Reactions of atomic and molecular ions with acetone, 1,1,1- trifluoroacetone, and hexafluoroacetone: An investigation of the effects of molecular structure on the dynamics and kinetics of ion-molecule reactions

A selected ion flow tube study of the reactions of a series of gas-phase atomic cations (S⁺, Xe⁺, O⁺, Kr⁺, N⁺, Ar⁺ and Ne⁺) and molecular ions (SF _n⁺ (n = 1-5), CF_n⁺ (n = 1-3), CF₂Cl⁺, H₃O⁺, NO⁺, N ₂O⁺, CO₂⁺, CO⁺, and N₂⁺) spanning a large range of recombination energies (6.3-21.6 eV), with acetone, 1,1,1-trifluoroacetone, and hexafluoroacetone has been undertaken with the objective of exploring the nature of the reaction ion chemistry as the methyl groups in acetone are substituted for CF₃. The reaction rate coefficients and product ion branching ratios for all 66 reactions, measured at 298 K, are reported. The experimental reaction rate coefficients are compared to theoretically calculated collisional values. Several distinct reaction processes were observed among the large number of reactions studied, including charge transfer (non-dissociative and dissociative), abstraction, ion-molecule associations and, in the case of the reactions involving the reagent ion H₃O⁺, proton transfer. 

Joint Leverage and Maturity Choices in Real Estate Firms: The Role of the REIT Status

We explore the interdependence of leverage and debt maturity choices in Real Estate Investment Trusts (REITs) and unregulated listed real estate investment companies in the U.S. for the period 1973-2011. We find that the leverage and maturity choices of all listed real estate firms are interdependent, but in contrast to industrial firms, they are not made simultaneously. Across the different types of real estate firms considered, we find substantial differences in the nature of the relationship between leverage and maturity. Leverage determines maturity in non-REITs, whereas maturity is a determinant of leverage in REITs. We suggest that the observed differences reflect the effects of the REIT regulation, rather than solely being a function of real estate as the underlying asset class. We also present novel evidence that the relationship between leverage and maturity in both firm types can be used to moderate the effects of other exogenous financing policies.

The Genesis Of The Mycenaean Citadel: A Philosophical Quest For The Origins Of The Architectural Forms

This thesis deals with the origins of the architectural forms as expressed in the Homeric Mycenaean citadel. The Genesis of the Mycenaean Citadel is a philosophical quest which reveals the poetic dimension of the Mycenaean architecture. The Introduction deals with general theories on the subject of space, which converge into one, forming the spinal idea of the thesis. The ‘process of individuation’, the process by which a person becomes ‘in-dividual’ that is a separate, indivisible unity or ‘whole’, is a process of transformation and renewal which at collective level takes place within the citadel. This is built on the archetype which expresses both the nature of the soul as a microcosm and of the divinely ordered Cosmos. The confrontation of the rational ‘ego’ with the unconscious is the process which brings us to the ‘self’, that organising center of the human psyche which is symbolised through the centre of the citadel. . Chapter I refers to ‘the Archetype of the Mycenaean citadel’. The Mycenaean citadel, which is built on a certain pattern of placement and orientation in relation to landscape formations, reproduces images which belong to the category of the ‘archetypal mother’. On the other hand, its adjustment to a central point with ‘high’ significance, recalls the archetypal image of Shiva-Shakti. The citadel realises the concept of a Kantian ‘One-all embracing space’; it is a cosmogonic symbol but also a philosophical one. Chapter II examines the column in its dual meaning, which is expressed in one structure; column and capital unite within their symbolism the conscious and unconscious contents of the human psyche and express the archetype of wholeness and goal of the individuation process. 33 Chapter III is a philosophical research into the ‘symbolism of the triangle’, the sacred Pythagorean symbol which expresses certain cosmological beliefs about the relation between human nature and the divinely ordered Cosmos. The triangular slab over the Lion Gate is a representation of the Dionysiac ‘palingenesia’, that is the continuity of One life, which was central to the Mycenaean religion. Chapter IV deals with the tripartite ‘megaron’. The circular hearth within the four-columned hall expresses the ‘quaternity of the One’, one of the oldest religious symbols of humanity. Zeus is revealed in the ‘fiery monadic unit-cubit’ as an all-embracing god next to goddess Hestia, symbolised by the circular hearth. The ‘megaron’ expresses the alchemical quaternity and the triad but also the psychological stages of development in the process towards wholeness. In the Conclusions it is emphasised that the Mycenaean citadel was created as if in a repetition of a cosmogony. It is a ‘mandala’, the universal image which is identified with God-image in man. Moreover it is built in order to be experienced by its citizen in the process of his psychological transformation towards the ‘self’, the divine element within the psyche which unites with the divinely ordered Cosmos

Nanostructured catalysts for the development of the hydrogen economy

La catalyse joue un rôle essentiel dans de nombreuses applications industrielles telles que les industries pétrochimique et biochimique, ainsi que dans la production de polymères et pour la protection de l’environnement. La conception et la fabrication de catalyseurs efficaces et rentables est une étape importante pour résoudre un certain nombre de problèmes des nouvelles technologies de conversion chimique et de stockage de l’énergie. L’objectif de cette thèse est le développement de voies de synthèse efficaces et simples pour fabriquer des catalyseurs performants à base de métaux non nobles et d’examiner les aspects fondamentaux concernant la relation entre structure/composition et performance catalytique, notamment dans des processus liés à la production et au stockage de l’hydrogène. Dans un premier temps, une série d’oxydes métalliques mixtes (Cu/CeO2, CuFe/CeO2, CuCo/CeO2, CuFe2O4, NiFe2O4) nanostructurés et poreux ont été synthétisés grâce à une méthode améliorée de nanocasting. Les matériaux Cu/CeO2 obtenus, dont la composition et la structure poreuse peuvent être contrôlées, ont ensuite été testés pour l’oxydation préférentielle du CO dans un flux d’hydrogène dans le but d’obtenir un combustible hydrogène de haute pureté. Les catalyseurs synthétisés présentent une activité et une sélectivité élevées lors de l’oxydation sélective du CO en CO2. Concernant la question du stockage d’hydrogène, une voie de synthèse a été trouvée pour le composét mixte CuO-NiO, démontrant une excellente performance catalytique comparable aux catalyseurs à base de métaux nobles pour la production d’hydrogène à partir de l’ammoniaborane (aussi appelé borazane). L’activité catalytique du catalyseur étudié dans cette réaction est fortement influencée par la nature des précurseurs métalliques, la composition et la température de traitement thermique utilisées pour la préparation du catalyseur. Enfin, des catalyseurs de Cu-Ni supportés sur silice colloïdale ou sur des particules de carbone, ayant une composition et une taille variable, ont été synthétisés par un simple procédé d’imprégnation. Les catalyseurs supportés sur carbone sont stables et très actifs à la fois dans l’hydrolyse du borazane et la décomposition de l’hydrazine aqueuse pour la production d’hydrogène. Il a été démontré qu’un catalyseur optimal peut être obtenu par le contrôle de l’effet bi-métallique, l’interaction métal-support, et la taille des particules de métal.

Towards balanced exploitation and management of the fishery resources of Uganda

A casual study of the hydrological map of Uganda would convince every serious fisherman and fisheater that he is most favoured to be in Uganda. The extent and distribution of the country's aquatic system plus the rich variety of fish species there is promises a fishery potential of considerable magnitude: The open waterways comprised by the Uganda portions of Lakes Victoria, Albert and Edward; and Lakes Kyoga, George plus minor lakes Wamala, Kijanebarora, mutanda, etc. occupy about 15% of the total surface area (91,000 m2; Depart. Land Survey, 1962). Most of the nation's fish supplies are currontly from this source. 1.2. A rich network of permanent and seasonal rivers and streams filling and/or emptying various water systems covers most of Uganda. This aquatic network is associated with a fish fauna whose immense significance as a source of protein is perhaps better appreciated by the local subsistance fisherman and consumer than by the fisheries scientist and manager in this country. Many species of this fish fauna have strong affinities with the open water systems while some are typically riverine. 1.3. Then there are wetlands composed mainly of expanses of swamp, but including some areas of bog. These cover about 2% of the country. While the variety of fish fauna found here is limited by the rather hostile nature of the environment (comparatively de-oxygenated under a canopy of dense stands of emergont vegetation) several specialised fishes e.g. Clarias spp. and Protpterus aethiopicus (Kamongo) occur here. Availability of permanent and seasonal sources of water, well distributed throughout most areas of Uganda, opens up immense potential for a variety of aquaculture practices. However, while active exploitation of much of these fishery resources is currently underway, important questions regarding the magnitudes of the various resource potentials and dynamics, and about suitable levels and modes of exploitation, are yet unanswered. These gaps in knowledge go about the fishery resources of Uganda would hinder formulation of adequate development and management schemes. This short paper examines some of the above problems and suggests some approaches towards balanced oxploitation and management of the fisheries of Uganda.

Organizational responses to technological discontinuities: the case of the American College of Radiology (ACR)

A long history of organizational research has shown that organizations are affected significantly by changes in technology. Scholars have given particular attention to the effects of so-called disruptive or discontinuous technological changes. Studies have repeatedly shown that established, incumbent organizations tend to suffer deep performance declines (and even complete demise) in the face of such changes, and researchers have devoted much attention to identifying the organizational conditions and processes that are responsible for this persistent and widespread pattern of adaptation failure. This dissertation, which examines the response of the American College of Radiology (ACR) to the emergence of nuclear magnetic resonance imaging technology (NMR), aims to contribute to this well-established research tradition in three distinct and important ways. First, it focuses on a fundamentally different type of organization, a professional association, rather than the technology producers examined in most prior research. Although technologies are well known to be embedded in “communities” that include technology producers, suppliers, customers, governmental entities, professional societies, and other entities, most prior research has focused on the responses and ultimate fate of producers alone. Little if any research has explored the responses of professional organizations in particular. Second, the study employs a sophisticated process methodology that identifies the individual events that make up the organization’s response to technological change, as well as the overall sequence through which these events unfold. This process approach contrasts sharply with the variance models used in most previous studies and offers the promise of developing knowledge about how adaptation ultimately unfolds (or fails to). Finally, the project also contributes significantly through its exploration of an apparently successful case of adaptation to technological change. Though nuclear magnetic resonance imaging posed a serious threat to the ACR and its members, this threat appears to have been successfully managed and overcome. Although the unique nature of the organization and the technology under study place some important limits on the generalizablity of this research, its findings nonetheless provide some important basic insights about the process through which social organizations can successfully adapt to discontinuous technological changes. These insights, which may also be of substantial relevance to technology producer organizations, will also be elaborated.

Causal structure of the entanglement renormalization ansatz

We show that the multiscale entanglement renormalization ansatz (MERA) can be reformulated in terms of a causality constraint on discrete quantum dynamics. This causal structure is that of de Sitter space with a flat space-like boundary, where the volume of a spacetime region corresponds to the number of variational parameters it contains. This result clarifies the nature of the ansatz, and suggests a generalization to quantum field theory. It also constitutes an independent justification of the connection between MERA and hyperbolic geometry which was proposed as a concrete implementation of the AdS-CFT correspondence.

An examination of the dynamic validities of cognitive ability and personality measures with performance

Prior research shows that both cognitive ability (Schmidt & Hunter, 1998) and personality measures (Poropat, 2009; Hough & Furnham, 2003) are valid predictors of job performance. The dynamic nature of the relationships between cognitive ability and personality measures with performance over time spent on the job is less understood and thus this paper explores their relationships. Although there is much research to suggest that the predictive relationship between cognitive ability and performance decreases over years of tenure (e.g., Hulin, Henry, & Noon, 1990), other research suggests that the relationship between cognitive ability and performance will increase over time (Kolz, McFarland, & Silverman, 1988). In regard to personality, this study provides a critical test of two competing theories. The first position holds that the validity of personality degrades over time. Support for this position comes from the “ubiquitous” nature of the simplex pattern in individual differences (Humphreys, 1985). It follows that personality validities should perform like cognitive ability in this respect, and thus decline over time. In contrast to this viewpoint, the alternative position contends that the predictive relationship between personality variables and performance increases over time, with the correlation becoming larger in magnitude and more positive in direction over years of tenure. The results of this study support the latter position; personality validities predicted long term performance outcomes.

Bioinformatics analysis of the Pedobacter sp. NL19 genome

The last decades of the 20th century defined the genetic engineering advent, climaxing in the development of techniques, such as PCR and Sanger sequencing. This, permitted the appearance of new techniques to sequencing whole genomes, identified as next-generation sequencing. One of the many applications of these techniques is the in silico search for new secondary metabolites, synthesized by microorganisms exhibiting antimicrobial properties. The peptide antibiotics compounds can be classified in two classes, according to their biosynthesis, in ribosomal or nonribosomal peptides. Lanthipeptides are the most studied ribosomal peptides and are characterized by the presence of lanthionine and methylanthionine that result from posttranslational modifications. Lanthipeptides are divided in four classes, depending on their biosynthetic machinery. In class I, a LanB enzyme dehydrate serine and threonine residues in the C-terminus precursor peptide. Then, these residues undergo a cyclization step performed by a LanC enzyme, forming the lanthionine rings. The cleavage and the transport of the peptide is achieved by the LanP and LanT enzymes, respectively. Although, in class II only one enzyme, LanM, is responsible for the dehydration and cyclization steps and also only one enzyme performs the cleavage and transport, LanT. Pedobacter sp. NL19 is a Gram-negative bacterium, isolated from sludge of an abandon uranium mine, in Viseu (Portugal). Antibacterial activity in vitro was detected against several Gram-positive and Gram-negative bacteria. Sequencing and in silico analysis of NL19 genome revealed the presence of 21 biosynthetic clusters for secondary metabolites, including nonribosomal and ribosomal peptides biosynthetic clusters. Four lanthipeptides clusters were predicted, comprising the precursor peptides, the modifying enzymes (LanB and LanC), and also a bifunctional LanT. This result revealed the hybrid nature of the clusters, comprising characteristics from two distinct classes, which are poorly described in literature. The phylogenetic analysis of their enzymes showed that they clustered within the bacteroidetes clade. Furthermore, hybrid gene clusters were also found in other species of this phylum, revealing that it is a common characteristic in this group. Finally, the analysis of NL19 colonies by MALDI-TOF MS allowed the identification of a 3180 Da mass that corresponds to the predicted mass of a lanthipeptide encoded in one of the clusters. However, this result is not fully conclusive and further experiments are needed to understand the full potential of the compounds encoded in this type of clusters. In conclusion, it was determined that NL19 strain has the potential to produce diverse secondary metabolites, including lanthipeptides that were not functionally characterized so far.

Fully Anisotropic Solution of the Three Dimensional Boltzmann Transport Equation

The development of accurate modeling techniques for nanoscale thermal transport is an active area of research. Modern day nanoscale devices have length scales of tens of nanometers and are prone to overheating, which reduces device performance and lifetime. Therefore, accurate temperature profiles are needed to predict the reliability of nanoscale devices. The majority of models that appear in the literature obtain temperature profiles through the solution of the Boltzmann transport equation (BTE). These models often make simplifying assumptions about the nature of the quantized energy carriers (phonons). Additionally, most previous work has focused on simulation of planar two dimensional structures. This thesis presents a method which captures the full anisotropy of the Brillouin zone within a three dimensional solution to the BTE. The anisotropy of the Brillouin zone is captured by solving the BTE for all vibrational modes allowed by the Born Von-Karman boundary conditions.

Tutors as mediators of exchange student experiences: evaluation of the international student tutor system at the University of Turku

As academic student mobility is increasing, improving the functionality of international operations is recognised as a competitive advantage at tertiary education institutions. Although many scholars have researched the experiences of exchange students, the role of student tutors and their contribution to exchange students’ experiences is still an unknown factor. This research examines international tutoring at the University of Turku, and aims to understand better the way tutoring contributes to exchange experiences and to explore the functionality of the tutor system and discover areas for improvements. To achieve these goals, the research seeks to answer the fundamental research question: What is the role of tutors in mediating exchange experiences? The theoretical framework combines literature on mediating exchange experiences, the phenomenon of studying abroad, the process of adaptation, the importance of cross-cultural communication, and the role of student tutors as mediators. Based on the literature review, a theoretical model for studying the mediation of exchange experiences is introduced. The model’s applicability and validity is examined through a case study. Three methods were used in the empirical research: surveys, participant observations, and interviews. These methods provided extensive data from three major parties of the tutor system: tutors, exchange students, and the international office. The findings of the research reveal that tutoring – instrumental leading and social and cultural mediating – generates both negative and positive experiences depending on the individuals’ expectations, motivations, relationships, and the nature of the tutoring. Although functional, there are a few weaknesses in the tutor system. Tutors tend to act as effective instrumental leaders, but often fail to create a friendship and contribute to the exchange students’ experience through social and cultural mediation, which is significantly more important in the exchange students’ overall experience in terms of building networks, adapting, gaining emotional experiences, and achieving the stage of personal development and mental change. Based on the weaknesses, three improvements are suggested: (1) increasing comprehensive sharing of information, effective communication, and collective cooperation, (2) emphasising the importance of social and cultural mediation and increasing the frequency of interaction between tutors and exchange students, and (3) improving the recruitment and training, revising the process of reporting and rewarding, and finally, enhancing services and coordination.

A preliminary examination of the relationship between compulsive exercise and shame in individuals with an eating disorder: and clinical research portfolio

Objective: To explore the relationship between compulsive exercise and shame in a clinical sample of eating disorder patients. Method: In a cross-sectional study, individuals with an eating disorder (n=21) completed self-report measures of compulsive exercise, internal shame, external shame, bodily shame, anxiety and depression. Results: Internal shame was moderately associated with compulsive exercise (r=.496, p<.05). No further variables were significantly related to compulsive exercise. Individuals with Anorexia-Nervosa and Bulimia-Nervosa did not significantly differ on any of the study variables. Discussion: Hypotheses regarding the possible nature of the relationship between compulsive exercise and shame are suggested. For instance, that compulsive exercise may serve a role in the regulation of internal shame. That compulsive exercise may act as a compensatory behaviour and be a consequence of high levels of shame. Or that internal shame may result as a response to negative perceptions of one’s exercise habits. The results are discussed in line with current literature.

Texture and composition of the Rosa Marina beach sands (Adriatic coast, southern Italy): a sedimentological/ecological approach

Beach sands from the Rosa Marina locality (Adriatic coast, southern Italy) were analysed mainly microscopically in order to trace the source areas of their lithoclastic and bioclastic components. The main cropping out sedimentary units were also studied with the objective to identify the potential source areas of lithoclasts. This allowed to establish how the various rock units contribute to the formation of beach sands. The analysis of the bioclastic components allows to estimate the actual role of organisms regarding the supply of this material to the beach. Identification of taxa that are present in the beach sands as shell fragments or other remains was carried out at the genus or family level. Ecologi- cal investigation of the same beach and the recognition of sub-environments (mainly distinguished on the basis of the nature of the substrate and of the water depth) was the key topic that allowed to establish the actual source areas of bioclasts in the Rosa Marina beach sands. The sedimentological analysis (including a physical study of the beach and the calculation of some statistical parameters concerning the grain-size curves) shows that the Rosa Marina beach is nowadays subject to erosion.

A multi-method study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the activation pathway

The change in the carbonaceous skeleton of nanoporous carbons during their activation has received limited attention, unlike its counterpart process in the presence of an inert atmosphere. Here we adopt a multi-method approach to elucidate this change in a poly(furfuryl alcohol)-derived carbon activated using cyclic application of oxygen saturation at 250 °C before its removal (with carbon) at 800 °C in argon. The methods used include helium pycnometry, synchrotron-based X-ray diffraction (XRD) and associated radial distribution function (RDF) analysis, transmission electron microscopy (TEM) and, uniquely, electron energy-loss spectroscopy spectrum-imaging (EELS-SI), electron nanodiffraction and fluctuation electron microscopy (FEM). Helium pycnometry indicates the solid skeleton of the carbon densifies during activation from 78% to 93% of graphite. RDF analysis, EELS-SI, and FEM all suggest this densification comes through an in-plane growth of sp2 carbon out to the medium range without commensurate increase in order normal to the plane. This process could be termed ‘graphenization’. The exact way in which this process occurs is not clear, but TEM images of the carbon before and after activation suggest it may come through removal of the more reactive carbon, breaking constraining cross-links and creating space that allows the remaining carbon material to migrate in an annealing-like process.

Development of the Andalusian Registry of Patients Receiving Community Case Management, for the follow-up of people with complex chronic diseases.

Background: Complex chronic diseases are a challenge for the current configuration of Health services. Case management is a service frequently provided for people with chronic conditions and despite its effectiveness in many outcomes, such as mortality or readmissions, uncertainty remains about the most effective form of team organization, structures, and the nature of the interventions. Many processes and outcomes of case management for people with complex chronic conditions cannot be addressed with the information provided by electronic clinical records. Registries are frequently used to deal with this weakness. The aim of this study was to generate a registry-based information system of patients receiving case management to identify their clinical characteristics, their context of care, events identified during their follow-up, interventions developed by case managers, and services used. Methods and design: The study was divided into three phases, covering the detection of information needs, the design and its implementation in the healthcare system, using literature review and expert consensus methods to select variables that would be included in the registry. Objective: To describe the essential characteristics of the provision of ca re lo people who receive case management (structure, process and outcomes), with special emphasis on those with complex chronic diseases. Study population: Patients from any District of Primary Care, who initiate the utilization of case management services, to avoid information bias that may occur when including subjects who have already been received the service, and whose outcomes and characteristics could not be properly collected. Results: A total of 102 variables representing structure, processes and outcomes of case management were selected for their inclusion in the registry after the consensus phase. Total sample was composed of 427 patients, of which 211 (49.4%) were women and 216 (50.6%) were men. The average functional level (Barthel lndex) was 36.18 (SD 29.02), cognitive function (Pfeiffer) showed an average of 4.37 {SD 6.57), Chat1son Comorbidity lndex, obtained a mean of 3.03 (SD 2.7) and Social Support (Duke lndex) was 34.2 % (SD 17.57). More than half of patients include in the Registry, correspond lo immobilized or transitional care for patients discharged from hospital (66.5 %). The patient's educational level was low or very low (50.4%). Caregivers overstrain (Caregiver stress index), obtained an average value of 6.09% (SD 3.53). Only 1.2 % of patients had declared their advanced directives, 58.6 had not defined the tutelage and the vast majority lived at home 98.8 %. Regarding the major events recorded at RANGE Registry, 25.8 % of the selected patients died in the first three months, 8.2 % suffered a hospital admission at least once time, 2.3%, two times, and 1.2% three times, 7.5% suffered a fall, 8.7% had pressure ulcer, 4.7% had problems with medication, and 3.3 % were institutionalized. Stroke is the more prevalent health problem recorded (25.1%), followed by hypertension (11.1%) and COPD (11.1%). Patients registered by NCMs had as main processes diabetes (16.8%) and dementia (11.3 %). The most frequent nursing diagnoses referred to the self-care deficit in various activities of daily living. Regarding to nursing interventions, described by the Nursing Intervention Classification (NIC), dementia management is the most used intervention, followed by mutual goal setting, caregiver and emotional support. Conclusions: The patient profile who receive case management services is a chronic complex patient with severe dependence, cognitive impairment, normal social support, low educational level, health problems such as stroke, hypertension or COPD, diabetes or dementia, and has an informal caregiver. At the first follow up, mortality was 19.2%, and a discrete rate of readmissions and falls.