Nanopartículas de ouro são \"blocos de construção\" muito versáteis para a preparação de novos nanomateriais híbridos funcionais. Suas propriedades físico-químicas permitem a criação de sistemas capazes de absorver luz, transportar elétrons ou, ainda, interagir com moléculas e biomoléculas. Nesta tese foram estudados os fatores que influenciam o Espalhamento Raman Intensificado pela Superfície (SERS), visando o aumento da sensibilidade da técnica pela formação de compósitos com nanopartículas magnéticas, além de explorar a estratégia de montagem coordenativa para a preparação de nanomateriais híbridos contendo complexos de rutênio visando o desenvolvimento de sensores para moléculas e/ou íons moleculares. Assim, foi demonstrado como é possível aumentar o sinal de espalhamento Raman obtido em pelo menos 30%, através do controle da relação número de moléculas/ nanopartícula de ouro. Ou seja, verificou-se que a melhor relação sinal ruído foi alcançado com cerca de 16 mil moléculas de fenantrolina por nanopartícula de ~42 nm, gerando espectros mais definidos e sem a presença de bandas indesejáveis, por exemplo associadas aos agentes estabilizantes. Essa propriedade das nanopartículas de ouro foi potencializada por meio da associação com nanopartículas superparamagnéticas de óxido de ferro gerando substratos SERS sensíveis, reprodutíveis, de preparação simples e baratos. A interação entre as nanopartículas de ouro e as nanopartículas superparamagnéticas foram monitoradas por espectroscopia eletrônica no ultravioleta-visível, microscopias eletrônicas de varredura e de transmissão e microscopias de campo escuro e hiperespectral. Verificou-se que as nanopartículas interagem fortemente entre si gerando materiais supramoleculares que podem ser atraídas e concentradas utilizando-se um imã, para a realização de medidas de espectroscopia Raman/SERS. Essa nova metodologia e substrato SERS possibilitaram a quantificação de azul de metileno e de fenantrolina em concentrações na faixa de 5x10-9 a 5x10-11 mol dm-3. De fato, foi observado um aumento do sinal Raman de até 60 vezes, quando comparado ao sinal sem a concentração magnética. Finalmente, a interação das nanopartículas de ouro com três diferentes clusters trigonais de acetato de rutênio (ou, simplesmente, clusters de rutênio) simétricos, com os ligantes 4-cianopiridina, 4,4\'-bispiridina e trans-1,2-bis(4-piridil)etileno como substituintes axiais foi explorado para a preparação de polímeros de coordenação funcionais. Os clusters de rutênios foram caracterizadas por espectroscopia eletrônica no ultravioleta-visível, eletroquímica e espectroeletroquímica. A seguir os clusters de rutênio foram utilizados como \"réguas molecular\", explorando a diferença de tamanho e o fato delas funcionarem como \"moléculas-pontes\", para a realização de estudos de acoplamento plasmônico, acompanhando-se tal fenômeno por espectroscopia eletrônica no ultravioleta-visível. A interação entre as nanopartículas de ouro e os clusters de rutênio puderam ser estudadas por espectroscopia de ressonância plasmônica de superfície (SPR), onde foi investigado o processo de formação de filmes por meio da técnica. Estes foram caracterizados por espectroscopia Raman utilizando lasers de excitação de 532 e 785 nm, onde foram observados as bandas vibracionais dos clusters de rutênio e as contribuições ressonante, eletromagnética e de transferência de cargana intensificação Raman. Esses nanomateriais híbridos foram ainda imobilizados sobre eletrodos de vidro condutor e utilizados como sensores eletroquímicos para detecção de nitrito na faixa de concentrações entre 0,5x10-6 e 1x10-3 mol dm-3. / Gold nanoparticles are \"building blocks\" very versatile for the preparation of new functional hybrid nanomaterials . Their physicochemical properties allow the creation of systems capable of absorbing light, electron transportation, or even interact with molecules and biomolecules. In this thesis we studied the factors that influence the surface enhanced Raman scattering (SERS), in order to increase the sensitivity of the technique by forming composites with magnetic nanoparticles, as well as explore the coordinative assembly strategy for the preparation of hybrid nanomaterials containing complexes ruthenium for the development of sensors for molecules and/or molecular ions . Thus, it was shown how is possible to increase the Raman signal obtained by at least 30 % just controlling the relative number of molecules/gold nanoparticle. That is, it was found that the best signal to noise ratio was achieved with about 16 thousand of molecules per nanoparticle ~ 42 nm, more defined and generating spectra without the presence of undesirable bands, for example, associated with stabilizers. This property of gold nanoparticles was enhanced by association with superparamagnetic nanoparticles of iron oxide generating sensitive SERS substrates, reproducible, with simple preparation methodology and inexpensive. The interaction between the gold nanoparticles and superparamagnetic nanoparticles were monitored by electronic spectroscopy in the ultraviolet -visible, scanning electron microscopy and transmission electron microscopy and dark field and hyperspectral microscopy. It was found that the nanoparticles interact strongly which can be attracted and concentrated using a magnet for the realization of Raman spectroscopy measurements / SERS. This new methodology, and SERS substrate, allowing the quantification of methylene blue concentrations and phenantroline in the range of 5x10-9 to 5x10-11 mol dm-3. In fact , we observed an increase in the Raman signal up to 60 times when compared to the signal without the magnetic concentration. Finally, the interaction of gold nanoparticles with three different clusters trigonal ruthenium acetate (or simply ruthenium clusters) symmetrical with the ligand 4- cyanopyridine, 4,4\'-bispiridina and trans-1,2-bis(4-pyridyl) ethylene axial been explored as substituents for the preparation of functional coordination polymers. Ruthenium Clusters were characterized by electron spectroscopy in the ultraviolet-visible, electrochemical and spectroelectrochemical. After that, the ruthenium clusters were used as \"molecular rulers\", exploring the size difference and the fact that they can act as \" molecules-bridges \" for studies of plasmon coupling, following up this phenomenon by electronic spectroscopy in the ultraviolet - visible. The interaction between the gold nanoparticles and ruthenium clusters could be studied by spectroscopy, surface plasmon resonance (SPR), where it investigated the process of formation of films by the technique. These were characterized by Raman spectroscopy using laser excitation of 532 and 785 nm, which were observed vibrational bands of ruthenium clusters and contributions resonant electromagnetic and transfer cargana Raman enhancement. These hybrid nanomaterials were also immobilized on glass electrodes and conductive used as electrochemical sensors for the detection of nitrite concentrations in the range of 0.5 x10-6 to 1x10-3 mol dm-3.

This thesis is concerned with the study of biomedical scientific research work that is intensely distributed, i.e. socially distributed across multiple institutions, sites, and disciplines. Specifically, this PhD probes the ways in which scientists co-operating on multi-sited crossdisciplinary projects, design, use and maintain information-based resources to conduct and coordinate their experimental activities. The research focuses on the roles of information artefacts, i.e. the tools, media and devices used to store, track, display, and retrieve information in paper or electronic format, in helping the scientists integrate their activities to achieve concerted action. To examine how scientists in globally distributed settings organise and co-ordinate their scientific work using information artefacts, a multi-method multi-sited study informed by different ethnographic perspectives was conducted focused on a large European crossdisciplinary translational research project in nanodiagnostics. Situated interviews with project scientists, participant observations and participatory learning exercises were designed and deployed. From the data analysis, several abstractions were developed to represent how the joined utilisations of key information artefacts support the co-ordination of experimental activities. Subsequently, a framework was developed to highlight key interactional strategies that need to be managed by experimenters when using artefacts to organise their work cooperatively. This framework was then used as a guiding device to identify innovative ways to design future digital interactive systems to support the co-ordination of intensely distributed scientific work. From this study, several key findings came to light. We identify the role of the experimental protocol acts as a co-ordinative map that is co-designed dynamically to disseminate various instantiations of experimental executions across sites. We have also shed light on the ways the protocol, the lab book and the material log are used jointly to support the articulation of scientific work. The protocol and the lab book are used both locally and across co-operating sites to support four repeatability and reproducibility levels that are key to experimental validation. The use of the local protocol / lab book dyads at each site is further integrated with that of a centralised material log artefact to enable a system of exchange of scientific content (e.g. experimental processes, intermediate results and observations) and experimental materials (both physical materials and key information). We have found that this integration into a co-ordinative cluster supports awareness and the articulation of experimental activities both locally and across remote labs. From this understanding, we have derived several sensitising tensions to frame the strategies that scientific practitioners need to manage when designing their multi-sited experimental work and technologists should consider when designing systems to support them: (1) formalisation / flexibility; (2) articulability / local appropriateness; (3) scrutiny / tinkering; (4) accountability / applicability; (5) traceability / improvisation and (6) lastingness / immediacy. Lastly, based on these tensions, we have suggested a number of implications for the design of interactive information artefacts that can help manage both local and multi-sited co-ordination in intensely distributed scientific projects.

Nanopartículas de ouro são \"blocos de construção\" muito versáteis para a preparação de novos nanomateriais híbridos funcionais. Suas propriedades físico-químicas permitem a criação de sistemas capazes de absorver luz, transportar elétrons ou, ainda, interagir com moléculas e biomoléculas. Nesta tese foram estudados os fatores que influenciam o Espalhamento Raman Intensificado pela Superfície (SERS), visando o aumento da sensibilidade da técnica pela formação de compósitos com nanopartículas magnéticas, além de explorar a estratégia de montagem coordenativa para a preparação de nanomateriais híbridos contendo complexos de rutênio visando o desenvolvimento de sensores para moléculas e/ou íons moleculares. Assim, foi demonstrado como é possível aumentar o sinal de espalhamento Raman obtido em pelo menos 30%, através do controle da relação número de moléculas/ nanopartícula de ouro. Ou seja, verificou-se que a melhor relação sinal ruído foi alcançado com cerca de 16 mil moléculas de fenantrolina por nanopartícula de ~42 nm, gerando espectros mais definidos e sem a presença de bandas indesejáveis, por exemplo associadas aos agentes estabilizantes. Essa propriedade das nanopartículas de ouro foi potencializada por meio da associação com nanopartículas superparamagnéticas de óxido de ferro gerando substratos SERS sensíveis, reprodutíveis, de preparação simples e baratos. A interação entre as nanopartículas de ouro e as nanopartículas superparamagnéticas foram monitoradas por espectroscopia eletrônica no ultravioleta-visível, microscopias eletrônicas de varredura e de transmissão e microscopias de campo escuro e hiperespectral. Verificou-se que as nanopartículas interagem fortemente entre si gerando materiais supramoleculares que podem ser atraídas e concentradas utilizando-se um imã, para a realização de medidas de espectroscopia Raman/SERS. Essa nova metodologia e substrato SERS possibilitaram a quantificação de azul de metileno e de fenantrolina em concentrações na faixa de 5x10-9 a 5x10-11 mol dm-3. De fato, foi observado um aumento do sinal Raman de até 60 vezes, quando comparado ao sinal sem a concentração magnética. Finalmente, a interação das nanopartículas de ouro com três diferentes clusters trigonais de acetato de rutênio (ou, simplesmente, clusters de rutênio) simétricos, com os ligantes 4-cianopiridina, 4,4\'-bispiridina e trans-1,2-bis(4-piridil)etileno como substituintes axiais foi explorado para a preparação de polímeros de coordenação funcionais. Os clusters de rutênios foram caracterizadas por espectroscopia eletrônica no ultravioleta-visível, eletroquímica e espectroeletroquímica. A seguir os clusters de rutênio foram utilizados como \"réguas molecular\", explorando a diferença de tamanho e o fato delas funcionarem como \"moléculas-pontes\", para a realização de estudos de acoplamento plasmônico, acompanhando-se tal fenômeno por espectroscopia eletrônica no ultravioleta-visível. A interação entre as nanopartículas de ouro e os clusters de rutênio puderam ser estudadas por espectroscopia de ressonância plasmônica de superfície (SPR), onde foi investigado o processo de formação de filmes por meio da técnica. Estes foram caracterizados por espectroscopia Raman utilizando lasers de excitação de 532 e 785 nm, onde foram observados as bandas vibracionais dos clusters de rutênio e as contribuições ressonante, eletromagnética e de transferência de cargana intensificação Raman. Esses nanomateriais híbridos foram ainda imobilizados sobre eletrodos de vidro condutor e utilizados como sensores eletroquímicos para detecção de nitrito na faixa de concentrações entre 0,5x10-6 e 1x10-3 mol dm-3. / Gold nanoparticles are \"building blocks\" very versatile for the preparation of new functional hybrid nanomaterials . Their physicochemical properties allow the creation of systems capable of absorbing light, electron transportation, or even interact with molecules and biomolecules. In this thesis we studied the factors that influence the surface enhanced Raman scattering (SERS), in order to increase the sensitivity of the technique by forming composites with magnetic nanoparticles, as well as explore the coordinative assembly strategy for the preparation of hybrid nanomaterials containing complexes ruthenium for the development of sensors for molecules and/or molecular ions . Thus, it was shown how is possible to increase the Raman signal obtained by at least 30 % just controlling the relative number of molecules/gold nanoparticle. That is, it was found that the best signal to noise ratio was achieved with about 16 thousand of molecules per nanoparticle ~ 42 nm, more defined and generating spectra without the presence of undesirable bands, for example, associated with stabilizers. This property of gold nanoparticles was enhanced by association with superparamagnetic nanoparticles of iron oxide generating sensitive SERS substrates, reproducible, with simple preparation methodology and inexpensive. The interaction between the gold nanoparticles and superparamagnetic nanoparticles were monitored by electronic spectroscopy in the ultraviolet -visible, scanning electron microscopy and transmission electron microscopy and dark field and hyperspectral microscopy. It was found that the nanoparticles interact strongly which can be attracted and concentrated using a magnet for the realization of Raman spectroscopy measurements / SERS. This new methodology, and SERS substrate, allowing the quantification of methylene blue concentrations and phenantroline in the range of 5x10-9 to 5x10-11 mol dm-3. In fact , we observed an increase in the Raman signal up to 60 times when compared to the signal without the magnetic concentration. Finally, the interaction of gold nanoparticles with three different clusters trigonal ruthenium acetate (or simply ruthenium clusters) symmetrical with the ligand 4- cyanopyridine, 4,4\'-bispiridina and trans-1,2-bis(4-pyridyl) ethylene axial been explored as substituents for the preparation of functional coordination polymers. Ruthenium Clusters were characterized by electron spectroscopy in the ultraviolet-visible, electrochemical and spectroelectrochemical. After that, the ruthenium clusters were used as \"molecular rulers\", exploring the size difference and the fact that they can act as \" molecules-bridges \" for studies of plasmon coupling, following up this phenomenon by electronic spectroscopy in the ultraviolet - visible. The interaction between the gold nanoparticles and ruthenium clusters could be studied by spectroscopy, surface plasmon resonance (SPR), where it investigated the process of formation of films by the technique. These were characterized by Raman spectroscopy using laser excitation of 532 and 785 nm, which were observed vibrational bands of ruthenium clusters and contributions resonant electromagnetic and transfer cargana Raman enhancement. These hybrid nanomaterials were also immobilized on glass electrodes and conductive used as electrochemical sensors for the detection of nitrite concentrations in the range of 0.5 x10-6 to 1x10-3 mol dm-3.

Αντικείμενο μελέτης της παρούσας εργασίας αποτελεί ο βαθμός επιρροής της κεφαλής κατά την ανάγνωση παρατακτικών συνθέτων από ασθενείς με neglect dyslexia (ND). Ενώ η πλειοψηφία των συνθέτων της ελληνικής, τα επονομαζόμενα ‘υποτακτικά’ (subordinative compounds), υπακούουν στον νόμο της δεξιόστροφης κεφαλής (Williams, 1981) (π.χ. ελαφο-κυνηγός), τα παρατακτικά σύνθετα (coordinative compounds) δεν εμφανίζουν αυτή την κανονικότητα στη θέση της κεφαλής τους (π.χ αλατο-πίπερο). Κάποιοι θεωρητικοί μορφολόγοι θεωρούν ότι κανένα από τα δύο συστατικά δεν αποτελεί τη βάση του συνθέτου, ούτε μορφολογικά ούτε σημασιολογικά (Ralli, 2005: 174), άλλοι υποστηρίζουν ότι τα παρατακτικά εμφανίζουν δύο κεφαλές, τόσο στο α’ όσο και στο β’ συνθετικό (Kageyama, 2009), ενώ δεν λείπουν και αυτοί που επιχειρηματολογούν για την υπεροχή του δεύτερου συστατικού, λόγω του ότι αυτό καθορίζει το γένος, τον αριθμό και την πτώση των συνθέτων (Guevara & Scalise, 2008). Στο πλαίσιο αυτό, θα προσπαθήσουμε να απαντήσουμε στο ερώτημα της θεωρητικής μορφολογίας σχετικά με τη θέση της κεφαλής στα παρατακτικά [ΟΟ] και [ΕΕ] σύνθετα της Νέας Ελληνικής, καθώς και στο ερώτημα της κλινικής γλωσσολογίας σχετικά με το ρόλο της κεφαλής στην ανάκληση και επεξεργασία των συνθέτων από ασθενείς με neglect dyslexia. Ένα ιδιαίτερα σημαντικό χαρακτηριστικό των ασθενών με ND είναι η ικανότητά τους να αναγνωρίζουν και να σέβονται τα όρια των δύο συστατικών κατά την ανάγνωση των συνθέτων (Behrmann et al., 1990). Επιπλέον, οι Semenza et al. (2011) αναφέρουν για τα Ιταλικά ότι τα λάθη στο α’ συνθετικό είναι πολύ πιο συχνά στα σύνθετα των οποίων η κεφαλή συμπίπτει με το β’ συνθετικό, παρά όταν συμπίπτει με το πρώτο. Ο εξισορροπητικός ρόλος της κεφαλής ως προς την εμφάνιση λαθών πάνω στο συστατικό της, αναμένουμε να έχει αντίκτυπο και στη δική μας περίπτωση: τα υποτακτικά σύνθετα με την κεφαλή στα δεξιά θα πρέπει να εμφανίζουν περισσότερα λάθη στο α’ συνθετικό από τα παρατακτικά, εφόσον τα τελευταία έχουν δύο κεφαλές. Στο πείραμα ανάγνωσης που σχεδιάσαμε, συμπεριλάβαμε 31 παρατακτικά σύνθετα, ονοματικά και επιθετικά (π.χ. ψωμοτύρι ‘bread-cheese’ και κοντόχοντρος αντιστοίχως) και 32 υποτακτικά σύνθετα, επίσης ονοματικά και επιθετικά (π.χ. ερημονήσι και χοντροαλεσμένος αντιστοίχως), τα οποία είχαμε ελένξει ως προς όλες τις σημαντικές ψυχογλωσσολογικές και μορφολογικές παραμέτρους ανά γραμματική κατηγορία. Το πείραμα αυτό το διεξάγαμε σε μία ασθενή 79 ετών, η οποία έχει υποστεί ΔΕ αγγειακό εγκεφαλικό επεισόδιο (ΑΕΕ) και με βάση την επίδοσή της στο BELLS test έχει διαγνωσθεί με left-sided neglect dyslexia. Ενώ στα παρατακτικά σύνθετα της ονοματικής κατηγορίας, η ασθενής τείνει να παραλείπει ή να υποκαθιστά το α΄συστατικό των συνθέτων αυτών εξίσου συχνά με αυτό των υποτακτικών, δεν ισχύει το ίδιο και για τα επιθετικά παρατακτικά, κατά την ανάγνωση των οποίων ο ασθενής κάνει στατιστικά σημαντικά λιγότερα λάθη στο α’ συστατικό απ’ ότι στην ανάγνωση των αντίστοιχων υποτακτικών ( x²= 3.970, p < 0.05). Η συμβολή της παρούσας μελέτης μπορεί να συνοψιστεί στα ακόλουθα σημεία: Πρώτον, αποδεικνύεται ότι οι λεξικοί παράγοντες μπορούν να επηρεάσουν την επιλεκτική προσοχή σε μεγάλο βαθμό. Δεύτερον, παρέχονται τεκμήρια ότι η θεωρητική έννοια της κεφαλής έχει επίδραση στην επεξεργασία των συνθέτων, καθώς η εστίαση της προσοχής επηρεάζεται από και επικεντρώνεται στο συστατικό που λειτουργεί ως κεφαλή, έπειτα από την σιωπηρή ανάγνωση ολόκληρης της λέξης. Τρίτον, ως προς την επίδραση της κεφαλής στα παρατακτικά σύνθετα της ΚΝΕ, από την έρευνά μας προκύπτει ότι ένας διαχωρισμός ανάμεσα στα ονοματικά και τα επιθετικά παρατακτικά σύνθετα, με τα πρώτα να συμπεριφέρονται όπως τα υποτακτικά, ενώ τα δεύτερα να εμφανίζουν μια διευκόλυνση στην ανάγνωση ως απόρροια της ύπαρξης δύο κεφαλών. Στην τελευταία αυτή περίπτωση, ίσως η ανάγνωση επηρεάζεται από την δυνατότητα εναλλαγής της σειράς των όρων ορισμένων επιθετικών παρατακτικών συνθέτων (π.χ. μακρόστενος ~ στενόμακρος), αλλά αυτό είναι κάτι που απαιτεί περαιτέρω μελέτη. / Reading coordinative compound words is investigated in neglect dyslexia in order to assess the influence of ‘headedness’. While the majority of Modern Greek compounds, the so called ‘subordinative compounds’, comply with Williams’ (1981) ‘Righthand Head Rule’ (e.g. elafo-kinigos ‘deer-hunter’), coordinative compounds do not demonstrate clear headedness (e.g. alato-pipero ‘salt-pepper’). Some theoretical morphologists argue that none of the two constituents serves as the basis of the formation, neither morphologically nor semantically (Ralli, 2005: 174), others attest that the formations’ head coincides with their second constituent, because of the second’s constituent inflectional suffix which determine the gender, number and case of the compound (Guevara & Scalise, 2008), while others argue that coordinative compounds are double-headed (Kageyama, 2009). In this context, the theoretical morphology’s question regarding the position of the head in coordinative [NN] and [AA] Greek compounds will be addressed, as well as the question about the function of headedness in compounds’ retrieval and processing by patients suffering from neglect dyslexia. When reading compounds in neglect dyslexia, a common finding is that patients seem to respect the boundaries between the first and the second component (Behrmann et al., 1990). Moreover, Semenza et al. (2011) ascertained that left-headed Italian compounds are read better than right-headed compounds, indicating that the appearance of head on the first constituent, counterbalance the deficit at the processing of this first constituent. According to these findings, it seems reasonable to hypothesize that, if coordinative compounds are indeed headless or double-headed, patients with neglect dyslexia will make fewer mistakes in reading their left constituents compared to subordinative compounds, which have a clear head. A female 79-year old patient, who suffered RH damage and was affected by left-sided neglect dyslexia as diagnosed based on BELLS test, had to read 32 subordinative [NN] and [AA] compounds (e.g. domatosalata ‘tomato-salad’ and piknokatikimenos ‘densely populated’ respectively) and 32 coordinative [NN] and [AA] compounds (e.g. psomotiri ‘bread-cheese’ and glikopikros ‘sweet-bitter’ respectively). Compounds and their constituents were matched for frequency, familiarity, imageability, age of acquisition and orthographic neighbors. Patient performed significantly fewer substitution and omission errors on the left constituent of coordinative compounds when reading compound adjectives (x²= 3.970, p < 0.05), but the same amount of errors in subordinative and coordinative compounds when reading compound nouns. The contribution of the study can be summarized in the following points: First, it showed that lexical factors can influence selective attention to a great extent. Second, it showed that the theoretical concept of headedness does have a processing effect, with the head capturing more attention after implicit reading of the whole word. Third, as for headedness in Greek coordinative compounds, the study revealed a dissociation depending on grammatical class (adjectival vs. nominal compounds) with adjectival coordinative compounds behaving as double-headed while nominal coordinative compounds patterning with subordinative ones. A key factor here might be the interchangeable word order that characterizes adjectival coordinative compounds (e.g makrostenos ‘long-narrow’ ~ stenomakros ‘narrow-long’), but this is something that requires further research.

Depuis plusieurs années, les quadruplexes de guanine ou G4, structures particulières de l’ADN, suscitent un intérêt grandissant. Ces structures, largement étudiées in vitro, sont encore peu connues in vivo mais semblent jouer un rôle important dans la régulation de l’expression génétique. Elles ont rapidement été considérées comme des cibles thérapeutiques potentielles pour certaines maladies telles que le cancer. Le premier indice de leur existence dans les cellules n’a été obtenu qu’en 2013 par immunodétection sur des cellules fixées. Les recherches sont actuellement tournées vers le développement de nouveaux outils moléculaires qui permettraient la visualisation des G4 dans des cellules vivantes.C’est dans ce cadre que nous avons conçu et développé une série de complexes polyazaaromatiques de ruthéniumII à base de ligands plans étendus (heptacycle dpqp et octacycle dppqp). La combinaison des propriétés photophysiques des complexes de RuII associée à la présence d’un large plan étendu devant permettre l’interaction avec les G4, positionne ces molécules comme outils potentiels pour l’étude des G4 in vivo.La première partie de ce projet porte sur la synthèse de ces nouveaux complexes de ruthénium. Une méthode originale de "chimie sur complexe" a permis d'obtenir, entre autres, un complexe possédant le ligand dpqp, fonctionnalisé par une triple liaison. Il a également été possible, « par chimie sur complexe », de construire un cycle supplémentaire sur le ligand heptacyclique (dpqp) chélaté pour obtenir les complexes [Ru(L)2dppqp]2+. Les propriétés photophysiques des différents complexes ont été étudiées. Seuls deux complexes, [Ru(phen)2dpqp-Cl]2+ et [Ru(TAP)2dpqp-Cl]2+, présentent un comportement s’approchant de celui des complexes de référence; c’est à dire des rendements quantiques comparables à [Ru(bpy)3]2+ et des durées de vie de l’état excité de l’ordre de la centaine de nanosecondes. Les autres complexes sont non luminescents et l’hypothèse d’un quenching par transfert de proton à l’état excité a été avancée pour expliquer ce comportement.Les complexes ont aussi été évalués vis à vis de différentes structures oligonucléotidiques G4 et duplexes. Tous les complexes possèdent une affinité correcte envers les G4. Comme nous l'espérions, le complexe porteur du ligand octacyclique semble être particulièrement sélectif envers les G4 par rapport à l'ADN double brin. Il a aussi été montré que deux des complexes testés peuvent être utilisés comme sondes moléculaires "light-switch ON" pour les structures G4 en milieu cellulaire. Certains des complexes synthétisés sont donc d’excellents candidats en tant qu’outils moléculaires pour l’étude des G4 in vivo. / The interest for some unusual structures of DNA, the G4 quadruplexes was growing these past few years. Those structures were extensively studied in vitro, but a lot remains unkwown about their existence in vivo. Intererstingly, G4 structures seem to play key regulatory roles in gene expression and are therefore potential therapeutic targets for diseases such as cancer. Consequently, visualisation of those structures in cells is the present challenge today, and the use of small molecules with luminescent properties is promising in this context.In this framework, we designed a series of new rutheniumII complexes chelating a large planar aromatic ligand, (heptacycle dpqp or octacycle dppqp). The combination of the photophysical properties of RuII complexes with proposed favorable stacking properties of the ligand with G4, would make these complexes promising molecular tools for G4 visualization.The first part of this project focusses on the synthesis of ruthenium complexes and their specific ligands. One particular ligand is formed by the condensation between acridine and phenanthroline moieties. A chemistry on the complex approach enabled us 1) to functionnalize the chelated ligand by a triple bond that will be used for the formation of an heterodimer by click chemistry, and 2) to build an additional cycle on the chelated ligand. Photophysical properties were evaluated and only two complexes, [Ru(phen)2dpqp-Cl]2+ and [Ru(TAP)2dpqp-Cl]2+, exhibit the same photophysical behaviour than the reference complexes. Indeed, the quantum yields are in the same order of magnitude than for [Ru(bpy)3]2+ and the excited state lifetime are of a few hundred nanosecondes. The other complexes are non-luminescent and a quenching by excited state proton transfer was hypothesised to explain this unusual behaviour. Interaction properties with G4 DNA were evaluated. All complexes display good affinity towards G4 and as expected, the complexe bearing the octacyclic ligand shows a strong selectivity towards G4 compared to dsDNA. Two of the complexes were proven to be potential luminescent light-switch ON probes for G4 detection in cells. In conclusion, this work highlights the possibility to use some of the newly synthetized complexes as efficient molecular tools for G4 visualization in cells.

Le principal objectif de cette thèse est d'expliquer en quoi l’efficience statique (static efficiency), l’efficience de coordination (coordinative efficiency) et l’efficience créative (creative efficiency) jouent un rôle déterminant dans la conception de la gouvernance à l'ère numérique. Il s’agit également d’étudier des mécanismes originaux de gouvernance, au-delà de la traditionnelle dimension marché-hiérarchie, pouvant faciliter les processus de coordination intégrative (integrative coordination) ainsi que de création collective dans les organisations.La thèse comprend trois essais. Le premier est une contribution de nature théorique montrant que l’économie des coûts de transaction (Williamson 1979, 1991, 1996, 2002) ne permet pas de rendre compte de façon satisfaisante de la conception de la gouvernance à l’ère numérique. Le modèle conceptuel normatif proposé contribue à repenser celle-ci dans une perspective pluraliste intégrant complexité et variété. Les choix de gouvernance ne sont ainsi plus limités à la seule dimension marché-hiérarchie comme le laisse penser l’économie des coûts de transaction. Une perspective intégrant la construction sociale des modes d’organisation (Giddens, 1985; Greenwood et al. 2011) permet de définir une variété de formes de gouvernance. Il est possible de représenter, dans un espace à trois dimensions (efficience statique, efficience de coordination et efficience créative), les différentes configurations de gouvernance sous la forme d’un triangle. Cette représentation peut être appliquée afin de rendre compte des choix de gouvernance possibles à différents niveaux organisationnels.Les deux essais suivants sont à dominante empirique. Ils visent à prolonger le premier en étudiant le lien entre des configurations innovantes de gouvernance et la performance des organisations en matière d’efficacité de coordination et d’efficacité créative. Le deuxième essai se concentre sur la coordination d’intégration dans les organisations. Des structures organisationnelles distribuées à plusieurs couches ou layered distributed organizational structures (Simon, 1962), des plans définis ex ante de façon imprécise ou broad-brushed ex ante plans (Edmondson, Bohmer et Pisano, 2001), ainsi que des semi-structures (Brown et Eisenhardt, 1997) s’avèrent utiles au processus de coordination lorsque les interdépendances sont complexes et incertaines. Le troisième essai porte sur la performance des organisations en matière de créativité collective. Il s’intéresse notamment aux dispositifs organisationnels facilitant l’émergence d’une telle créativité tout en préservant stabilité et efficacité. Plusieurs formes de perturbation qualifiées d’ordonnées (ordered disruption), tant au niveau spatial (ordered spatial disruption) que temporel (ordered temporal disruption) et affectif (ordered affective disruption), contribuent à l'émergence de la créativité collective.Le matériel empirique utilisé dans les deuxième et troisième essais provient d’une étude des modes de gouvernance de différents projets de villes intelligentes (smart-cities) nécessitant une collaboration entre plusieurs organisations. / The main objective of this dissertation is to explain why coordinative efficiency, creative efficiency, together with static efficiency are all critical goals of governance design in digital age, and to explore innovative governance arrangements, beyond the one-dimensional line defined by “market” and “hierarchy”, that can facilitate the processes of integrative coordination, and collective creation in organizations.The dissertation is composed of three essays. Essay 1 is a theory paper that provides the overall theoretical arguments about why transaction cost economics (Williamson 1979, 1991, 1996, 2002) is no longer a satisfactory theoretical framework for governance design in the digital age, and offers a normative model which suggest possibilities of much more nuanced, complicated and pluralistic governance choices than suggested by transaction cost economics. It is argued that potential governance choices are not solely situated on a one-dimensional line between hierarchy and market, as transaction cost economics asserts. The rich connotations of socially constructed agency (Giddens, 1985; Greenwood et al. 2011) provide diverse possibilities of governance arrangements, which spread across a triangular plane in a three-dimensional space defined by static efficiency, coordinative efficiency and creative efficiency (see Figure 1). This paper provides both graphic and mathematical presentations of this three-dimensional model for governance design, which can be applied to different levels of organizing.Essay 2 and 3 are two empirical papers that endeavor to extend Essay 1 by finding out the exact relationship between certain innovative governance arrangements with organizations’ performance in coordinative and creative efficiencies. Essay 2 focuses on the realization of integrative coordination in organizations. It found out that layered distributed organizational structure (Simon, 1962), broad-brushed ex ante plan (Edmondson, Bohmer and Pisano, 2001), and semi-structures (Brown and Eisenhardt, 1997) are beneficial in facilitating an ongoing coordination process when interdependencies are complex and uncertain. Essay 3 focuses on organizations’ performance in collective creativity (Shalley et al., 2004; George, 2007), especially on what governance arrangements can best allow collective creativity to emerge without overly sacrificing organizational stability and efficiency. It is discovered that “ordered disruption”, including ordered spatial disruption, ordered temporal disruption and ordered affective disruption, have positive effects on the emergence of collective creativity. Both Essay 2 and Essay 3 use collaborative organizations on smart city projects as the empirical setting. The findings of these two empirical papers are grounded on multiple case studies on those collaborative organizations.

Recent studies have indicated a further need to investigate the role of motivation in workingmemory (WM) training and that time perception affects motivation. We addressed whethersubjectively perceived time on task in reference to objective time on task could serve as animplicit measure of motivation, while controlling for individual differences in timeperception. Here, the relationship between different measures of time perception, WM, andmotivation was explored in healthy children. Fifty children in three natural groups (ages: 6-7,8-9, 10-11) at a Swedish school participated. WM scores changed with age as expected.However, the absence of correlations between WM performance and intrinsic motivationwere inconsistent with previous findings, presumably due to the low statistical sensitivity.Nevertheless, time perception accuracy (r=0.318, p=0.043) and state motivation (r=0.434,p=0.005) correlated with performance on task interference, but not WM. With somereservations due to low sensitivity, time perception accuracy appears to be linked tocoordinative capacity required for shifting attention, but to a lesser degree sequential working memory capacity.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal