<p>The present body of work has focused on the development of the chemistry of iron complexes of macrocyclic ligands, specifically HMC and HMTI. This has proceeded along two distinct, though related, lines. First, metal-alkynyl complexes have been synthesized, and the effects of the macrocyclic ligand on the metal center – and therefore on the metal-alkynyl bond – have been extensively explored. This is first described for a mono- and bis-alkynyl pair in Chapter 2, in which the general structural and electrochemical features of the Fe(HMTI) motif are delineated. In Chapter 3, the detailed characterization of an iron HMC/HMTI family of complexes is described, which is accompanied by spectroelectrochemical (SEC) analyses and extensive DFT and TD-DFT. Finally, as described in Chapter 4, the understanding gained in the aforementioned works is leveraged to control the properties of mixed-valent complexes based on Fe(HMC/HMTI) bis-alkynyl motif, with a motivation to explore fundamental questions for the development of molecular wires.</p> <p><br></p> <p>The second realm of exploration has been concerned with understanding ferrous complexes of HMTI at a deeper level – which species have been previously reported but largely uninvestigated. Collaborative efforts have shown that these FeII(HMTI) species can have unusually long excited state lifetimes under the appropriate conditions, as discussed in Chapter 5. Further (unpublished) characterization of this family of complexes is the focus of Chapter 6, which highlights the relationship between the energy of the charge-transfer absorption band and the nature of the axial ligand.</p> <p><br></p> <p>The novel work outlined above is preceded by introductory material (Chapter 1). This chapter serves to briefly contextualize the body which follows within the landscape of the earlier established (though limited) literature on Fe(HMTI) species. Chapter 1 thus represents an attempt to illustrate the ties throughout what might otherwise (and perhaps still does) appear a disjointed conglomerate of text.</p>

This paper deals with the semantic and constructional variation of the Spanish verb hablar and offers a description of the multiple contexts in which this verb can appear, based on the study of the focalization semantics of its root and the temporal configuration of the event in the model of Wotjak (2010, 2012).

Les dictionnaires de valence sont utiles dans plusieurs tâches en traitement automatique des langues. Or, les dictionnaires de qualité de ce type sont créés au moins en partie manuellement; ils nécessitent donc beaucoup de ressources et sont difficiles à mettre à jour. De plus, plusieurs de ces ressources ne prennent pas en compte les différents sens des lemmes, qui sont pourtant importants puisque les arguments sélectionnés ont tendance à varier selon le sens du verbe. Dans ce mémoire, nous créons automatiquement un dictionnaire de valence des verbes du français qui tient compte de la polysémie. Nous extrayons 20 000 exemples de phrases pour chacun des 2 000 verbes les plus fréquents du franc¸ais. Nous obtenons ensuite les plongements lexicaux de ces verbes en contexte à l’aide d’un modèle de langue monolingue et de deux modèles de langue multilingues. Puis, nous utilisons des algorithmes de regroupement pour induire les différents sens de ces verbes. Enfin, nous analysons automatiquement les phrases à l’aide de différents analyseurs syntaxiques afin de trouver leurs arguments. Nous déterminons que la combinaison du modèle de langue français CamemBERT et d’un algorithme de regroupement agglomératif offre les meilleurs résultats dans la tâche d’induction de sens (58,19% de F1 B3), et que pour l’analyse syntaxique, Stanza est l’outil qui a les meilleures performances (83,29% de F1). En filtrant les cadres syntaxiques obtenus à l’aide d’une estimation de la vraisemblance maximale, une méthode statistique très simple qui permet de trouver les paramètres les plus vraisemblables d’un modèle de probabilité qui explique nos données, nous construisons un dictionnaire de valence qui se passe presque complètement d’intervention humaine. Notre procédé est ici utilisé pour le français, mais peut être utilisé pour n’importe quelle autre langue pour laquelle il existe suffisamment de données écrites. / Valency dictionaries are useful for many tasks in automatic language processing. However, quality dictionaries of this type are created at least in part manually; they are therefore resource-intensive and difficult to update. In addition, many of these resources do not take into account the different meanings of lemmas, which are important because the arguments selected tend to vary according to the meaning of the verb. In this thesis, we automatically create a French verb valency dictionary that takes polysemy into account. We extract 20 000 example sentences for each of the 2 000 most frequent French verbs. We then obtain the lexical embeddings of these verbs in context using a monolingual and two multilingual language models. Then, we use clustering algorithms to induce the different meanings of these verbs. Finally, we automatically parse the sentences using different parsers to find their arguments. We determine that the combination of the French language model CamemBERT and an agglomerative clustering algorithm offers the best results in the sense induction task (58.19% of F1 B3), and that for syntactic parsing, Stanza is the tool with the best performance (83.29% of F1). By filtering the syntactic frames obtained using maximum likelihood estimation, a very simple statistical method for finding the most likely parameters of a probability model that explains our data, we build a valency dictionary that almost completely dispenses with human intervention. Our procedure is used here for French, but can be used for any other language for which sufficient written data exists.

(EN) Valency Dictionary of Arabic Verbs PhDr. Viktor Bielický This dissertation serves as a theoretical background for creating a valency dictionary of verbs in Modern Standard Arabic (MSA) which is primarily in the form of an electronic database. The Functional Generative Description is used as a theoretical framework for the description of verbal valency in Arabic. Chapter 1 introduces the verbal system of MSA with an emphasis on semantic relations within the system of verbal morpho- semantic patterns (verbal stems). Chapter 2 outlines the current research status of valency in Arabic including various research projects focused on creating electronic databases for Arabic verbs. Chapter 3 presents an overview of a valency theory developed within the Funtional Generative Description and it also provides a brief description of two broad coverage valency dictionaries for the Czech language - VALLEX and PDT-Vallex. Chapter 4, the core of the study, analyses semantics and the surface realization of different types of valency complemens in MSA, i.e. actants, quasi-valency and free (adverbial) complements. The final chapter, Chapter 5, describes the methodology and the structure of the valency dictionary the printed version of which is attached to the thesis. Key words: verbal valency, Modern Standard...

Lipid bilayers are key components of biomembranes; they are self-assembled two-dimensional structures, primarily serving as barriers to the leakage of cell's contents. Lipid bilayers are typically charged in aqueous solution and may electrostatically interact with each other and with their environment. In this work, we investigate electrostatics of charged lipid bilayers with the main focus on the binding and bending of the bilayers. We first present a theoretical approach to charge-correlation attractions between like-charged lipid bilayers with neutralizing counterions assumed to be localized to the bilayer surface. In particular, we study the effect of nonzero ionic sizes on the attraction by treating the bilayer charges (both backbone charges and localized counterions) as forming a two-dimensional ionic fluid of hard spheres of the same diameter <i>D</i>. Using a two-dimensional Debye-H??ckel approach to this system, we examine how ion sizes influence the attraction. We find that the attraction gets stronger as surface charge densities or counterion valency increase, consistent with long-standing observations. Our results also indicate non-trivial dependence of the attraction on separations <i>h</i>: The attraction is enhanced by ion sizes for <i>h</i> ranges of physical interest, while it crosses over to the known <i>D</i>-independent universal behavior as <i>h</i> &rarr; &infin;; it remains finite as <i>h</i> &rarr; 0, as expected for a system of finite-sized ions. We also study the preferred curvature of an asymmetrically charged bilayer, in which the inner leaflet is negatively charged, while the outer one is neutral. In particular, we calculate the relaxed area difference &Delta; <i>A</i>₀ and the spontaneous curvature <i>C</i>₀ of the bilayer. We find &Delta; <i>A</i>₀ and <i>C</i>₀ are determined by the balance of a few distinct contributions: net charge repulsions, charge correlations, and the entropy associated with counterion release from the bilayer. The entropic effect is dominant for weakly charged surfaces in the presence of monovalent counterions only and tends to expand the inner leaflet, leading to negative &Delta; <i>A</i>₀ and <i>C</i>₀. In the presence of even a small concentration of divalent counterions, however, charge correlations counterbalance the entropic effect and shrink the inner leaflet, leading to positive &Delta; <i>A</i>₀ and <i>C</i>₀. We outline biological implications of our results.

Lipid bilayers are key components of biomembranes; they are self-assembled two-dimensional structures, primarily serving as barriers to the leakage of cell's contents. Lipid bilayers are typically charged in aqueous solution and may electrostatically interact with each other and with their environment. In this work, we investigate electrostatics of charged lipid bilayers with the main focus on the binding and bending of the bilayers. We first present a theoretical approach to charge-correlation attractions between like-charged lipid bilayers with neutralizing counterions assumed to be localized to the bilayer surface. In particular, we study the effect of nonzero ionic sizes on the attraction by treating the bilayer charges (both backbone charges and localized counterions) as forming a two-dimensional ionic fluid of hard spheres of the same diameter <i>D</i>. Using a two-dimensional Debye-Hückel approach to this system, we examine how ion sizes influence the attraction. We find that the attraction gets stronger as surface charge densities or counterion valency increase, consistent with long-standing observations. Our results also indicate non-trivial dependence of the attraction on separations <i>h</i>: The attraction is enhanced by ion sizes for <i>h</i> ranges of physical interest, while it crosses over to the known <i>D</i>-independent universal behavior as <i>h</i> &rarr; &infin;; it remains finite as <i>h</i> &rarr; 0, as expected for a system of finite-sized ions. We also study the preferred curvature of an asymmetrically charged bilayer, in which the inner leaflet is negatively charged, while the outer one is neutral. In particular, we calculate the relaxed area difference &Delta; <i>A</i>₀ and the spontaneous curvature <i>C</i>₀ of the bilayer. We find &Delta; <i>A</i>₀ and <i>C</i>₀ are determined by the balance of a few distinct contributions: net charge repulsions, charge correlations, and the entropy associated with counterion release from the bilayer. The entropic effect is dominant for weakly charged surfaces in the presence of monovalent counterions only and tends to expand the inner leaflet, leading to negative &Delta; <i>A</i>₀ and <i>C</i>₀. In the presence of even a small concentration of divalent counterions, however, charge correlations counterbalance the entropic effect and shrink the inner leaflet, leading to positive &Delta; <i>A</i>₀ and <i>C</i>₀. We outline biological implications of our results.

Microbeam radiation therapy (MRT) is an experimental form of radiation treatment which causes less damage to normal tissue in comparison with customary broad-beam radiation treatment. In this method the synchrotron generated X-ray beam is passed through a multislit collimator and applied to the tumor in the form of an array of planar microbeams. MRT dosimetry is an extremely challenging task and no current detector can provide the required wide dynamic rang and high spatial resolution. In this thesis, fluorophosphate (FP) and fluoroaluminate (FA) glass plates doped with trivalent samarium (Sm3+) are characterized towards developing a potential X-ray detector suitable for MRT dosimetry. The detection is based on the difference in the photoluminescence signatures of Sm3+ ions and Sm2+ ions; the latter are formed under X-ray irradiation. This valency conversion is accompanied by the formation of defects including hole centers (HCs) and electron centers (ECs) in the glass structure which absorb light in the UV and visible regions (induced absorbance). Both FP and FA glasses show promising dynamic range for MRT and may be used as a linear sensor up to ~150 Gy and as a nonlinear sensor up to ∼2400 Gy, where saturation is reached. X-ray induced defects saturate at the same dose. The optimum doping concentration is in the 0.001˗ 0.2 at.% range. Doping with higher concentrations will decrease the conversion efficiency. The glass plates also show a very promising spatial resolution (as high as a few microns) for recording the dose profile of microbeams which is readout using a confocal fluorescence microscopy technique. These plates are restorable as well and the response is reproducible. The effects of previous X-ray exposure including samarium valency conversion as well as induced absorbance may be erased by annealing at temperatures exceeding the glass transition temperature Tg while annealing at TA < Tg enhances the response. This enhancement is explained by a thermally stimulated relaxation of host glass ionic matrix surrounding X-ray induced Sm2+ ions. Optical erasure is another practical means to erase the recorded data. Nearly complete Sm2+ to Sm3+ reconversion (erasure) is achieved by intense optical illumination at 405 nm. While, existing X-ray induced bands would be only partially erased. Electron spin resonance (ESR) and optical absorbance spectroscopy are used to investigate the nature of X-ray induced defects and their correlation with Sm valency conversion. A model based on competition between defect center formation and the Sm3+ ⇆ Sm2+ conversion successfully explains the different processes occurring in the glass matrix under X-ray irradiation.

Dans le cadre des approches constructionistes, cette thèse étudie les verbes labiles de l’anglais, qui peuvent manifester des configurations syntaxiques variées sans changer de forme. L’étude de la complémentation de ces verbes montre que leur catégorisation en familles sémantiques est pertinente mais pas suffisante pour expliquer leur comportement. La thèse défend une approche syncrétique de la complémentation du verbe qui rend compte de son importante productivité et de ses limites parfois arbitraires. Une analyse montre que les verbes ont tous une configuration syntaxique par défaut, qui n’est pas signifiante et qui permet simplement au verbe d’exprimer ses arguments de façon non marquée, en accord avec certains principes de cohérence conceptuelle. À l’inverse, lorsque la complémentation du verbe a un apport sémantique identifiable, l’existence de schémas de complémentation pleinement signifiants est postulée. Il s’agit d’ensembles de compléments dont le sens est distinct de celui du verbe auquel ils sont associés et se retrouve de façon régulière avec des verbes de catégories diverses. Il est démontré que les schémas de complémentation doivent être considérés comme des unités linguistiques de plein droit de l’anglais. Cela implique qu’en synchronie, ces schémas sont emmagasinés par les locuteurs plutôt que le résultat d’un processus d’analogie avec des constructions existantes. Leur statut d’unité linguistique permet d’étudier leur sémantisme de la même façon que des unités lexicales plus classiques. S’ils sont en majorité polysémiques, certains schémas ont des emplois difficiles à relier sémantiquement et doivent donc être considérés comme des homonymes. / Within a constructionist framework, this thesis studies English labile verbs, which can enter into various syntactic configurations without changing form. A study of their complementation shows that categorizing them into semantic families is relevant but not sufficient to explain their behavior. The thesis defends a syncretic approach to verb complementation to that accounts for its important productivity and its sometimes arbitrary limits. It is shown that all verbs have a default syntactic configuration, which is not meaningful and which simply allows the verb to express its arguments in an unmarked way, in accordance with certain principles of conceptual coherence. Conversely, when the complementation of the verb has an identifiable semantic contribution, the existence of fully meaningful patterns of complementation is posited. These are defined as sets of complements, whose meaning is distinct from that of the verb with which they are associated and is found regularly with verbs of diverse categories. It is shown that patterns of complementation should be considered fully-fledged English linguistic units. This implies that synchronically, these patterns are mentally stored by speakers rather than the result of a process of analogy with existing constructions. Their status as linguistic units makes it possible to study their meaning in the same way as more classical lexical units. Although most of them are polysemic, some patterns of complementation exhibit uses that are difficult to link semantically and must therefore be viewed as homonyms.

Le terme d’antipassif, qui s’inscrit depuis quarante ans dans le système des langues ergatives, désigne une construction intransitive ayant pour caractéristique générale la destitution du patient. Cette thèse remet en question l’opinion traditionnelle selon laquelle les constructions antipassives sont identifiées exclusivement dans les langues à alignement ergatif, et non dans les langues à alignement accusatif. Étant donné qu’une certaine proportion de langues ergatives utilise pour dériver l’antipassif le morphème polysémique réfléchie et/ou réciproque, dans cette étude nous nous sommes intéressée aux langues accusatives dont la marque antipassive présente la même caractéristique, d’où l’intérêt porté aux langues austronésiennes, Niger-Congo et Nilo-sahariennes, turciques, slaves et romanes. Dans la mesure où nous avons décidé de travailler sur les constructions antipassives dérivées par une marque étant à l’origine polysémique, l’impact sémantique de cette dernière sur l’ensemble de la construction apparaît comme non négligeable. Cette étude présente ainsi le double intérêt de s’appuyer sur une approche translinguistique, impliquant différentes familles de langues, et sur une vision bipolaire relative aux domaines de la syntaxe et de la sémantique. / The antipassive term, associated with ergative system since forty years, denotes an intransitive construction in which the patient argument is syntactically demoted. This study calls into question a traditional opinion according to which the antipassive phenomenon is encountered in ergative languages but not in those of accusative alignment. Since in some ergative languages the antipassive construction is triggered by a polysemous reflexive and/or reciprocal morpheme, this study deals exclusively with those accusative languages in which the antipassive marker presents the same characteristics (cf. Austronesian, Niger–Congo, Nilo-Saharan, Turkic, Slavonic, Romance languages). Building on the polysemous nature of such marker, its possible semantic impact on the whole derivation should also be taken into consideration. The aim of this study is to analyse the antipassive construction both from semantic and syntactic point of view in a crosslinguistic perspective.

Sammanfattning   Titel: Digitaliserad word of mouth, en betydande faktor för WTA   Nivå: Examensarbete på Grundnivå (kandidatexamen) i ämnet företagsekonomi   Författare: Andreas Ståhl och Markus Westblad   Handledare: Jonas Kågström, Benny Berggren   Datum: 2019 – Juni    Syfte: Syftet med denna studie är att öka förståelsen för hur eWOMs volym och valens påverkar konsumenters WTA i valet av tjänst från säljare. I denna studie har en undersökning av begrepp som WTA och eWOM ställts emot varandra i en experimentell design som sedan genom resultatet delat en förståelse för hur volym och valens påverkar valet av en fastighetsmäklare. Studien har genom tidigare forskning önskats applicerats på andra branscher än tidigare utförda vilket vi anser att denna studie uppfyller genom den replikerade metod som använts.   Metod: Denna studie är utförd genom en kvantitativ forskningsstrategi med en replikerande metod med experimentell design. Den data som samlats in som underlag för studiens resultat och analys har samlats in genom en digital enkät med manipulerade mäklarprofiler genom rekommendationssajten ”Reco”. Datan har sedan analyserats genom programvaran ”Jamovi” genom deskriptiva analyser samt genom en korrelationsanalys.   Resultat &amp; slutsats: Studien har visat resultat som motsäger tidigare forskning med bland annat att volym är mer avgörande i valet av en tjänst i relation till valens.   Detta resultat visar även på att fler bör studera sina branscher för att öka sin förståelse för hur kraftigt vissa faktorer är inom digitaliserad marknadsföring.   Examensarbetets bidrag: Studien presenterar ett teoretiskt såväl som praktiskt bidrag i det avslutande kapitlet som i kort visar på hur volym och valens kan variera i jämförelse med den tidigare forskningen som utförts och vad som bör beaktas och noggrant analyseras för att i framtiden kunna appliceras på företagsnivå inom marknadsföring såväl som rekommendationer.   Förslag till fortsatt forskning: Jämförande studie av de två begreppen eWOM och WOM, vilket är det mer traditionella uttryck för att beskriva en word of mouth effekt. Hur särskiljer sig dessa åt i resultat, och är de skillnader i effektivitet mot den som faktiskt blir rekommenderad.   Studien ger även förslag på att använda sig av demografiska data som underlag för tolkningen utav statistiken, vilket inte gjorts inom denna studie. Vi anser det även intressant med en mer övergripande manipulering av de olika profilerna, såsom att tillägga fabrik eller varumärke och se hur dessa skiljer sig åt.   Nyckelord: WTA, WTP, IRP, eWOM, WOM, Valens och Volym. / Abstract Title: Digitized word of mouth, an important factor for WTA   Level: Student thesis, final assignment for Bachelor Degree in Business Administration   Author: Andreas Ståhl and Markus Westblad   Supervisor: Jonas Kågström, Benny Berggren   Date: 2019 – June   Aim: The purpose of this study is to increase the understanding of how eWOM's volume and valency affects consumers' WTA in the choice of service from sellers. In this paper, a study of concepts such as WTA and eWOM has been compared in an experimental design which then through the result shared an understanding of how volume and valency affects the choice of a real estate agent. Through the previous research, the study has been desired to be applied to other industries previously performed, which we believe this study fulfills through the replicated method used.   Method: This study is conducted through a quantitative research strategy with a replicating method with experimental design. The data collected for the study's results and analysis has been collected through a digital survey with manipulated profiles through the recommendation site "Reco". The data has then been analyzed through the software "Jamovi" through descriptive analyzes and through a correlation matrix.   Result &amp; Conclusions: The study has shown results that contradict previous research, among other things, that volume is more crucial in the choice of a service in relation to valency. This result also shows that companies should study their industries to increase their understanding of how strongly certain factors are within digitalized marketing.   Contribution of the thesis: The study presents a theoretical as well as practical contribution in the final chapter, which briefly shows how volume and valency can vary widely in relation to the previous research carried out and what should be considered and carefully analyzed in order to be able to apply at company level in marketing in the future. as recommendations.   Suggestions for future research: Comparative study of the two terms eWOM and WOM, which is the more traditional expression to describe a word of mouth effect. How do they differentiate in results, and are the differences in efficiency against the one that is actually recommended. The study also proposes to use demographic data as a basis for the interpretation of the statistics, which has not been done in this study. We also consider it interesting with a more general manipulation of the different profiles, such as adding factory or brand and seeing how these differ.   Key words: WTA, WTP, IRP, eWOM, WOM, Valency and Volume.