Dissertations / Theses on the topic 'Valency'
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Sawicki, Lea. "Verb-valency in contemporary Polish : a study of the major valency-types /." Tübingen : G. Narr Verlag, 1988. http://catalogue.bnf.fr/ark:/12148/cb35508851z.
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Vihman, Virve-Anneli. "Valency reduction in Estonian." Thesis, University of Edinburgh, 2004. http://hdl.handle.net/1842/25272.
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Theories of voice based on a model of passivisation such as that exhibited by English tend to characterise valency modifications as primarily a syntactic phenomenon, involving the mapping of semantic roles to non-canonical syntactic argument positions. This dissertation finds such an approach insufficient to account for the observed phenomena in the more complex domain of voice in Estonian. The thesis provides a thorough description of the Estonian voice category, through an in-depth study of four valency-reducing constructions: the impersonal, personal passive, generic apersonal, and anticausative. These all involve semantic and lexical-level changes to the argument structure of a predicate. In order to arrive at a satisfactory theoretical account of voice in Estonian, the analysis must consider semantic and pragmatic information alongside the realignment of syntactic rules linking grammatical functions with argument places. The status of verbal arguments undergoing demotion in valency-changing operations is shown to be crucial to the interpretations that the various constructions give rise to. The thesis establishes a hierarchy of implicit arguments as a key element of these differnces in interpretation. The impersonal argument, although non-overt, is shown to be psychologically and linguistically salient, being present for both semantic interpretation and such syntactic purposes as anaphoric reference. The impersonal actor is argued to be only slightly demoted, the more important property assigned to the actor argument of impersonals being that of non-specificity. Following the impersonal on the proposed Demotion Hierarchy is the personal passive, with a true demoted agent, which can, however, be re-established through an agentive adverbial. Generic apersonal constructions have a less accessible actor referent, whose interpretation crucially involves pragmatic inferencing. The anticausative retains only a single undergoer argument in its logical structure, which reveals both proto-agent and proto-patient characteristics. Only this derivationally formed predicate truly deletes its actor argument.
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How, Siew-Eng. "Multiple valency and assay amplification." Thesis, University of Southampton, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.415237.
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Dlayedwa, Ntombizodwa Cynthia. "Valency-reducing processes in Xhosa." Thesis, University of Essex, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.394291.
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Khare, Niraj. "Hypergraphs with restricted valency and matching number." The Ohio State University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=osu1275880336.
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Zhao, Yilu. "Distributional criteria for verbal valency in Chinese /." Leuven : Peeters, 1996. http://catalogue.bnf.fr/ark:/12148/cb38955510z.
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Fischer, Klaus. "Investigations into verb valency : contrasting German and English." Thesis, University of Wales Trinity Saint David, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.683145.
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Ladlow, Caroline Betty. "Rates of metals extraction and stripping involving valency change." Thesis, University of Bradford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.254014.
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Matsushita, Yana. "Superconductivity and mixed valency in thallium-doped lead telluride /." May be available electronically:, 2007. http://proquest.umi.com/login?COPT=REJTPTU1MTUmSU5UPTAmVkVSPTI=&clientId=12498.
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Man, Wing Yang. "Carbon rich organometallics : from mixed valency to redox active ligands." Thesis, Durham University, 2013. http://etheses.dur.ac.uk/6901/.
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This thesis sets out to explore the electronic structures and redox properties of organometallic complexes. The mixed valence states of these complexes have been investigated and classified. Chapter 1 introduces the general area and provides a brief summary of the theory to electron transfer. The concepts discussed in Chapter 1 are developed further in subsequent Chapters. A trimetallic molecular assembly featuring two redox-active organoiron fragments connected via a central ruthenium tetramesitylporphyrin socket through pendant pyridyl moieties was investigated using electrochemical and UV-vis-NIR/IR spectroelectrochemical studies. Electrochemical studies reveal three reversible oxidation waves, the first two of which can be attributed to the stepwise oxidation of the iron centres. The redox separation between these iron redox waves was found to be constant regardless of electrolyte composition, suggesting a “through bond” mechanism for electronic interactions between the iron centres. An analysis of the near-IR band in the mixed valence state suggests the assignment of [{Cp*(dppe)(Py-4-C≡C)Fe}2(µ-Ru(TMP))]+ as a strongly coupled, Class II mixed valence complex in which the NIR band arises from genuine metal to metal charge transfer (IVCT) processes. Iron alkynyl complexes Fe(C≡CR)(PP)(Cp’) are well known to exhibit metal localised redox properties, whilst the alkynyl ligand in analogous alkynyl ruthenium complexes is redox-active. In order to tune the metal coordination sphere, to explore further the redox activity of carbon rich ligands bound to ruthenium, a series of complexes of the general form Ru(CH=CHC6H4R-4)(CO)(PPh3)Tp where R = N(C6H4Me)2, OMe, CH3, CO2Me, NO2 were synthesised, crystallographically characterised and investigated using electrochemical, UV-vis-NIR/IR spectroelectrochemical studies and DFT computational methods. IR spectroelectrochemical studies and DFT computations are consistent, with descriptions of the vinyl ligand as being redox-active, as developed by Winter and co-workers for some related mono- and bimetallic ruthenium vinyl complexes. Studies of Ru(CH=CHC6H4R-4)(CO)(PPh3)Tp, Ru(CH=CHC6H4Me-4)Cl(CO)Cl(PMe3)3 and [{(PMe3)3(CO)ClRu}2(µ-CH=CHC6H4CH=CH)] reveal that the bridging ligand is also heavily involved in the oxidation process. A three state model in which the bridge is appreciably involved in the stabilisation of charge is required to rationalise experimental data including electronic spectra, consistent with theoretical findings. In seeking to fine tune the electronic character of ruthenium based [{LnRu}2(µ-bridge)]n+, vinyl and alkynyl complexes featuring a dithia[3.3]cyclophane moiety were investigated. In both cases, the bridging moiety was found to be heavily involved in the oxidation processes. The triarylamine ligand moiety has attracted attention due to its potential to promote electronic interactions between three metal sites, through a central nitrogen atom. The synthesis, crystallographic characterisation, electrochemical and spectroelectrochemical response of one, two and three cluster centres on a triarylamine core have been examined. Experimental results point towards a localised structure, with no electronic interaction between the cluster moieties, which are examples of Class I Robin and Day mixed valence complexes. Pre-formed gold alkynyl and diyndiyl complexes can be cross-coupled with aryl halides in the presence of both Pd(II) and Cu(I) catalysts under mild conditions in ether based solvents at room temperature, without the need for an additional base. These gold-mediated Sonogashira reactions likely proceed via the transmetallation of the alkynyl fragment from Au(I) to Cu(I), prior to entry to a conventional Sonogashira reaction. These reactions present alternative methods to prepare differentially substituted diynes, without the need to expose the C-H functionality of longer chain polyynes, which can be inherently unstable.
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Nakagawa, Takeshi. "Rare-earth based fullerides : tuning the onset of valency transitions." Thesis, Durham University, 2009. http://etheses.dur.ac.uk/2112/.
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In this thesis, the recent advances in studies on rare-earth metal intercalated fullerene solids with emphasis on their structural, electronic, and magnetic properties. The investigations on the rare-earth based fullerides have been concentrated on their structural, electronic, and magnetic properties. Intercalation of C(_60) with rare-earth metals results in interesting compounds not only for the appearance of superconductivity but also for the magnetic properties and mixed valence phenomena related to the localised 4f electrons. Of particular interest, I discuss the results obtained from various experiments on rare-earth based mixed valence fullerides, of which displays a remarkable sensitivity of rare-earth valency to external stimuli, such as temperature and pressure. Among the family of rare-earth fullerides, Sm(_2.75)C(_60) was the first known molecular-based material to show valence fluctuation associated with the highly-correlated narrow-band behaviour of the 4f electrons in Sm ions. Improvement in the synthetic technique to produce single-phase rare-earth doped fullerides have opened the way to carry out detailed and systematic study of the structural properties of the RE(_2.75)C(_60) (RE = Sm, Eu, and Yb) as a function of temperature and pressure, which were carried out using the synchrotron X-ray powder diffraction technique. The obtained results have lead us to find a rich variety of temperature- and pressure-driven abrupt or continuous valence transitions. In addition, we have observed that by taking precise control on the nature of dopants, the tuning of the onset temperature and pressure of this valence transition were possible. Direct measurements on the valence states of the rare-earth ions in the fulleride salts as a function of temperature were carried out using X-ray absorption spectroscopy using the alkaline-earth and rare-earth mixed compound, (Sm(_2/3)Ca9_1/3))(_2.75) C(_60). The obtained spectra have provided clear evidence to confirm the electronic nature of the low-temperature first-order valence transition.
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Swartz, Eric Allen. "2-arc transitive polygonal graphs of large girth and valency." The Ohio State University, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=osu1243923530.
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Borisov, Vladislav Verfasser], Ingrid [Akademischer Betreuer] [Mertig, Steffen [Akademischer Betreuer] Trimper, and Maria-Roser [Akademischer Betreuer] Valenti. "Multiferroic interfaces of mixed valency systems studied from first principles / Vladislav Borisov. Betreuer: Ingrid Mertig ; Steffen Trimper ; Maria-Roser Valentí." Halle, Saale : Universitäts- und Landesbibliothek Sachsen-Anhalt, 2015. http://d-nb.info/106820821X/34.
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Arunkumar, Nandini. "The effects of antigen valency and CpG ODN on B cells." College Park, Md. : University of Maryland, 2007. http://hdl.handle.net/1903/6720.
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Thesis (Ph. D.) -- University of Maryland, College Park, 2007.Thesis research directed by: Cell Biology & Molecular Genetics. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Reichardt, Renate. "Valency sentence patterns and meaning interpretation : case study of the verb 'consider'." Thesis, University of Birmingham, 2013. http://etheses.bham.ac.uk//id/eprint/4645/.
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This thesis explores the interrelationship of local grammar, meaning, and translation equivalence, using a case study of the English verb CONSIDER, compared in a monolingual study with its near-synonyms BELIEVE, FEEL and THINK, and in a contrastive analysis with their German translation equivalents. The methodology fuses corpus linguistics and valency grammar, analysing and comparing monolingual and parallel corpora. Corpus investigation is found to be a reliable tool in identifying key translation equivalents and in verifying sentence patterns. Valency theory is argued to be more successful than related approaches in distinguishing between different levels of language analysis. Its flexibility regarding complement categorisation types make it possible to define categories that can be applied to both German and English appropriately in a contrastive study, in spite of the surface differences between the two languages. The findings highlight the problems of investigating the interplay of lexis and grammar in a contrastive context, and indicate that from the perspective of translation, language is much less rule-based and less phraseological than is often assumed. Applications of the research to the field of bilingual lexicography are discussed. Based on the corpus analysis and the valency analysis some sample dictionary entries are proposed.
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Du, Plessis Melissa. "A qualitative investigation into the relationship between self-concept and the propensity for role uptake in a small group." Diss., University of Pretoria, 2011. http://hdl.handle.net/2263/30160.
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When regarding the history of role theory, one becomes aware of the fact that, although much knowledge is available specifically pertaining to roles in small group settings (e.g. expectations about behaviour, types of roles, flexibility of locus, appropriateness of the role system, dynamic nature of role formation and development as well as typologies dividing roles into categories), not much literature is available specifically pertaining to what the impact of an individual’s self-concept is on his/her propensity to either assume or avoid certain roles in such a setting. Accordingly, this study aimed to explore the above-mentioned aspect of role division in small groups. Research was done by means of a case study research design, with a constructivist/interpretevist meta-theoretical paradigm as research approach. This paradigm holds that there are multiple subjective realities involved when studying human interactions and the consequences thereof. The study was furthermore conducted from a psychodynamic and systems theory perspective. Data was collected from a sample of postgraduate students, who participated in a training group as part of their Industrial and Organisational Psychology master’s degree programme at the University of Pretoria, by means of three different methods, namely video and voice recordings, a document study, as well as semi-structured interviews. Data was furthermore analysed by Atlas.ti, a qualitative data analysis programme, according to the principles of constructivist grounded theory. When regarding current literature on the subject, it is implied by some that an individual will only allow roles to be imposed on him/her if he/she is predisposed to assuming such roles, and if he/she can accordingly integrate the responsibility somehow with his/her self-concept. Accordingly, the results obtained showed some connection between an individual’s self-concept and the role(s) that was assumed by the individual in the small group setting. More specifically, the results showed that an individual is more likely to change roles with ease should the alternate role requirements also be in line with elements of the individual’s self-concept. The results further indicated that it might be difficult for an individual to adapt and change to another role should the roles, which are required in the small group setting, be in conflict with the individual’s self-concept. These findings thus imply that an individual’s self-concept might have an impact on an individual’s propensity to either assume or avoid certain roles (role valency) in a small group setting.Dissertation (MCom)--University of Pretoria, 2011.
Human Resource Management
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Marchal, Michelle. "La valence du ligand du récepteur à la transferrine 1 (TfR1) détermine son routage intracellulaire." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS418.
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Le récepteur à la transferrine (TfR1) est un récepteur très bien conservé au cours de l’évolution qui permet l’entrée du fer (Fe) lié à la transferrine (Fe-Tf) dans les cellules. Une fois internalisé, le fer se détache de la Tf et est exporté dans le cytoplasme tandis que le complexe Tf/TfR1 est recyclé à la membrane plasmique. Le TfR1 est internalisé par un mécanisme clathrine dépendant et peut être soit recyclé à la membrane plasmique par la voie rapide, soit être dirigé vers le compartiment endosomal de recyclage (ERC). Une fois dans l’ERC, le TfR1 peut être soit recyclé à la membrane plasmique par la voie lente, soit être dirigé vers les lysosomes. De nombreuses protéines régulent le routage des protéines internalisées comme les protéines Rab. Il s’agit de petites GTPases impliquées dans les échanges moléculaires entre les différents compartiments cellulaires.Etant la principale voie d’entrée du fer dans la cellule,le TfR1 est exprimé par la plupart des cellules et est surexprimé par les cellules hautement prolifératives dont certaines cellules cancéreuses. Le TfR1 est très étudié comme cible thérapeutique dans le développement de nouvelles stratégies anti-cancéreuses. A24 est un anticorps murin anti-TfR1 dont l’action anti-proliférative et pro-apoptotique ont été démontrées dans plusieurs hémopathies malignes.Nous nous sommes demandés comment la fixation de A24 sur le TfR1 peut produire des effets différents de la fixation de la Fe-Tf. En générant un fragment Fab, nous avons d’abord démontré que le routage du TfR1 dépend de la valence de son ligand. Nous avons ensuite démontré que la fixation monovalente du TfR1 par la Fe-Tf et le Fab induisent son recyclage sans passer par l’ERC. Nous avons également démontré que la fixation divalente du TfR1 par A24 induit son routage depuis l’ERC vers les lysosomes par une voie dépendante de Rab12The transferrin receptor (TfR1) is a highly conserved receptor that allows the entry of iron (Fe) linked to transferrin (Fe-Tf) into cells. Once internalized, Fe separates from the Tf and is exported in the cytoplasm whereas the complex Tf/TfR1 is recycled to the cell membrane. TfR1 is internalized by a clathrin mediated endocytosis and can be either recycled to the cell membrane through the rapid pathway or be routed towards the endosomal recycling compartment (ERC). Once in the ERC, the TfR1 can be either recycled to the cell membrane through the slow pathway or be routed towards lysosomes. Many proteins regulates the routing of internalized proteins such as Rab proteins. They are small GTPases involved in molecular exchanges between the different cellular compartments.Being the main mode of entry of iron into cells, TfR1is expressed by almost every cells and is overexpressed by highly proliferative cells including some cancer cells. TfR1 is extensively studied as a therapeutic target for the development of new anti-cancer strategies. A24 is a murine anti-TfR1 whose anti-proliferative and pro-apoptotic roles were demonstrated in several hematological malignancies.We wondered how A24 binding on TfR1 can produce different effects from Fe-Tf binding. By the manufacturing of a Fab fragment, we first demonstrated that TfR1 fate depends on its ligand’s valency. We then demonstrated that the monovalent binding of TfR1 with Fe-Tf or the Fab leads to its recycling without going through the ERC. We also showed that the divalent binding of the TfR1 by A24 leads to its routing from the ERC to lysosomes through a Rab12 dependent pathway
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Tarhuni, Sarah. "Mixed valency in redox-active, all-carbon bridged bimetallic complexes of iron and molybdenum." Thesis, University of Manchester, 2016. https://www.research.manchester.ac.uk/portal/en/theses/mixed-valency-in-redoxactive-allcarbon-bridged-bimetallic-complexes-of-iron-and-molybdenum(8e081a41-817f-4e98-bc89-c2e1a44e10fe).html.
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This thesis describes the development of new procedures for the synthesis of homo- and hetero-bimetallic complexes [M-(C≡C-C≡C)-M*] linked by a butadiyndiyl (-C≡C-C≡C-) bridge (where M, M* = Mo(dppe)(η-C7H7) and Fe(dppe)Cp) and also of the diethynyl-anthracenyl bridged complex [{Mo(dppe)(-C7H7)}2(μ-C≡CC14H8C≡C)] in which an anthracenyl group is inserted into the butadiyndiyl bridge. The redox chemistry and mixed valence character of these systems are investigated by a range of synthetic, electrochemical and spectroscopic techniques. Chapter 1: (Introduction) presents a literature review related to all-carbon bridged bimetallics including their synthesis, redox chemistry and mixed valence properties. Chapter 2: describes the synthesis of the key precursor [FeI(dppe)Cp] in multi-gram quantities. A new synthetic protocol has been developed to vinylidene [Fe(C=CH2)(dppe)Cp][PF6] and acetylide [Fe(C≡CH)(dppe)Cp] complexes starting from the iodo precursor [FeI(dppe)Cp] which can be conveniently used in place of the chloro precursor [FeCl(dppe)Cp]. We also identified the carbene species [Fe{C(OMe)Me}(dppe)Cp][PF6], which is formed as a by-product from the reaction of the vinylidene with a molecule of methanol solvent. Chapter 3: describes the synthesis and characterisation of butadiyndiyl bridged [{Fe(dppe)Cp}2(-CCCC)]n+ (n = 0, 1, 2). The electronic structure of [{Fe(dppe)Cp}2(-CCCC)]n+ has been investigated in all thermally accessible oxidation states (0, 1, 2, 3) and compared directly with the closely related ruthenium analogue [{Ru(dppe)Cp}2(-CCCC)]n+. Particular focus was given to the formally 'mixed valent' radical cations [{Fe(dppe)Cp}2(-CCCC)]+ and [{Ru(dppe)Cp}2(-CCCC)]+, where the spectroscopic data highlight significant differences between the iron and ruthenium complexes. Furthermore, in this chapter the heterobimetallic complex [{Fe(dppe)Cp}(µ-C≡C-C≡C){Mo(dppe)(C7H7)}] was successfully synthesised and characterised by microanalysis, IR, mass spectrometry and cyclic voltammetry. Chapter 4: discusses the synthesis of the diethynyl-anthracene bridged complexes [{Mo(dppe)(-C7H7)}2(μ-C≡CC14H8C≡C)]n+ (n = 0, 1, 2). The focus of the investigation is to determine the effect of a diethynyl-benzene vs. diethynyl-anthracene bridge in bimetallics supported by the Mo(dppe)(C7H7) end cap. In the mixed valence (n = +1) state, the odd electron should be more localised on the ligand bridge of the anthracene derivative and this principle was investigated by EPR spectroscopy.
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Nahra, Joe. "Synthesis of low-valency neoglycoconjugates using transition metal-catalyzed reactions and synthesis of phenylethanoid glycosides." Thesis, University of Ottawa (Canada), 2002. http://hdl.handle.net/10393/6166.
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In the first part of this thesis, a series of rigid glycodimers were synthesized from sugar alkenes and alkynes, using transition metal catalyzed reactions. The synthesis of these dimers depended on the formation of a new carbon-carbon bond between their monomeric units. Sugars containing terminal alkenes were homodimerized using the olefin metathesis reaction, catalyzed by Grubbs' ruthenium catalyst. Terminal alkene carbohydrate derivatives were also coupled with aryl halide carbohydrates by the Heck coupling reaction, using Pd (0) catalyst, to form homo- and hetero-carbohydrate dimers selectively. Glycodimers were also obtained from sugar alkynes, using the Sonogashira coupling reaction. The dimerization of aryl halide carbohydrate derivatives using Pd (0) catalyst, and the cyclotrimerization of alkyne carbohydrates, using Grubbs' catalyst, were also attempted but were not successful. In the second part of this thesis, phenylethanoid glycosides were synthesized by glycosidation reactions. This family of compounds was shown to have numerous biological activities. A multi-step synthesis of Echinacoside, a phenylethanoid glycoside, was attempted.
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Davies, Damian Walford. "Archetypes and antitypes : the valency of five figures in the culture and literature of the 1790s." Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324861.
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Ståhl, Andreas, and Markus Westblad. "Digitaliserad word of mouth, en betydande faktor för WTA : En experimentell studie applicerad på valet av mäklare." Thesis, Högskolan i Gävle, Företagsekonomi, 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:hig:diva-34830.
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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 & 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 & 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.
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Ziehm, Christopher. "Ground State and Excited State Mixed Valency in Metal-Metal Quadruply Bonded Complexes Supported by Extended π Ligands." The Ohio State University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=osu1469017749.
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Liu, Bingcan. "Design and transition metal-mediated synthesis of multivalent neoglycoconjugates bearing terminal galactosides with various valency and structural features." Thesis, University of Ottawa (Canada), 2003. http://hdl.handle.net/10393/29058.
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In the past ten years, with the emergency of multivalent neoglycoconjugates such as glycopolymers, glycodendrimers, and glycoclusters, carbohydrates have gained a lot of attention in the hope of developing potent carbohydrate-based therapeutics, as well as the opportunities to investigate glycobiology.
So far many strategies have been explored to effectively assemble multivalent neoglycoconjugates. This work contains a discussion of the design and transition metal-mediated synthesis of terminal galactoside-carrying glycoclusters and glycodendrimers in detail.
Propargyl alpha-galactoside antigen monomer was synthesized using conventional glycosidation methods. Then analogues of alpha-galactoside antigen clusters were prepared utilizing the Sonogashira reaction as the key step. Various conditions for the Sonogashira have been investigated and an interesting finding is that this reaction does occur with Cu (I). These synthetic alpha-galactoside antigens have shown enhanced binding affinity toward human anti-alpha-galactoside antigen antibodies in biochemical assays.
Likewise, galactoclusters were prepared as potential galectin inhibitors. However, these fully deprotected compounds were barely soluble in aqueous conditions. To solve this problem, analogues of lactoclusters, having an extra glucosyl residue, with various valencies and structural features were synthesized. Kinetic precipitation tests demonstrated that most lactoclusters cross-linked with galectin-3 formed insoluble complexes quickly and this phenomenon was observed for the first time, thus suggesting the clustering of the receptors upon contact.
A sequence of olefin cross-metathesis, Sonogashira reaction, and cyclotrimerization was performed to assemble a hexameric C-linked glycopeptidomemetic.
Olefin cross-metathesis mediated by the second generation Grubbs catalyst was successfully effected to prepare extended glycoallyl halides and unnatural amino acids. These glycoallyl halides were proven to be useful in the synthesis of high order glycoclusters.
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Kulkarni, Amit. "Surface Modification of Carboxyl-functionalized Polymeric Nanoparticles for Attachment of Targeting Peptides." University of Cincinnati / OhioLINK, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1242986910.
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Janic, Katarzyna. "L’antipassif dans les langues accusatives." Thesis, Lyon 2, 2013. http://www.theses.fr/2013LYO20109/document.
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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 sémantiqueThe 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
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Gérardin, Hélène. "Les verbes intransitifs primaires et dérivés en géorgien : description morphosyntaxique, sémantique et dérivationnelle." Thesis, Sorbonne Paris Cité, 2016. http://www.theses.fr/2016USPCF025/document.
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Cette thèse a pour objet le classement et la description des verbes intransitifs monoactanciels en géorgien, dans une perspective linguistique typologique. L’analyse comporte deux phases : d’une part un classement des verbes, et d’autre part une réflexion critique sur la complexité du système mis en évidence ainsi que sur la notion d’intransitivité en général. Le classement proposé commence par séparer les verbes non dérivés d’autres verbes (‘intransitifs primaires’) de ceux dont la morphologie indique un processus de dérivation détransitive (‘intransitifs dérivés’). Les verbes monoactanciels primaires se divisent en deux classes, ayant chacune une unité à la fois sémantique et morphosyntaxique : les verbes téliques (comme ‘mourir’) et les verbes atéliques (comme ‘vivre’). Les verbes biactanciels sont ensuite brièvement décrits selon une échelle de transitivité. Puis sont abordés les verbes monoactanciels dérivés, qui peuvent avoir jusqu’à quatre interprétations : passive, décausative, autocausative et antipassive, et enfin les couples de verbes dont les deux membres transitif et intransitif sont marqués morphologiquement. L’intransitivité monoactancielle en géorgien n’a pas encore été traitée de façon globale, en particulier certains aspects comme l’antipassif, dont on propose une étude détaillée. Le présent travail entend apporter une contribution à la fois aux études kartvéliennes et aux récentes réflexions générales sur les concepts de transitivité, de valence et de voix. En effet, par son grand nombre de classes verbales et par le lien étroit qu’il fait entre morphosyntaxe et sémantique, le géorgien a des données de premier choix à fournir à l’étude de ces conceptsThe topic of this PhD thesis is a classification and description of one-argument intransitive verbs in Georgian in a typological perspective. The analysis consists of two steps: firstly, the classification of the various types of verbs and secondly, a critical investigation of the complexity of the system under study and on the concept of intransitivity in general. The proposed classification begins by separating verbs not derived from other verbs (‘primary intransitives’) from those whose morphology indicates a process of de-transitive derivation (‘derived intransitives’). Primary one-argument verbs, in turn, are divided into two classes, each consisting of verbs with the same morphological, as well as semantic properties: telic verbs (such as “to die”) and atelic verbs (e.g. “to live”). Two-argument verbs are briefly described according to a transitivity scale. Discussed next are derived one-argument verbs which may have up to four readings: passive, decausative, autocausative and antipassive, and finally, verb pairs whose members, one transitive and one intransitive, are both morphologically marked. One-argument intransitivity in Georgian has not yet been investigated thoroughly; this particularly applies to some of its aspects such as the antipassive, of which a detailed study is offered here. The present work is intended to contribute to Kartvelian studies and at the same time, to recent discussion in general linguistics on the concepts of transitivity, valency and voice. Indeed, owing to its large number of verb classes and the close connection between morphosyntax and semantics, Georgian offers excellent data for the study of these concepts
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MARQUES, ANA LUCIA DE ANDRADE. "THE RELATIONSHIPS BETWEEN VERBS OF MOVEMENT AND THEIR LOCATIVE COMPLEMENTS OF ORIGEN AND GOAL ACCORDING TO THE VALENCY GRAMMAR APROACH." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2002. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=3532@1.
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PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRONa descrição do português do Brasil, as expressões adverbiais locativas de origem e de meta, exigidas pela valência de verbos de movimento tetravalentes, apresentam peculiaridades quanto à realização nos enunciados. Neste trabalho, a análise realizada é de caráter qualitativo, com base nas propostas da gramática de valências. Examina a possibilidade de realização de cada argumento citado e as motivações, os efeitos gerados na sua relação com os verbos de que dependem. Os locativos que indicam meta e que complementam o quarto espaço dos verbos de movimento/direção possuem freqüência maior de realização, quando os verbos inferem transferência de lugar. Este trabalho considera o valor das preposições que acompanham os complementos e os advérbios que indicam o espaço dêitico.
In the description of the Brazilian Portuguese, the valency of verbs of movement opens four spaces which are fullfilled by adverbial expressions considered locatives of origen and goal. These expressions present peculiarities regarding the realization in utterances. Based on the proposals of the valency grammar, an analysis of qualitative aspect was provided aiming to examine the possibility of realization of each argument mentioned and the motivations and results generated in their relationship with the verbs on which they depend. The locatives that indicate goal and complement the fourth space of the verbs of movement / direction occur more often when these verbs infer location transferance. This dissertation considers the value of prepositions that accompany the complements and the adverbs that indicate the deitic space.
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Mondal, Sudipta [Verfasser], and Wolfgang [Akademischer Betreuer] Kaim. "Transition metal complexes with 1,2-dicarbonylhydrazine : a study on mixed-valency and non-innocent ligand behaviour / Sudipta Mondal ; Betreuer: Wolfgang Kaim." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2018. http://d-nb.info/1169653715/34.
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Delhem, Romain. "Verbes labiles et schémas de complémentation en anglais." Thesis, Sorbonne université, 2018. http://www.theses.fr/2018SORUL068.
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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 homonymesWithin 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
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Raudienė, Irena. "Procesus ribojantys cirkumstantai." Master's thesis, Lithuanian Academic Libraries Network (LABT), 2005. http://vddb.library.lt/obj/LT-eLABa-0001:E.02~2005~D_20050603_174551-37160.
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The present paper is an attempt to examine the restriction (determination) of the Process by circumstantial elements. Although the Process can be used absolutely, more often than not it is accompanied by other elements – non-circumstantial (objective complements) and circumstantial. The choice of a circumstantial element is mostly determined by the type of Process, tense and aspect. Two types of circumstantial elements are distinguished: 1) non-specific (i.e. circumstantial elements common to all Process types); 2) specific (i.e. circumstantial elements peculiar to a Process type).
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Karches, Clara [Verfasser], and Sebastian [Akademischer Betreuer] Kobold. "Characterization of the influence of antibody valency on murine synthetic agonistic receptor-transduced T cell activation and action / Clara Karches ; Betreuer: Sebastian Kobold." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2019. http://d-nb.info/1202011861/34.
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Mehta, Akash. "Nitridonickelates: Preparation, Structure and Properties." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2005. http://nbn-resolving.de/urn:nbn:de:swb:14-1131358344355-22352.
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Low valent nickel (less than +1) complexes are rare in nature, however they are regularly encountered in nitridonickelate chemistry. Ternary alkaline earth nitridonickelates exhibit a variety of interesting crystal structures with respect to their covalently bonded nitridonickelate anionic framework. The coordination geometry of low valent nickel in these compounds presents a unique structural feature with nickel being in linear coordination by nitrogen atoms. The nitridonickelate frameworks of compounds investigated in this work are: Ba2[Ni3N2]: The first ternary alkaline earth nitridonickelates with 2D Ni-N anionic network. The formal oxidation state of Ni is +0.67. Ba2(Ba6N)[NiN]6: The structure is made of o1D helical Ni-N anionic chains. Also, the structural stability of this compound´s structure type was found to occur over a wide range of substitution of Ba by Ca and Sr; a max. of 70 percent Ba could be successfully replaced by Sr and Ca atoms retaining the same structure type. The formal oxidation state of Ni is +0.83. Ba[NiN] and the solid solution series Ba[CuxNi1-xN]: The structure is made of 1D zig-zag Ni-N chains. The solid-solution series is isostructural to Ba[NiN] at lower content of Cu while, at higher content it resembles Ba[CoN] structure type, however at very high Cu content it again transforms to Ba[NiN] structure type. The formal oxidation state of Ni is +1.0. Sr2[Ni(CN)N]: The structure consists of N-Ni-(CN) dumbbells. The compound is the first example of cyano-nitridonickelate. The formal oxidation state of Ni is 0. The handling of the ternary alkaline earth nitridonickelates in specific and also of the other nitridometalates in general suffers greatly due to their being air and moisture sensitive. This requires synthetic methods suitable for air and moisture sensitive samples and also the respective instrumental setup for the measurement of their physical properties under inert atmosphere. Up to now no comprehensive investigation of the physical properties of the ternary alkaline earth nitridonickelates has been made. In this work an emphasis was given to systematically investigate the physical properties of the ternary alkaline earth nitridonickelates and to understand their structure specific physical properties. The common features of the investigated ternary alkaline earth nitridonickelates are: 1. the low valency of nickel. 2. the linear coordination of Ni and octahedral coordination of N. During this investigation the low valent character of nickel was experimentally confirmed with the help of X-ray absorption spectroscopy and the interpretation of magnetic susceptibility data where the magnetic moments of the nickel atoms were always consistent with that of a low valent nickel species. The results obtained from the magnetic measurements and electrical conductivity shows that the alkaline earth nitridonickelates order antiferromagnetically at low temperatures and show temperature dependent metallic conductivity whereas the cyano-nitridonickelate Sr2[Ni(CN)N] does not order at low temperature, is paramagnetic, and exhibits semiconducting behaviour. This investigation has provided a better understanding of ternary alkaline earth nitridonickelates with respect to the different structure they exhibit and their associated physical properties. This work motivates to extend the investigations of the physical properties of other nitridometalates. These also exhibit different crystal structures with respect to their nitridometalate anionic framework and thus, structure specific physical properties are also to be expected.
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Li, Yang. "Electrostatics of the Binding and Bending of Lipid Bilayers: Charge-Correlation Forces and Preferred Curvatures." Thesis, University of Waterloo, 2004. http://hdl.handle.net/10012/1282.
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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 D. 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 h: The attraction is enhanced by ion sizes for h ranges of physical interest, while it crosses over to the known D-independent universal behavior as h → ∞; it remains finite as h → 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 Δ A0 and the spontaneous curvature C0 of the bilayer. We find Δ A0 and C0 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 Δ A0 and C0. 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 Δ A0 and C0. We outline biological implications of our results.
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Bresson-Maximova, Elena. "Les réfléchis en français, en anglais et en russe." Paris 3, 2008. http://www.theses.fr/2008PA030092.
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Cette thèse a pour objet l’étude des réfléchis et de la réflexivité en anglais, en français et en russe. Nous distinguons les pronoms réfléchis « forts » (himself, sebja), les clitiques (SE/SI dans les langues romanes) et les affixes (_sja en russe). Contrairement au russe où sebja et svoj sont des pronoms réfléchis stricto sensu, ni le français, ni l’anglais ne disposent de pronoms réfléchis au sens strict ; les pronoms en question sont à l’origine intensifs ou contrastifs. Les clitiques réfléchis dans les langues romanes (et slaves également) sont des épels du trait de personne du sujet. Ils fonctionnent, premièrement, comme des morphèmes changeurs de valence produisant un prédicat inaccusatif. Deuxièmement, ce sont des marquers de voix. Nous définissons la vois au sens large : c’est la manière d’exprimer le sujet de la proposition. Tout comme SE/SI, -sja est un morphème de voix, mais ce n’est pas un clitique, mais un affixe ayant subi la morphologisation qui a pour résultat le syncrétisme de personne, nombre et cas. Nous émettons également une hypothèse concernat la cause de la disparition des clitiques pronominaux en russe ( le changement du paradigme de conjugaison et la disparition de l’auxiliaire de ce paradigme)This thesis deals with reflexive pronouns in English, French and Russian. We distinguish between strong reflexive pronouns (like himself in English or sebja in Russian), reflexive clitics (like SE/SI in Romance) and affixes (like Russian –sja). Unlike Russian, where svoj and sebja can be considered as reflexives in the strict sense of the word, neither French nor English have at their disposal the pronouns used merely as reflexive ones. Those pronouns are of intensive or contrastive origin ; their reflexive meaning is not systematic. As for reflexive clitics in Romance, they are merely spell-outs of the person feature of the subject. They function as valency-changing morphemes which produces unaccusative predicates. Secondly, they can be analysed as voice markers (where Voice is a functional head). We define the Voice as a manner of expression of the sentence subject. Like SE/SI, Russian –sja is a voice morpheme, but it is not a clitic, but an affix, because it has undergone morphologisation, the result of which is its person, number and case syncretism. We argue that Russian has lost its pronominals clitics because of the changements in the conjugation paradigm, the verb having lost the majority of its tense and the use of auxiliairies
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D'accriscio, Florian. "Complexes de nickel caméléons : exploration de tous ses degrès d'oxydation pour la formation de liaisons C-C et C-CF3." Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30216.
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Ce projet de recherche porte sur l’étude de complexes de nickel à différents degrés d’oxydation (de 0 à +IV) dans le but de promouvoir la formation de liaisons C–C et C–CF3. Dans une première partie, l’étude porte sur l’utilisation de complexes de nickel à basse valence en tant que catalyseurs pour les réactions de couplage croisé de Negishi et de Suzuki-Miyaura. Si la formation de liaisons C–C est une réaction parfaitement maîtrisée au palladium, l’emploi de complexes de nickel comme catalyseurs est plus difficile à appréhender d’un point de vue mécanistique. Dans ce travail, l’utilisation d’un ligand bis-phosphine a permis de synthétiser et d’isoler des complexes de nickel(0). Une étude mécanistique complète alliant expériences et calculs DFT démontre que la réaction de Negishi fonctionne uniquement sur un régime Ni(0)/Ni(II). Des études préliminaires montrent en revanche que le mécanisme est tout autre lorsqu’on s’intéresse à la réaction de Suzuki-Miyaura. Dans une deuxième partie, l’objectif est la formation de liaisons C–CF3 en utilisant des complexes de nickel à haute valence. La formation de ces liaisons à partir de métaux de transition reste un défi puisque les méthodologies utilisées à ce jour au niveau industriel nécessitent l’utilisation de conditions drastiques et conduisent à la formation de composés nocifs pour l’environnement. Ce n’est que très récemment que des travaux de recherche ont porté sur l’utilisation du nickel comme support à la formation de liaisons C–CF3. Ce projet décrit la synthèse de complexe de nickel(III) portant deux groupements CF3 et l’utilisation d’un complexe dimérique de nickel(III) comme plateforme pour l’accès à d’autres complexes [NiIII(CF3)2]. Si ces complexes ne permettent pas de former de liaisons C–CF3, une espèce de nickel(IV) permet la formation de telles liaisons. Il s’agit de plus du premier complexe de nickel(IV) portant deux atomes de fluor et deux groupements CF3 capable de promouvoir l’activation de liaisons C–HThis research project aims at the study of nickel complexes in different oxidation states (from 0 to +IV) in order to promote C–C and C–CF3 bond formation. In a first part, low-valent nickel complexes are used as catalysts to perform Negishi and Suzuki-Miyaura cross-coupling reactions. If the C–C bond formation is a well-known reaction using palladium catalysts, the use of nickel complexes as catalysts is more complicated to understand in the mechanistic aspect. In this work, the key point is the use of a bis-phosphine ligand which allows the synthesis and isolation of nickel(0) complexes. A full mechanistic study via stoichiometric reactions as well as DFT calculations confirms that the Negishi cross-coupling works only on a Ni(0)/Ni(II) catalytic cycle. Surprisingly, preliminary studies on the Suzuki-Miyaura cross-coupling reactions show that the mechanism pathway is completely different. In a second part, our interest is focused on the C–CF3 bond formation using high-valent nickel complexes. In chemical industries, the C–CF3 bond formation requires harsh conditions and also produces toxic waste for the environment. This mainly explains why the use of transition metals is still challenging in this topic. However in the last few years, the interest for the use of nickel complexes as coupling agent for C–CF3 bond formation has grown. This work deals with the synthesis of nickel(III) complexes bearing two CF3 substituents and the use of a dimeric nickel(III) complex as a building block for the formation [NiIII(CF3)2] type complexes. If these species do not promote the C–CF3 cross coupling, a nickel(IV) complex shows its ability to create this bond. Moreover, this is the first nickel(IV) species bearing both fluorine and CF3 substituents at the same metal center and promoting C–H bond activation
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Febrer, Romaguera Manuel Vicente. "Cartas pueblas de las morerías valencianas y documentación complementaria /." Zaragoza : Anubar ed, 1991. http://catalogue.bnf.fr/ark:/12148/cb36664424j.
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Allain-Castrillo, Monique Hierro S. Pescador José Bousoño Carlos. "Paul Valéry y el mundo hispánico." Madrid : Gredos, 1995. http://catalogue.bnf.fr/ark:/12148/cb369739352.
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Bertoldi, Anderson. "A semântica dos adjetivos: como e por que incluí-la em uma ontologia de domínio jurídico." Universidade do Vale do Rio do Sinos, 2007. http://www.repositorio.jesuita.org.br/handle/UNISINOS/2555.
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A meta principal desta pesquisa é realizar um estudo da semântica dos adjetivos objetivando a sua representação em uma ontologia jurídica. O fato motivador desse interesse foi o estudo de ontologias e léxicos computacionais jurídicos e a constatação de que os adjetivos não recebem um tratamento sistemático nessas ferramentas computacionais de conhecimento especializado. A partir dessa constatação, partiu-se para o estudo de ontologias e léxicos computacionais de linguagem não-especializada, buscando elementos práticos e teóricos para a inclusão sistemática, e não ocasional, de adjetivos em uma ontologia jurídica. Esta pesquisa defende que a eficiência no tratamento computacional da linguagem requer uma combinação de teorias. Assim, a metodologia adotada combina diferentes abordagens teóricas. Através do estudo do corpus e construção da ontologia jurídica, percebe-se a importância dos adjetivos para a organização do conhecimento especializado. Nos domínios de conhecimento especializados, os adjetivos têm a fu
The main goal of this research is to study the semantics of the adjectives in order to codify them into a legal ontology. Through a search for legal ontologies and lexicons one verifies that adjectives are not codified systematically into specialized lexicons and ontologies. Taking the codification of adjectives into a legal ontology as the target of this work, one analyzes non-specialized language ontologies and lexicons. The purpose of such analysis is to find practical and theoretical elements for including adjectives systematically into a legal ontology. This research defends the position that integrating linguistic approaches is more fruitful to natural language processing. Therefore, the methodology applied here combines different theoretical approaches. The corpus analysis and legal ontology construction shows the importance of adjectives in organizing the specialized knowledge. In the specialized domains, adjectives have the main function of classifying entities
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Silva, Marcelo Lopes da. "As construções com objeto cognato em português: análise baseada no uso de um desencontro sintático-semântico e sua modelagem formal pela gramática das construções." Universidade Federal de Juiz de Fora (UFJF), 2010. https://repositorio.ufjf.br/jspui/handle/ufjf/2712.
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Investigam-se as construções com objeto cognato (cOC) na língua portuguesa não apenas quanto às hipóteses gerativistas, mas principalmente com base nas hipóteses sociocognitivas e construcionista-unificacionistas. Verifica-se a ocorrência de tipos de cOC com os verbos intransitivo inergativo, intransitivo inacusativo e transitivo-opcional. Nas cOCs com os verbos intransitivos, ocorre um desencontro sintático-semântico que é licenciado no nível pragmático, para que eles suportem o termo cognato em posição de foco sintático: um espelhamento do padrão transitivo. Tal motivação se baseia, primariamente, na pressuposição de que seja instanciada alguma especificação como fator de identificabilidade para o nome cognato enfocado e, secundariamente, num apenas realce da noção verbal. Essas restrições contextuais para a ocorrência do objeto cognato são descritas nos níveis internos das relações sintático-semânticas, vinculando-se a elas um conjunto de efeitos estilístico-fonografêmicos e aspectualpsicológicos. Verificam-se os seguintes fatos: Que a nominalização efetua, simultaneamente, um recorte dos argumentos verbais e um livre preenchimento informacional no sintagma nominal cognato. Que a repetição do radical verbo-nome coocorre com outras licenças contextuais de repetição, por um lado, aparentando redundância, e por outro, valorizando cada informação nova como parte da cena reconstruída no discurso. Que numa cOC, a especificação, informação nova, concentrase no modificador e/ou no determinante forte e/ou nos sufixos do nome cognato. Que a variação quanto ao número de argumentos instanciados com um mesmo verbo confirma a hipótese de heranças múltiplas, referida como ‘valência emprestada’, associada às licenças pragmáticas para as cOCs serem adequadamente interpretáveis em contextos descritivos. A investigação empírica consiste na verificação de ocorrências no Google, classificadas e parcialmente anexadas no Corpus representativo das cOCs em Português; e a formalização dos dados teóricos consiste na implementação aplicativa aos modelos: Gramática das Construções (CxG), Gramática dos Enquadres Semântico-Cognitivos em Redes (FrameNet), e Gramática das Construções Baseada no Signo (SBCG). Pela investigação das cOCs é reconhecida a interferência direta do nível pragmático nos outros níveis que compõem a gramática, confirmando a maior plausibilidade de uma gramática de contexto ou uma Gramática (Sócio)Cognitiva e (Sócio)Construcionista.
The Portuguese cognate object construction (COC) research goes through generative hypothesis to find solid grounds in usage-based cognitivist and unificationalconstructionist lands. It is observed that COCs occur with optional transitive verbs, with unergative intransitive and also with unaccusative intransitive verbs. The COCs with intransive verbs instantiates a syntatic-semantic mismatch, which non-default relations are pragmatically licensed for them to support the cognate noun in a syntactic focus position: as in a transitive pattern mirrowing. This motivation is based, firstly, on the pressuposition that some specification will be structurally given to identify the cognate noun, and, secondly, it is based on the possibility of a CO to be constructed as a ‘single focus’ of that verbal scenic conceptual reconstruction. Such COCs’ contextual restrictions are explained within syntax-semantics relational levels, to which is bound a set of stylistic-fonographical and aspectual-psychological effects. These following facts are observed: Firstly, that nominalization, simultaneously, pruns verbal arguments and enables free informational filling-up in a cognate noun phrase. Secondly, that nounverbal root repetition occurs among other licenced repetitions, on the one hand, apparently just redundant stuffs, on the other hand, it valorizes each specific new information that, in COs, concentrates on a modifier and/or on a strong determiner and/or even on a cognate noun suffix. Thirdly, that the variation in number of instantiated arguments of a same verb confirms the ‘multiple inheritance’ hypothesis, referred to as ‘borrowed valence’, locally unified to pragmatic licences for adequate interpretability of COCs in descriptive contexts. The empirical approach amounts Google occurrences, partially annexed and classified in a ‘Representative Portuguese COCs Corpus’; and the formalization of theoretical data consists in an applied implementation to the following models: Construction Grammar (CxG), Semantic Frames Grammar (FrameNet), and Sign-Based Construction Grammar (SBCG). By the COCs inquiry, it is recognized a direct pragmatically leveled interference into the other grammatical levels, a sufficient condition to prove the plausibility of a contextual grammar or a (Socio)Cognitive and (Socio)Constructionist Grammar.
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Cristóvão, Heloá Ferreira. "Estudo de verbos codificadores de extensão ou escala no jogo da linguagem: uma perspectiva funcionalista." Universidade Federal do Espírito Santo, 2013. http://repositorio.ufes.br/handle/10/6263.
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Previous issue date: 2013-08-05A maioria dos gramáticos acolhe os verbos em duas sessões: uma que trata de aspectos morfológicos; em seguida, dentro de uma perspectiva sintático-semântica, que aborda os verbos quanto à predicação. Isso se configura um problema nesse modelo de análise, visto que, ao considerar os verbos como elementos discretos, em frases descontextualizadas, não se consideram as relações morfológicas, sintáticas, semânticas, pragmáticas e discursivas que só podem ser observadas a partir da língua em uso, dentro do jogo combinatório da linguagem. A partir dessas considerações, a concepção de língua que adotamos se coaduna com aquela proposta pelo Funcionalismo, que defende os estudos de fenômenos linguísticos a partir da análise das estruturas em uso real, priorizando as relações que se estabelecem no contexto comunicativo. Igualmente importante, foi o estudo da estrutura argumental da oração, formada pelo verbo e seus selecionados elementos obrigatórios (argumentos). Com relação aos verbos que serão objeto da pesquisa, orientamo-nos pela classificação realizada por Azeredo (2004, p.180), baseada na proposta de estudo de Cano Aguilar (1981) para a língua espanhola, que arrolou o grupo de verbos codificadores de extensão ou escala no português, entre eles: atravessar, percorrer, subir, abraçar, presidir, contornar, ocupar, preencher, inundar, medir 1 (ele mediu um terreno), medir 2 (o terreno mede 160 m), valer e durar (a viagem durou 80 dias). Em nossa pesquisa, analisaremos a transitividade de um recorte desse grupo, composto pelos verbos subir, ocupar, medir, durar, valer e seu uso na língua portuguesa, que, juntamente com a escolha do referencial teórico, justificam a importância deste estudo, visto que esse fenômeno é mais bem observado em condições reais de comunicação. O corpus é constituído de textos do âmbito jornalístico escrito e o levantamento de dados foi realizado por meio de ferramenta de pesquisa on-line no acervo digital da Revista Veja. Esperamos que o resultado desta pesquisa evidencie que um estudo que tenha como ponto de partida a língua em uso vá muito além das proposições das gramáticas
The most of grammarians welcome verbs in two sessions, namely: the first that deals with morphological aspects, then within a syntactic-semantic perspective, which deals with verbs as the predication. This creates the problem of proposal analysis, given that when considering verbs as discrete elements in non-contextualized sentences, the relationships are not considered morphological, syntactic, semantic, pragmatic and discoursive that can only be observed from the language in use, in game combinatorial language. From these considerations, the design language we adopt is consistent with that proposed by functionalism, which advocates the study of linguistic phenomena from the analysis of the structures in actual use, prioritizing the relationships established in the communicative context. Equally important was the study of argument structure of sentence, formed by the verb and its selected elements required (arguments). With respect to verbs that will be the object of research, we look to the classification performed by Azeredo (2004, p.180), based on the study proposal of Cano Aguilar (1981) for the Spanish language, that enrolled a group of verbs encoders of extent or scale in Portuguese, among them: cross, roam, rise, embrace, preside, contour, occupy, fill, flood, measure 1 (he measured a piece of land), measure 2 (the land measures 160 m), earn and last (the trip lasted 80 days). In our research, we analyze the transitivity of a clipping of this group, consisting of the verbs rise, occupy, measure, last, earn and their use in the Portuguese language, which, together with the choice of theoretical, justify the importance of this study, since this phenomenon is best observed in real communication. The corpus is composed of texts within the journalistic writing and data collection was conducted through a research tool on-line in digital collection of Veja Magazine. We hope that the result of this research it is clear that a study has as starting point the language used go far beyond the propositions of grammars
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Simon, Camille. "Morphosyntaxe et sémantique grammaticale du salar et du tibétain de l'Amdo : analyse d'un contact de langues." Thesis, Sorbonne Paris Cité, 2016. http://www.theses.fr/2016USPCA124/document.
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La présente étude s’inscrit dans le cadre plus vaste de la description des langues de l’aire linguistique Amdo. Cette région est caractérisée par la présence de langues sinitiques, mongoliques, tibétiques et turciques et, pour le salar et le tibétain, une situation de contact linguistique long d’environ sept siècles. Le salar est l’une des langues turciques les moins décrites et elle présente de nombreuses particularités dues à son isolement par rapport aux autres langues turciques. Il n’existe pas non plus de description des variétés de tibétain parlées dans la région salarophone, périphérique dans la tibétosphère. La perspective que nous adoptons ici est donc à la fois descriptive et comparative. Après un exposé des caractéristiques historiques et sociolinguistiques de cette situation de contact, nous analysons de façon détaillée des catégories grammaticales indexées dans le syntagme nominal et dans le prédicat. En particulier, nous proposons une nouvelle analyse des morphèmes de Temps-Aspect-Mode en salar et montrons que cette langue a copié en partie ses catégories évidentielles sur le modèle de celles du tibétain de l’Amdo. Nous nous intéressons ensuite aux problématiques liées à la valence verbale et aux effets du contact linguistique sur l’organisation accusative et ergative qui caractérisent respectivement le salar et le tibétain de l’Amdo. Nous analysons les marques casuelles à la fois comme relateurs, au sein du prédicat verbal, mais également comme converbe ou au sein des formes converbiales. Enfin, nous décrivons les catégories de voix grammaticalisées en salar et en tibétain, et montrons que celles-ci sont quasiment identiques dans les deux languesThis study falls within the larger description of the languages of the Amdo linguistic area. This area is characterized by the coexistence of Sinitic, Mongolic, Tibetic and Turkic languages, and, regarding Salar and Tibetan, an approximately seven-century-long contact situation. Salar language remains one of the less described Turkic languages and, because of its isolation from the other Turkic languages, displays many specificities. There exists no description of the Amdo-Tibetan variety spoken in the Salar-speaking region either, this region being very peripheral in the Tibetosphere. The perspective taken in this study is thus both descriptive and comparative. After a depiction of the historical and sociolinguistic characteristics of this contact-situation, we analyse in detail the grammatical categories indexed in the nominal phrase and in the predicate. Notably, we suggest a new analysis of the Tense-Aspect-Mood morphemes in Salar and we show that the Amdo-Tibetan evidential categories have been partly copied in Salar. Then, the question of verb valency is addressed, and the effects of language contact on the Turkic accusative and on the Tibetic ergative organisation are explored. We analyze the case markers not only as markers of syntactic dependancy within the verb predicate, but also in their role as or in converbs. Finally, we describe the grammatical voices attested in Salar and in Amdo Tibetan, and show that the syntactic and semantic characteristics are almost identical in the two languages
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Khachaturyan, Maria. "Grammaire de la langue mano (mandé-sud) dans une perspective typologique." Thesis, Paris, INALCO, 2014. http://www.theses.fr/2014INAL0030/document.
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L’objectif de ce travail est de présenter une description grammaticale aussi complète que possible de la langue mano (près de 400 000 locuteurs en Guinée et au Libéria) tout en la plaçant dans un contexte typologique, en comparant le mano avec d’autres langues mandé, mais aussi en distinguant des particularités typologiques à un niveau plus large. Le texte de la thèse est divisé en six chapitres: Phonologie et phonétique; Morphologie; Groupe nominal; Groupe verbal; Système prédicatif; Syntaxe de l'énoncé. Justifiant l'orientation typologique de la thèse, chaque chapitre se conclut par une section présentant des caractéristiques typologiques. Les thèmes suivants ont été examinés en détail: étude quantitative de phonotactique, étude de la catégorie du nombre, y compris l’expression du nombre et l’accord en nombre ; le système des quantificateurs ; la structure argumentale ; l’étude de corpus de distribution des marqueurs prédicatifs ; la syntaxe de l’énoncé, notamment la syntaxe de l’énoncé relatif. Les annexes à la fin de la thèse représentent des compléments d'information importants, notamment les paradigmes verbaux complets. Deux de ces annexes sont des textes glosésThis work aims to present a grammatical description – as complete as possible – of a South Mande language, Mano (400,000 speakers in Guinea and Liberia), placing it into a typological context, comparing the language with other Mande languages and distinguishing general typological particularities. The text of the thesis is divided into six chapters: Phonology and phonetics; Morphology; Noun phrase; Verb phrase; Predicative system; Syntax of the clause. Justifying the typological orientation of the thesis, each chapter is concluded by a section providing typological particularities of the data presented in it. A detailed analysis was given, among others, on the following themes: quantitative study of phonotactics; study of the category of number, including its expression and alignment by number; the system of quantification markers; argument structure, corpus study of predicative markers’ distribution; syntax of the clause, especially syntax of the relative clause.The appendices at the end of the thesis contain some important complementary information, including, for instance, complete verbal paradigms. Two of these appendices comprise of glossed texts
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Henadeerage, Kumara, and kumara henadeerage@anu edu au. "Topics in Sinhala Syntax." The Australian National University. Faculty of Arts, 2002. http://thesis.anu.edu.au./public/adt-ANU20060426.142352.
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This study is a detailed investigation of a number of issues in colloquial
Sinhala morphosyntax. These issues primarily concern grammatical relations,
argument structure, phrase structure and focus constructions. The
theoretical framework of this study is Lexical Functional Grammar.¶Chapter
1 introduces the issues to be discussed, followed by a brief introduction
of some essential aspects of colloquial Sinhala as background for the
discussion in the following chapters. In Chapter 2 we present basic
concepts of the theoretical framework of Lexical Functional Grammar.¶ The
next three chapters mainly concern grammatical relations, argument
structure and clause structure in colloquial Sinhala. Chapter 3 examines
grammatical relations. The main focus lies in establishing the subject
grammatical relation in terms of various subjecthood diagnostics. We show
that only a very small number of diagnostics are reliable, and that the
evidence for subject is weaker than assumed previously. All the subjecthood
diagnostics that were examined select the most prominent argument in the
argument structure as the subject, i.e. 'logical subject'. However, there
appear to be no processes in the language that are sensitive to the subject
in the grammatical relations structure, i.e. 'gr-subject'. Further, there
is no evidence for other grammatical relations like objects. In Chapter 4
we discuss the agentless construction and related valency alternation
phenomena. It was previously assumed that the agentless construction,
valency alternation phenomena and the involitive construction are all
related. We argue that the agentless construction should be treated as a
different construction from the involitive construction. We also show that
the agentless construction and the involitive construction have contrasting
characteristics, and that treatment of them as separate constructions can
account for some phenomena which did not receive an explanation previously.
The valency alternation phenomena are related to the agentless
construction, therefore there is no valency alternation in involitive
constructions. It will be shown that verbs undergoing the valency
alternation can be distinguished from the other verbs in terms of the
lexical semantic properties of individual verbs. Chapter 5 examines the
structure of non-verbal sentences in terms of a number of morphosyntactic
phenomena. It was previously argued that verbal sentences and non-verbal
sentences in colloquial Sinhala differ in terms of clause structure.
However, the present study shows evidence to the contrary.¶ The next two
chapters deal with modelling contrastive focus and the phrase structure of
the language. Chapter 6 is a detailed analysis of the contrastive focus
(cleft) construction in various clause types in the language, and proposes
a unified syntactic treatment of contrastive focus. Contrastive focus is in
some constructions morphologically encoded, while in others it involves
both morphological and configurational assignment of focus. The complex
interaction between focus markers and verb morphology in various focus
constructions is accounted for by general well-formedness conditions
applying to the f-structure, and the principles of Functional Uncertainty
and Morphological Blocking. In Chapter 7, we discuss the phrase structure
of the language, in particular such issues as its non-configurational
nature and the lack of evidence for VP. We propose non-configurational S
and some functional projections to account for word order freedom under S
and to explain certain morphosyntactic phenomena, such as configurational
focus assignment. Finally, Chapter 8 summarises the conclusions made in
previous chapters.
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Balsan, Alain. "Valence au grand siècle /." Valence : E & R, 2000. http://catalogue.bnf.fr/ark:/12148/cb38805647c.
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Derr, Julien. "Valence, magnétisme et conduction dans les composés à valence intermédiaire : Le cas SmB6." Phd thesis, Université Joseph Fourier (Grenoble), 2006. http://tel.archives-ouvertes.fr/tel-00133598.
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Le composé SmB6 est un exemple typique de la physique étrange qui peut résulter d'un équilibre de valence. La première configuration du Samarium (Sm2+) correspond à un état isolant non magnétique alors que la seconde (Sm3+) donnerait théoriquement un état magnétique et conducteur. Des mesures de microcalorimétrie sous pression ont permis d'établir le diagramme de phase magnétique de SmB6 : une nouvelle phase magnétique ordonnée à longue distance a été mise en évidence pour des pressions supérieures à 10GPa. D'un autre coté, des mesures de transport réalisées sous pression hydrostatique permettent de situer la transition isolant-métal pour la même pression. Le diagramme de phase sous pression est désormais bien établi et l'observation pour la première fois d'une anomalie magnétique dans les courbes de résistivité au delà de 10GPa permet d'affirmer que la coïncidence des deux phénomènes a bien lieu. Ce changement de comportement du système est discuté dans un nouveau cadre théorique prenant en compte la température Kondo du réseau comme paramètre clef pour la renormalisation de la fonction d'onde vers l'une ou l'autre configuration de valence entière alors que la valence mesurée est toujours nettement intermédiaire. Cette idée générale semble par ailleurs s'appliquer à d'autres composés à valence intermédiaire étudiés (SmS, TmSe). En parallèle, des mesures de résistivité sous contraintes uniaxiales ont été réalisées. Elles mettent en évidence un fort effet d'anisotropie dans le composé SmB6. La comparaison de ces expériences avec les résultats obtenus dans des conditions de pression très hydrostatiques permettent de revisiter le problème de la nature du gap de SmB6.
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Davis, M. J. "Valence-Electron-Only Valence Bond calculations on the low lying states of Na-S." Thesis, University of Bristol, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.384414.
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Faraon, Montathar. "Valence asymmetry in impression formation." Thesis, Kristianstad University College, Department of Behavioural Sciences, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:hkr:diva-4402.
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Are implicit attitudes as easily formed as explicit attitudes? Fifty-four participants carried out an experiment regarding the behaviors of a fictional protagonist. Attitudes were obtained by the Implicit Association Test (IAT) and by explicit evaluations. The results in the current study showed tendency towards a significant persistence effect for explicit attitudes and a positivity bias effect for implicit attitudes.
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Gonen, Ozgur. "Modeling planar 3-valence meshes." Texas A&M University, 2007. http://hdl.handle.net/1969.1/85883.
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In architectural and sculptural practice, the eventual goal is constructing the
shapes that have been designed. Due to fabrication considerations, shapes with planar
faces are in demand for these practices.
In this thesis, a novel computational modeling approach to design constructible
shapes is introduced. This method guarantees that the resulting shapes are planar
meshes with 3-valence vertices, which can always be physically constructed using
planar or developable materials such as glass, sheet metal or plywood. The method
introduced is inspired by the traditional sculpture and is based on the idea of carving
a mesh by using slicing planes. The process of determining the slicing planes can
either be interactive or automated.
A framework is developed which allows user to sculpt shapes by using the in-
teractive and automated processes. The framework allows user to cut a source mesh
based on its edges, faces or vertices. The user can sculpt various kinds of developable
surfaces by cutting the parallel edges of the mesh. The user can also introduce in-
teresting conical patterns by cutting dierent vertex, edge, face combinations of the
mesh.
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Brown, Neil John. "Novel organometallic mixed valence complexes." Thesis, Durham University, 2010. http://etheses.dur.ac.uk/417/.
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Organometallic mixed valence complexes have been studied extensively over the past 30 years providing many synthetic and theoretical challenges. This thesis has sought to provide the field with a unique family of mixed valence complexes through which theories of electron transfer in weakly coupled systems can be tested. The metal fragment Mo(dppe)(η7-C7H7) is unique amongst its half-sandwich counterparts providing low formal oxidation states and a well resolved EPR signal and forms the basis of these studies. Before undertaking a study of the electronic structure of [{(Mo(dppe)(η7-C7H7)}2{μ- C≡CXC≡C}]n+ systems, and associated issues regarding mixed valence characteristics and carbon-chain mediated metal-metal interactions, mono-metallic molybdenum acetylide complexes that serve as model systems were studied in detail and their electronic structure fully rationalised. Thus, in Chapter two, a range of para substituted molybdenum aryl acetylides, Mo(C≡CC6H4X-4)(dppe)(η7-C7H7), featuring a range of electron-donating and -withdrawing substituents, are described. These compounds have been studied using a range of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and computational techniques establishing metal centred oxidation character. This is a consequence of cycloheptatrienyl ring destabilising the filled dz2 metal d-orbtial which then forms the HOMO. The poor symmetry match of this dz2 orbital and the alkynyl π-system effectively decouples the molybdenum fragment from the alkynyl substituent. As a precursor to the synthesis and understanding of bi-metallic complexes containing all-carbon bridging moieties, a series of mono-metallic compounds containing diynyl and triynyl ligands have been studied in Chapter three. The subsequent elucidation of the influence of the length of the carbon chain on the electronic structure has been studied using a combination of spectroelectrochemical and computational techniques. These studies reveal that the length of the carbon chain, and the identity of the supporting ligand, (bipyridine or dppe) increases the chain character of the frontier orbitals. Homo-bimetallic complexes containing a bis(ethynyl) substituted para-carborane bridging moiety were synthesised (Chapter four) together with the monometallic complex Mo(C≡CC2B10H11)(dppe)(η7-C7H7). The mono-metallic complex was first synthesised and studied to establish how the ethynyl carborane affects the electronic structure of the Mo(dppe)(η7-C7H7) centre and the nature of interaction between the molybdenum centre, the ethynyl fragment and the carborane cage. This preliminary work was followed by the synthesis of the bimetallic complex, [{Mo(dppe)(η7- C7H7)}2{μ-C≡C(C2B10H10)C≡C}]. Using a range of spectroscopic, spectroelectrochemical and computational techniques the electronic structure, and charge transfer process of [{Mo(dppe)(η7-C7H7)}2{μ-C≡C(C2B10H10)C≡C}]n+ (n = 0, 1 or 2) have been explored. The monocation [{Mo(dppe)(η7-C7H7)}2{μ- C≡C(C2B10H10)C≡C}]+ has shown to be a genuine example of a valence trapped, weakly coupled mixed valence complex allowing conventional descriptions of the intervalence transition to be compared with TD-DFT based interpretations. The literature surrounding the area of poly-carbon ligand chemistry indicates that the butadiyndiyl bridging moiety is an efficient conduit for electron transfer, due to its two orthogonal π-systems that span across the entirety of the ligand, leading to systems which are generally delocalised. An investigation of the mixed valence complex, [{Mo(dppe)(η7-C7H7)}2(μ-C≡CC≡C)]+ reveals a weakly coupled, localised mixed valence electronic structure, which is unique amongst its poly-carbon counterparts (Chapter five). Through using a range of spectroscopic timescales (EPR /IR /UV /vis) the rate of electron transfer has been estimated. To fully account for the number of transitions in the NIR region and the shape of the resulting absorption bands, it is necessary to employ a three state approximation (which explicity indicates the bridge state) when describing the electron transfer process. The complex [{Mo(dppe)(η7-C7H7)}2{μ-C≡C(C6H4)C≡C}]n+ has been studied using a range of spectroscopic, electrochemical and computational methods to establish the nature and rate of electron transfer of the mixed valence complex (Chapter six). It has been demonstrated that the 1,4-diethynylbenzene bridge mixes more efficiently with the Mo(dppe)(η7-C7H7) than the 1,3-butadiyndiyl bridge. Spectroscopic analysis revealed a moderately coupled, localised mixed valence complex, where the rate of electron transfer is much faster than the diynyl complex but not faster than the infrared spectroscopy timescale. The application of the three state model in the description of the charge transfer process allows the increased electron transfer rate to be explained through the increased mixing of the bridge with the Mo(dppe)(η7-C7H7) moiety, characterised by the lowering of the LMCT transition in comparison to carboranyl and diynyl containing complexes. Metal complexes containing the cyanoacetylide moiety, C≡CC≡N, have been known for several decades, but despite the obvious synthetic advantages of cyanoacetylide as a bridging moiety compared to a butadiyndiyl bridge, C≡CC≡C, the C≡CC≡N ligand has been largely ignored. Chapter seven summarises attempts made to provide a convenient route to complexes containing the cyanoacetylide moiety so that a greater variety bimetallic complexes can be synthesised, thus allowing the investigation of the charge transfer characteristics of [{LxM}(μ-C≡CC≡N){MLx}]n+ complexes. Reactions of cyanogen bromide with metal acetylide complexes yield novel mono- and di- bromovinylidenes rather than cyano containing complexes. The cyanation reagent of choice is 1-cyano-4-dimethylaminopyridinium tetrafluoroborate ([CAP]BF4) which allows the ready synthesis of mono- and di-cyanovinylidenes, as well as the synthesis of cyanoacetylide containing complexes. The cyanating agent [CAP]BF4 is able to cyanate a range of metal acetylides, thus expanding the number of potential bimetallic complexes. The hetero-bimetallic complex [{Fe(dppe)(η5-C5H5)}(μ- C≡CC≡N){Mo(dppe)(η7-C7H7)}]PF6 has been synthesised and studied using a range of techniques and has demonstrated that the cyanoacetylide bridge promotes a more delocalised electronic structure for dicationic complexes than is found for the other ethynyl based ligands described in this thesis.
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MINGUEZ, RUBIO RAMON. "L'affaire Dreyfus à Valence (Espagne)." Dijon, 1989. http://www.theses.fr/1989DIJOL001.
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La première partie est un rappel des données historiques, du contexte espagnol, elle insiste sur la spécificité de Valence (tradition républicaine, effervescence d'une presse diversifiée) qui est un terrain privilégié pour l'appropriation du modèle français. La deuxième partie est consacrée à l'analyse de la presse. Une fiche signalétique est consacrée à chacun des journaux dont la tendance idéologique est dégagée et mise en relation avec les groupes et les fractions politiques. Par ailleurs, la liste de tous les articles parus sur l'affaire Dreyfus est donnée par journal et par ordre chronologique. La dernière partie montre comment Valence se mobilise dans un climat passionnel, à propos de "l'affaire" et comment chaque journal est amené à définir sa conception de la société : ainsi s'opèrent des glissements et des regroupements. L'analyse des réactions face au problème juif, à l'église, à l'armée et à la république permet de cerner la question et de démontrer que se développent les pôles extrêmes, en suivant la dichotomie dreyfusards antidreyfusards, au détriment des positions modérées. L'affaire Dreyfus determine une recomposition du paysage politique valencienThe first part is a reminder of the historical facts, and of the Spanish context. It emphasizes the specificity of Valence, (the republican tradition, the effervescence of a diversified press) which is a privileged terrain for the appropriation of a French model. The second part is dedicated to an analysis of the press. Each of the newspapers is presented in turn, giving its ideological tendency in relation with political groups and factions. Likewise, the list of all the articles which appeared on the Dreyfus affair is classified by newspapers and in chronological order. The last part shows the passionate reaction of Valence to the Dreyfus affair and how each newspaper and political group was led to define its conception of society, thus operating shiftings and regroupings. An analysis of the various reactions to the Jewish problem, to the church, to the army and the republic leads to a closer interpretation of the problem. It is found that two extremes developed through the Dreyfus affair, defined by the dichotomy Dreyfusards anti-Dreyfusards, to the detriment of the moderates. Thus a new political landscape appeared in valence