were calculated for these properties, as was their sensitivity (i.e., the ratio between property range and number of rotatable bonds). RESULTS: Marked differences between diastereoisomers were seen in their experimental ionization constants and lipophilicity parameters. These differences are explained by molecular flexibility, configuration-dependent differences in intramolecular interactions, and accessibility of functional groups. Multiple linear equations correlated experimental lipophilicity parameters and ionization constants with PSA range and other calculated parameters. CONCLUSION: This study documents the differences in lipophilicity and ionization constants between diastereoisomeric dipeptides. Such configuration-dependent differences are shown to depend markedly on differences in conformational behavior and to be amenable to multiple linear regression. Chirality 24:566-576, 2012. © 2012 Wiley Periodicals, Inc.

Structural, metamorphic and geochronological relations between the Zanskar Shear Zone and the Miyar Shear Zone (NW Indian Himalaya): Evidence for two distinct tectonic structures and implications for the evolution of the High Himalayan Crystalline of Zanskar

The geologic structures and metamorphic zonation of the northwestern Indian Himalaya contrast significantly with those in the central and eastern parts of the range, where the high-grade metamorphic rocks of the High Himalayan Crystalline (HHC) thrust southward over the weakly metamorphosed sediments of the Lesser Himalaya along the Main Central Thrust (MCT). Indeed, the hanging wall of the MCT in the NW Himalaya mainly consists of the greenschist facies metasediments of the Chamba zone, whereas HHC high-grade rocks are exposed more internally in the range as a large-scale dome called the Gianbul dome. This Gianbul dome is bounded by two oppositely directed shear zones, the NE-dipping Zanskar Shear Zone (ZSZ) on the northern flank and the SW-dipping Miyar Shear Zone (MSZ) on the southern limb. Current models for the emplacement of the HHC in NW India as a dome structure differ mainly in terms of the roles played by both the ZSZ and the MSZ during the tectonothermal evolution of the HHC. In both the channel flow model and wedge extrusion model, the ZSZ acts as a backstop normal fault along which the high-grade metamorphic rocks of the HHC of Zanskar are exhumed. In contrast, the recently proposed tectonic wedging model argues that the ZSZ and the MSZ correspond to one single detachment system that operates as a subhorizontal backthrust off of the MCT. Thus, the kinematic evolution of the two shear zones, the ZSZ and the MSZ, and their structural, metamorphic and chronological relations appear to be diagnostic features for discriminating the different models. In this paper, structural, metamorphic and geochronological data demonstrate that the MSZ and the ZSZ experienced two distinct kinematic evolutions. As such, the data presented in this paper rule out the hypothesis that the MSZ and the ZSZ constitute one single detachment system, as postulated by the tectonic wedging model. Structural, metamorphic and geochronological data are used to present an alternative tectonic model for the large-scale doming in the NW Indian Himalaya involving early NE-directed tectonics, weakness in the upper crust, reduced erosion at the orogenic front and rapid exhumation along both the ZSZ and the MSZ.

Structure and kinematics of the Siviez-Mischabel nappe in the Mattertal (western Alps of Switzerland) = Structure et cinématique de la nappe de Siviez-Mischabel le long de la vallée de Zermatt (Alpes de Suisse occidentale)

Résumé Cette étude porte sur le flanc inverse de la nappe de Siviez-Mischabel et sur les unités tectoniques sous jacentes (zone de Stalden supérieur et zone Houillère) dans la vallée menant à Zermatt. L'étude structurale du granite permien de Randa (orthogneiss oeillé) permet de mieux comprendre les effets de la déformation alpine sur les roches de socle. La cartographie détaillée de l'orthogneiss et de son encaissant, ainsi que l'étude lithostratigraphique des terrains sédimentaires associés permettent de proposer un schéma structural et cinématique du flanc inverse de la nappe de Siviez-Mischabel et de mieux comprendre ses relations avec les unités tectoniques sous-jacentes. L'analyse structurale de l'orthogneiss de Randa et de son encaissant révèle la superposition de plusieurs phases de déformation ductile. Cet orthogneiss formé sous des conditions métamorphiques du faciès schiste vert possède une forte schistosité alpine avec au moins deux linéations d'extension. La première, L1, orientée NW-SE est associée à la mise en place de la nappe. La seconde, L2, orientée SW-NE, se corrèle au cisaillement ductile du Simplon. La quantification de la déformation au moyen de la méthode de Fry sur les faciès porphyriques donne des ellipses à rapports axiaux compris entre 1.9 et 5.3, en accord avec les valeurs obtenues par d'autres marqueurs {tourmalines étirées, fibres). Les valeurs mesurées parallèlement à L1 ou L2 sont très semblables. La méthode de Fry a nécessité une étude théorique préalable afin de vérifier son applicabilité aux orthogneiss oeillés. La méthode requiert une distribution spatiale homogène et isotrope des marqueurs utilisés. Les tests statistiques effectués ont révélé que les phénocristaux de feldspath alcalin satisfont à cette condition et qu'ils peuvent être utilisés comme marqueur de la déformation au moyen de la méthode de Fry. Les valeurs obtenues révèlent l'importance du cisaillement ductile du Simplon sur la géométrie de la nappe dans la région d'étude. Le levé cartographique a permis d'améliorer la lithostratigraphie de la base de la nappe de Siviez-Mischabel. Trois formations en position renversée peuvent être observées sous les gneiss formant le coeur de la nappe. Ces trois formations forment le coeur du synclinal de St-Niklaus qui connecte la nappe de Siviez-Mischabel à la zone de Stalden supérieur. La datation par U-Pb de zircons détritiques et magmatiques par LA-ICP-MS permet de contraindre l'âge des formations observées (probablement Carbonifère à Trias précoce). Ces données ont des répercussions importantes sur la structure de la nappe dans la région, prouvant l'existence de plusieurs plis avec des séries normales et renversées bien préservées. La définition et la datation de ces formations, ainsi que leur identification dans la-Zone- Houillère avoisinante permettent de mieux comprendre la géométrie initiale et les relations tectoniques des nappes du Pennique moyen dans la vallée de Zermatt. Summary This study investigates the overturned limb of the Siviez-Mischabel nappe and underlying tectonic units (Upper Stalden zone and Houillère zone) in the Mattertal area. Detailed structural analysis in the Permian Randa granite (augen orthogneiss) allows a better understanding of the Alpine deformation effects on basement rocks. Detailed mapping of this orthogneiss and surrounding rocks, and the study of the lithostratigraphy in the related sedimentary horizons allow the proposition of a structural and kinematic model for the overturned limb of the Siviez-Mischabel and to better understand the relations with the underlying tectonic units. The structural analysis of the Randa orthogneiss and surrounding rocks revealed the superposition of several phases of ductile deformation. This orthogneiss formed under greenschist facies metamorphic conditions displays a strong Alpine foliation with at least two stretching lineations. The first lineation, L1, is oriented NW-SE and is related to the nappe emplacement northward. The second one, L2, is related to the Simplon ductile shear zone. Strain estimation using the Fry method has been performed on porphyritic facies of the Randa orthogneiss. The obtained ellipses have axial ratios varying between 1.9 and 5.3, in agreement with strain estimation obtained from other markers (stretched turmalines, fringes). The strain values are very similar if measured parallel to L1 or to L2. A theoretical approach was necessary to verify the relevant application of the Fry method to augen orthogneiss. This method requires that the distribution of the used markers has to be homogeneous and isotropic. Statistical tests have been done and revealed that K-feldspar phenocrysts satisfy these conditions and can be used as strain markers with the Fry method. The obtained strain measurements revealed the importance of the Simplon ductile shear zone on the geometry of the nappe in the studied area. Mapping has improved the lithostratigraphy at the base of the Siviez-Mischabel nappe. Three overturned formations can be observed below the gneisses forming the core of the nappe. These three formations form the St-Niklaus syncline, which connects the Siviez-Mischabel nappe to the underlying Upper Stalden zone. U-Pb dating of detrital and magmatic zircons by LA-ICPMS allowed the age of the observed formations to be constrained (presumably Carboniferous to Early Triassic). This data has critical implications for nappe structure in the region, composed of few recumbent folds with well preserved normal and overturned limbs. The definition and dating of these formations, as well as their identification in the adjacent "Houillère Zone" improve the understanding of the geometry and tectonic relations of the Middle Penninic nappes in the Mattertal.

How Do Aggregate Fluctuations Depend on the Network Structure of the Economy?

[spa] En este artículo, analizamos la volatilidad agregada de una economía estilizada donde los agentes estann conectados en redes. Si hay relaciones estratégicas entre las acciones de los agentes, choques idiosincráticos pueden generar fluctuaciones agregadas. Demonstramos que la volatilidad agregada depende de la estructura de redes de la economía de dos maneras. Por un lado, si hay más conexiones en la economía en su conjunto, la volatilidad agregada es más baja. Por otro lado, si las conexiones están más concentradas, la volatilidad agregada es más alta. Presentamos una aplicación de nuestras predicciones teóricas que utiliza datos de EEUU de conexiones intrasectoriales y de diversificación de las empresas.

How Do Aggregate Fluctuations Depend on the Network Structure of the Economy?

[spa] En este artículo, analizamos la volatilidad agregada de una economía estilizada donde los agentes estann conectados en redes. Si hay relaciones estratégicas entre las acciones de los agentes, choques idiosincráticos pueden generar fluctuaciones agregadas. Demonstramos que la volatilidad agregada depende de la estructura de redes de la economía de dos maneras. Por un lado, si hay más conexiones en la economía en su conjunto, la volatilidad agregada es más baja. Por otro lado, si las conexiones están más concentradas, la volatilidad agregada es más alta. Presentamos una aplicación de nuestras predicciones teóricas que utiliza datos de EEUU de conexiones intrasectoriales y de diversificación de las empresas.

Vertical relations and local competition : an empirical approach

The analysis of vertical industry relations forms an essential element in the field of industrial organization. This paper tests hypotheses derived from transaction cost theory and the principal-agent problem in Chile’s petrol market. It shows that local competition plays an important role in the choice of a disintegrated vertical structure, and that low levels of service investment have the same effect. Conversely, the number of own-brand outlets and a high level of investment in services reduce the probability of disintegration. The paper demonstrates that vertical disintegration has a null effect on wholesale petrol prices and a positive effect on retail petrol prices of between 1.6 and 7 per cent, depending on fuel type.

Understanding the Racial Nature of Police and Immigrant Relations In Finland. The Case of Africans in Turku

The focus of this study is to examine the role of police and immigrants’ relations, as less is known about this process in the country. The studies were approached in two different ways. Firstly, an attempt was made to examine how immigrants view their encounters with the police. Secondly, the studies explored how aware the police are of immigrants’ experiences in their various encounters and interactions on the street level. An ancillary aim of the studies is to clarify, analyse and discuss how prejudice and stereotypes can be tackled, thereby contributing to the general debate about racism and discrimination for better ethnic relations in the country. The data in which this analysis was based is on a group of adults (n=88) from the total of 120 Africans questioned for the entire study (n=45) police cadets and (n=6) serving police officers from Turku. The present thesis is a compilation of five articles. A summary of each article findings follows, as the same data was used in all five studies. In the first study, a theoretical model was developed to examine the perceived knowledge of bias by immigrants resulting from race, culture and belief. This was also an attempt to explore whether this knowledge was predetermined in my attempt to classify and discuss as well as analyse the factors that may be influencing immigrants’ allegations of unfair treatment by the police in Turku. The main finding shows that in the first paper there was ignorance and naivety on the part of the police in their attitudes towards the African immigrant’s prior experiences with the police, and this may probably have resulted from stereotypes or their lack of experience as well as prior training with immigrants where these kinds of experience are rampant in the country (Egharevba, 2003 and 2004a). In exploring what leads to stereotypes, a working definition is the assumption that is prevalent among some segments of the population, including the police, that Finland is a homogenous country by employing certain conducts and behaviour towards ethnic and immigrant groups in the country. This to my understanding is stereotype. Historically this was true, but today the social topography of the country is changing and becoming even more complex. It is true that, on linguistic grounds, the country is multilingual, as there are a few recognised national minority languages (Swedish, Sami and Russian) as well as a number of immigrant languages including English. Apparently it is vital for the police to have a line of communication open when addressing the problem associated with immigrants in the country. The second paper moved a step further by examining African immigrants’ understanding of human rights as well as what human rights violation means or entails in their views as a result of their experiences with the police, both in Finland and in their country of origin. This approach became essential during the course of the study, especially when the participants were completing the questionnaire (N=88), where volunteers were solicited for a later date for an in-depth interview with the author. Many of the respondents came from countries where human rights are not well protected and seldom discussed publicly, therefore understanding their views on the subject can help to explain why some of the immigrants are sceptical about coming forward to report cases of batteries and assaults to the police, or even their experiences of being monitored in shopping malls in their new home and the reason behind their low level of trust in public authorities in Finland. The study showed that knowledge of human rights is notably low among some of the participants. The study also found that female respondents were less aware of human rights when compared with their male counterparts. This has resulted in some of the male participants focussing more on their traditional ways of thinking by not realising that they are in a new country where there is equality in sexes and lack of respect on gender terms is not condoned. The third paper focussed on the respondents’ experiences with the police in Turku and tried to explore police attitudes towards African immigrant clients, in addition to the role stereotype plays in police views of different cultures and how these views have impacted on immigrants’ views of discriminatory policing in Turku. The data is the same throughout the entire studies (n=88), except that some few participants were interviewed for the third paper thirty-five persons. The results showed that there is some bias in mass-media reports on the immigrants’ issues, due to selective portrayal of biases without much investigation being carried out before jumping to conclusions, especially when the issues at stake involve an immigrant (Egharevba, 2005a; Egharevba, 2004a and 2004b). In this vein, there was an allegation that the police are even biased while investigating cases of theft, especially if the stolen property is owned by an immigrant (Egharevba, 2006a, Egharevba, 2006b). One vital observation from the respondents’ various comments was that race has meaning in their encounters and interaction with the police in the country. This result led the author to conclude that the relation between the police and immigrants is still a challenge, as there is rampant fear and distrust towards the police by some segments of the participating respondents in the study. In the fourth paper the focus was on examining the respondents’ view of the police, with special emphasis on race and culture as well as the respondents’ perspective on police behaviour in Turku. This is because race, as it was relayed to me in the study, is a significant predictor of police perception (Egharevba, 2005a; Egharevba and Hannikianen, 2005). It is a known scientific fact that inter-group racial attitudes are the representation of group competition and perceived threat to power and status (Group-position theory). According to Blumer (1958) a sense of group threat is an essential element for the emergence of racial prejudice. Consequently, it was essential that we explored the existing relationship between the respondents and the police in order to have an understanding of this concept. The result indicates some local and international contextual issues and assumptions that were of importance tackling prejudice and discrimination as it exists within the police in the country. Moreover, we have to also remember that, for years, many of these African immigrants have been on the receiving end of unjust law enforcement in their various countries of origin, which has resulted in many of them feeling inferior and distrustful of the police even in their own country of origin. While discussing the issues of cultural difference and how it affects policing, we must also keep in mind the socio-cultural background of the participants, their level of language proficiency and educational background. The research data analysed in this study also confirmed the difficulties associated with cultural misunderstandings in interpreting issues and how these misunderstandings have affected police and immigrant relations in Finland. Finally, the fifth paper focussed on cadets’ attitudes towards African immigrants as well as serving police officers’ interaction with African clients. Secondly, the police level of awareness of African immigrants’ distrustfulness of their profession was unclear. For this reason, my questions in this fifth study examined the experiences and attitudes of police cadets and serving police officers as well as those of African immigrants in understanding how to improve this relationship in the country. The data was based on (n=88) immigrant participants, (n=45) police cadets and 6 serving police officers from the Turku police department. The result suggests that there is distrust of the police in the respondents’ interaction; this tends to have galvanised a heightened tension resulting from the lack of language proficiency (Egharevba and White, 2007; Egharevba and Hannikainen, 2005, and Egharevba, 2006b) The result also shows that the allegation of immigrants as being belittled by the police stems from the misconceptions of both parties as well as the notion of stop and search by the police in Turku. All these factors were observed to have contributed to the alleged police evasiveness and the lack of regular contact between the respondents and the police in their dealings. In other words, the police have only had job-related contact with many of the participants in the present study. The results also demonstrated the complexities caused by the low level of education among some of the African immigrants in their understanding about the Finnish culture, norms and values in the country. Thus, the framework constructed in these studies embodies diversity in national culture as well as the need for a further research study with a greater number of respondents (both from the police and immigrant/majority groups), in order to explore the different role cultures play in immigrant and majority citizens’ understanding of police work.

Making Sense of Shared Leadership. A case study of leadership processes and practices without formal leadership structure in the team context

Leadership is essential for the effectiveness of the teams and organizations they are part of. The challenges facing organizations today require an exhaustive review of the strategic role of leadership. In this context, it is necessary to explore new types of leadership capable of providing an effective response to new needs. The presentday situations, characterized by complexity and ambiguity, make it difficult for an external leader to perform all leadership functions successfully. Likewise, knowledge-based work requires providing professional groups with sufficient autonomy to perform leadership functions. This study focuses on shared leadership in the team context. Shared leadership is seen as an emergent team property resulting from the distribution of leadership influence across multiple team members. Shared leadership entails sharing power and influence broadly among the team members rather than centralizing it in the hands of a single individual who acts in the clear role of a leader. By identifying the team itself as a key source of influence, this study points to the relational nature of leadership as a social construct where leadership is seen as social process of relating processes that are co-constructed by several team members. Based on recent theoretical developments concerned with relational, practice-based and constructionist approaches to the study of leadership processes, this thesis proposes the study of leadership interactions, working processes and practices to focus on the construction of direction, alignment and commitment. During the research process, critical events, activities, working processes and practices of a case team have been examined and analyzed with the grounded theory –approach in the terms of shared leadership. There are a variety of components to this complex process and a multitude of factors that may influence the development of shared leadership. The study suggests that the development process of shared leadership is a common sense -making process and consists of four overlapping dimensions (individual, social, structural, and developmental) to work with as a team. For shared leadership to emerge, the members of the team must offer leadership services, and the team as a whole must be willing to rely on leadership by multiple team members. For these individual and collective behaviors to occur, the team members must believe that offering influence to and accepting it from fellow team members are welcome and constructive actions. Leadership emerges when people with differing world views use dialogue and collaborative learning to create spaces where a shared common purpose can be achieved while a diversity of perspectives is preserved and valued. This study also suggests that this process can be supported by different kinds of meaning-making and process tools. Leadership, then, does not reside in a person or in a role, but in the social system. The built framework integrates the different dimensions of shared leadership and describes their relationships. This way, the findings of this study can be seen as a contribution to the understanding of what constitutes essential aspects of shared leadership in the team context that can be of theoretical value in terms of advancing the adoption and development process of shared leadership. In the real world, teams and organizations can create conditions to foster and facilitate the process. We should encourage leaders and team members to approach leadership as a collective effort that the team can be prepared for, so that the response is rapid and efficient.