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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
81

The End of Sweden’s Nonalignment Policy and Generous RefugeePolicy, or EU as a Solution : Sweden’s National Self-determination in the EU Membership Debate,1987 – 1991

Maagaard, Sebastian January 2017 (has links)
This thesis examines how the parliamentary debate in Sweden saw the consequences of Swedenas a nation were to join the European Union. The nation is defined as a state based on nationalself-determination. The EU is regarded as a supra-state organisation and one of the moreextensive efforts of its kind. I specifically examine two themes in Swedish foreign policy. Theseare the nonalignment policy and migration policy. Through a discourse analysis I show that allpolitical parties perceive consequences for the self-determination and all argue selfdeterminationwill be lost in the event of membership. However, they are divided in what theybelieved this would lead to. Some parties support EU whereas others are sceptical of EU. Partiesthat support an EU-membership argue that it is inevitable to join and Sweden will lose selfdeterminationanyway. A membership opens the possibility to influence and participate, but anabstaining will lead forced acceptance of policies. Many of the supporters are even positive ofbeing a member in EU. Sceptics, on the other hand believe Sweden will lack influence and loseall self-determination. The organisation itself is against Sweden as it is a supra-stateorganisation, which may reduce the role of single member-states. For the nonalignment policy,the government initially use it as an argument against EU, but later support membership if thenonalignment policy can be kept. The other supporters acknowledge the nonalignment policy,but nevertheless assert that EU is compatible with the nonalignment policy. This is because ofthe changes in the geopolitical situation. Sceptics believe the nonalignment policy rejectmembership, mostly due to the still uncertain geopolitical situation and the suspicion EU willdeprive Sweden of its decision-making. Sometimes they suggest the self-determination andnonalignment policy are prerequisites for each other. In the migration policy, all parties supportgenerous migration policy, but
82

"Estudo duplo-cego comparativo entre prednisona e dexametasona na avaliação da reserva adrenal em crianças e adolescentes com leucemia linfocítica aguda" / Evaluation of adrenal reserve in children and adolescents with acute lymphocytic leukemia through a double-blind comparison between Prednisone and Dexamethasone

Kuperman, Hilton 30 November 2005 (has links)
Para avaliar a reserva adrenal após o uso de glicocorticóide na fase de indução de remissão em pacientes com Leucemia Linfocítica Aguda, estudo duplo-cego foi realizado em 29 crianças e adolescentes de 1,7 a 15,9 anos (média:6,8 anos], que receberam por escolha aleatória, Prednisona na dose de 40 mg/m²/dia ou Dexametasona, 6 mg/m²/dia, via oral, por um mês. Testes do ACTH em baixa dose (1,0 µg/m² EV) foram realizados antes e a cada 7 dias por 8 semanas para avaliar pico de cortisol após o estímulo. Não houve diferença significativa entre as médias dos picos de cortisol nos testes realizados em cada grupo e entre os dois grupos, mostrando reserva adrenal adequada. Não houve correlação entre os picos de cortisol nos dois grupos e a presença de infecção / In order to evaluate adrenal reserve after adminstration of glucocorticoid during induction phase in patients with Acute LymphociticLeukemia, a double-blind study was performed in 29 children and adolescents 1,7 to 15.9 years old (mean: 6.8 years old), who randomly were chosen to receive either Prednisone, 40 mg/m²/day or Dexamethasone, 6 mg/m²/day, PO, for one month. Low-dose ACTH tests (1.0 µg/m² IV), were performed before and every 7 days after glucocorticoid for 8 weeks. There were no significant differences of cortisol mean peak levels in the tests of each group and in both group, suggesting adequate adrenal reserve. There was no correlation of cortisol mean peak levels in both groups and the presence of infection
83

The Role of Attention and Response Based Learning in the Visual Hebb Supra-span Sequence Learning Task: Investigating Age-related Learning Deficits

Brasgold, Melissa 01 February 2012 (has links)
Using Hebb’s (1961) paradigm, it has been shown that older adults (OAs) fail to learn recurrent visuospatial supra-span sequence information (Turcotte, Gagnon, & Poirier, 2005); a deficit which has not been demonstrated on verbal versions of the same task or in younger adults (YAs). Since the Hebb paradigm is thought to rely on working memory and thus attention (Conway & Engle, 1996), one interpretation concerns an OA’s capacity to allocate the necessary attentional resources to carry out the various components of the task. Five studies investigated this proposal. The first three (Article 1) examined attention in a general manner by reducing the amount of attentional resources that a YA could devote to carrying out the visuospatial Hebb supra-span sequence learning task through the implementation of a verbal dual task (DT) procedure. The fourth (Article 2) further investigated the role of attention by using a DT induced at retrieval that overlapped extensively with the requirements (spatial and response features) of the visuospatial Hebb task. The final study (Article 3) aimed to use our previous findings to demonstrate learning among OAs in a visuospatial Hebb learning paradigm in which the motor response was replaced by a verbal response. Our findings confirm that attentional resources employed at the retrieval phase of the task appear to be particularly important for the demonstration of visuospatial sequence learning. The inclusion of a spatial and motor based DT at recall eliminated learning of the repeated sequence in YAs. Interestingly, the learning deficit of OAs was partially eliminated when the motor and spatial requirements at retrieval were reduced. Our findings offer strong support to the contention that supra-span learning of the Hebb type is not altered by the effect of age. However, learning deficits can be observed among OAs when the retrieval component of the task overly taxes attention-related processes. In the case of the visuospatial sequences, the basis of the deficit likely concerns an individual’s capacity to discriminate between responses made to previously presented sequences versus those that need to be made in reaction to the just seen sequence.
84

The Role of Attention and Response Based Learning in the Visual Hebb Supra-span Sequence Learning Task: Investigating Age-related Learning Deficits

Brasgold, Melissa 01 February 2012 (has links)
Using Hebb’s (1961) paradigm, it has been shown that older adults (OAs) fail to learn recurrent visuospatial supra-span sequence information (Turcotte, Gagnon, & Poirier, 2005); a deficit which has not been demonstrated on verbal versions of the same task or in younger adults (YAs). Since the Hebb paradigm is thought to rely on working memory and thus attention (Conway & Engle, 1996), one interpretation concerns an OA’s capacity to allocate the necessary attentional resources to carry out the various components of the task. Five studies investigated this proposal. The first three (Article 1) examined attention in a general manner by reducing the amount of attentional resources that a YA could devote to carrying out the visuospatial Hebb supra-span sequence learning task through the implementation of a verbal dual task (DT) procedure. The fourth (Article 2) further investigated the role of attention by using a DT induced at retrieval that overlapped extensively with the requirements (spatial and response features) of the visuospatial Hebb task. The final study (Article 3) aimed to use our previous findings to demonstrate learning among OAs in a visuospatial Hebb learning paradigm in which the motor response was replaced by a verbal response. Our findings confirm that attentional resources employed at the retrieval phase of the task appear to be particularly important for the demonstration of visuospatial sequence learning. The inclusion of a spatial and motor based DT at recall eliminated learning of the repeated sequence in YAs. Interestingly, the learning deficit of OAs was partially eliminated when the motor and spatial requirements at retrieval were reduced. Our findings offer strong support to the contention that supra-span learning of the Hebb type is not altered by the effect of age. However, learning deficits can be observed among OAs when the retrieval component of the task overly taxes attention-related processes. In the case of the visuospatial sequences, the basis of the deficit likely concerns an individual’s capacity to discriminate between responses made to previously presented sequences versus those that need to be made in reaction to the just seen sequence.
85

The Politics Of Local Economic Growth- A Critical Approach: The Case Of Manisa

Tunc, Gulcin 01 August 2010 (has links) (PDF)
The mainstream accounts on local growth politics, which generally conceptualize the current context around the globalization of investments and the prominent role of local entrepreneuralism, argue for the tendency towards local coalitions. In opposition, the main argument of the thesis is that an increasingly fragmented and conflictual local growth politics is the defining feature of the contemporary localities. Defining the current context around the increased involvement of the business actors in directing the path of local economic growth and of the local state institutions in entrepreneurial activities, it was shown in Manisa case that intra-local conflicts are likely to deepen under conditions of increased inter-urban competition. By critically employing the concept of local dependence, it was shown that different local dependence factors result in the differentiation of the local actors&rsquo / priorities and preferences with regard to the utilization of local resources. Thus, it is concluded that a common local interest is not possible and that conflicts and contentions (between different-fractions of capital and between local labor and capital) stemming from the existence of different local dependence factors mark the process of local growth politics. As a special dependence factor in terms of local politics, the generation of land-rent was identified to be a potential basis for local collaborations whereas it was also found out that such coalitions are likely to be temporary and open to political contention. On the other hand, the supra-local relations of actors, which are essential for the pursuasion of local interests, are observed to have a determinant effect on local conflicts.
86

The Role of Attention and Response Based Learning in the Visual Hebb Supra-span Sequence Learning Task: Investigating Age-related Learning Deficits

Brasgold, Melissa 01 February 2012 (has links)
Using Hebb’s (1961) paradigm, it has been shown that older adults (OAs) fail to learn recurrent visuospatial supra-span sequence information (Turcotte, Gagnon, & Poirier, 2005); a deficit which has not been demonstrated on verbal versions of the same task or in younger adults (YAs). Since the Hebb paradigm is thought to rely on working memory and thus attention (Conway & Engle, 1996), one interpretation concerns an OA’s capacity to allocate the necessary attentional resources to carry out the various components of the task. Five studies investigated this proposal. The first three (Article 1) examined attention in a general manner by reducing the amount of attentional resources that a YA could devote to carrying out the visuospatial Hebb supra-span sequence learning task through the implementation of a verbal dual task (DT) procedure. The fourth (Article 2) further investigated the role of attention by using a DT induced at retrieval that overlapped extensively with the requirements (spatial and response features) of the visuospatial Hebb task. The final study (Article 3) aimed to use our previous findings to demonstrate learning among OAs in a visuospatial Hebb learning paradigm in which the motor response was replaced by a verbal response. Our findings confirm that attentional resources employed at the retrieval phase of the task appear to be particularly important for the demonstration of visuospatial sequence learning. The inclusion of a spatial and motor based DT at recall eliminated learning of the repeated sequence in YAs. Interestingly, the learning deficit of OAs was partially eliminated when the motor and spatial requirements at retrieval were reduced. Our findings offer strong support to the contention that supra-span learning of the Hebb type is not altered by the effect of age. However, learning deficits can be observed among OAs when the retrieval component of the task overly taxes attention-related processes. In the case of the visuospatial sequences, the basis of the deficit likely concerns an individual’s capacity to discriminate between responses made to previously presented sequences versus those that need to be made in reaction to the just seen sequence.
87

Tendinose calcificante do músculo supra-espinhoso em cães

Mestieri, Maria Lígia de Arruda [UNESP] 01 December 2008 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:31:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-12-01Bitstream added on 2014-06-13T20:21:58Z : No. of bitstreams: 1 mestieri_mla_dr_jabo.pdf: 2694352 bytes, checksum: 4e6a0aa7574c83896fbcf276fbb312ff (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A tendinose calcificante do músculo supra-espinhoso é pouco conhecida em cães. Sua apresentação e relevância clínicas, bem como os padrões epidemiológicos, permanecem obscuros nesta espécie. Neste estudo, objetivou-se a descrição clínico-epidemiólogica da afecção e dos padrões radiográficos e ultrasonográficos das lesões. Para tal, foi realizado levantamento retrospectivo em 2164 cães submetidos à avaliação radiográfica dos ombros, atendidos na Clínica Cirúrgica de pequenos animais da Universidade de Giessen, Alemanha, no período compreendido entre janeiro de 1996 a julho de 2006. Alterações radiográficas compatíves com tendinose calcificante do supra-espinhoso foram observadas em 144 cães. Observouse, dentro da população estudada, que 93% dos cães era de raças de grande porte, especialmente Rottweilers, concentrados na faixa de 4 a 7,9 anos e machos. As lesões foram diagnosticadas unilateralmente em mais de 80% dos cães, sendo que 70% apresentavam sinais clínicos. A maioria destes cães (75%) era portadora de outra afecção ortopédica, destacando-se a fragmentação do processo coronóide medial da ulna, dificultando a confirmação da tendinose como causa da manifestação clínica. Adicionalmente, foram revisadas imagens radiográficas de 138 ombros acometidos pela afecção e ultra-sonográficas de 21 ombros, a fim de se detalhar os padrões de imagem existentes. As lesões observadas por meio de radiografia foram classificadas em cinco graus. Na maioria dos cães sintomáticos, não portadores de outra afecção ortopédica, as lesões foram classificadas como de graus 3 e 4 à radiografia e mostraram-se como áreas hiperecóicas com sombreamento acústico à ultra-sonografia. A avaliação ultrasonográfica permitiu acessar o parênquima tendíneo com detalhes e a presença de hipoecogenicidade circundante à área calcificada foi sugestiva de processo inflamatório. / Supraspinatus calcifying tendinosis is a relatively unknown disorder in dogs. Its clinical presentation, relevance and epidemiological pattern remain unclear. In the present study, we aimed its clinical-epidemiological, radiological and sonographic description performing a retrospective study in dogs presented to the Small Animal Surgery Clinics of the Giessen University, Germany, between January 1996 and July 2006. In 2164 dogs which shoulders were submitted to radiographies, 144 presented lesions compatible to supraspinatus calcifying tendinosis. It was observed that 93% were large breed dogs, specially Rottweilers, male, aging between 4 and 7,9 years old. The calcifying lesions were unilateral in 80% of the cases; 70% of the dogs showed clinical symptoms however, a great amount (75%) of them presented also some other orthopedic abnormality, speccially ulnae fragmented coronoid process, which was considered the clinical signs cause. Additionally, 138 shoulder radiographies and 21 shoulder sonographies were reviewed and their findings described. A radiological classification system in five degrees was proposed, according to the lesion appearance. In the major part of the symptomatic dogs, not affected by other orthopedic abnormality, the lesions were radiologically classified in degree 3 and 4 and showed a dense distal shadowing by sonographic evaluation. Sonography also allowed tendon parenchyma evaluation, providing tissue details. The presence of hypoechoic area surrounding the calcific lesion was sugestive of infflamatory process.
88

Obrigações político-criminais do Estado frente à criminalidade econômica

Silva, João Bernardo da [UNESP] 28 March 2007 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:24:14Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-03-28Bitstream added on 2014-06-13T19:30:53Z : No. of bitstreams: 1 silva_jb_me_fran.pdf: 763224 bytes, checksum: 69c8f925001e4fe7c2a9131383e7a279 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho enfoca a criminalidade econômica sob a perspectiva da obrigação do Estado de estabelecer uma política criminal condizente com a magnitude e seriedade desta espécie de delinqüência. A criminalidade econômica sempre existiu. A repressão estatal, porém, é tímida e ineficaz, em razão da posição política, social e econômica de seus agentes e sua influência no círculo do poder. A ação estatal de combate a essa forma de criminalidade precisa utilizar a concepção global das ciências criminais, buscando subsídios na criminologia, projetando estes dados na dogmática jurídico-penal, com a conseqüente adoção de políticas criminais adequadas. O trabalho enfoca a moderna concepção de criminalidade econômica, influenciada pela globalização e pela sociedade de risco. O Direito Penal Econômico contribui para a solução dos problemas apresentados ao dar nova interpretação a seus institutos e aceitar novos bens jurídicos, os supra-individuais. Os desafios da modernidade exigem novos paradigmas penais, na busca da justiça social. / This paper focus on economic criminality as being a State obligation to stablish a criminal policy suitable to the magnitude and the social damage of this kind of delinquency. The economic criminality has always existed. However, the reprimand applied by the State is inadequate and inept due to the agents political, social and economical position. The State action against this form of criminality needs to make use of the crime science global conception, looking for resources in the criminology, projecting these data into the criminal legal doctrine and, afterwards, adopting the adequate criminal policies. This paper focus on the modern conception of economic criminality influenced by the globalization and the risk society. The Economic Criminal Law contributes to solve the presented problems giving a new interpretation to its grounds and accepting new legal properties, that is, supraindividual properties. The modern challenges demand the adoption of new legal paradigms in the search for social justice.
89

Expressão do fator de transcrição nuclear kB (NF-kB) em neurônios ocitocinérgicos de ratos submetidos à sobrecarga salina : influência da dexametasona / Expression of nuclear transcription factor kB (NF-kB) in rat ocxytocinergic neurons submitted to salt loading : the influence of dexamethasone

Santos, Patricia Rabelo dos 27 January 2014 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The hypothalamic-neurohypophysial system is the main system through which the brain maintains homeostasis of bodily fluids. Specifically, the supraoptic (SON) and paraventricular (PVN) hypothalamic nuclei are directly involved with hydroelectrolytic equilibrium and are specialized in the synthesis and secretion of vasopressin and oxytocin (OT). Changes in the milieu intérieur are conceived as stressors by the central nervous system (CNS) and are modulated by the hypothalamic-pituitary-adrenal axis (HPA). Nuclear transcription factor kappa B (NF-κB) mediates immunosuppressant and anti-inflammatory of glucocorticoids. Thus, the aim of this study was to verify the expression profile of component p65 of the NF-κB classical pathway in SON and PVN oxytocinergic neurons in response to dehydration, glucocorticoid treatment, and in normal conditions. Methods: Wistar rats (250-300g) were maintained in controlled environment with temperature (23 ± 2ºC), light/dark cycle of 12 hours and water and food specific for rodents ad labitum until the beginning of experimental period. All procedures were approved by Ethical Comitee of Research with Animals from UFS (Protocol # 60/2012). Animals were grouped into Control (water ad libitum for 4 days, n = 6-7); Control + Dexa (water ad libitum and treated with dexamethasone, n = 6-7); SL4 (salt overloading ad libitum, 1.8% NaCl for 4 days, n = 6-7); SL4 + Dexa (salt overloading ad libitum, 1.8% NaCl for 4 days and dexamethasone, n = 6-7). Dexamethasone (10 mg/kg i.p.) was administered 12 and 2 hours before perfusion and removal of brains for OT/p65 immunofluorescence, or before sacrifice for blood sampling and angiotensin II (ANGII) dosage. We applied two-way ANOVA and Bonferroni posthoc test to analyze behavioral and hormonal dosage data. Results obtained from imunohistochemestry for evaluation of oxytocin and/or p65 neuronal activity, were subjected to qualitative evaluation. We verified SL4 animals ingested more fluid than control, on second (p<0.01), third (p<0.01) and forth (p<0.001) experimental day. SL4 also increased plasmatic concentration of ANGII (p<0.01). Qualitative analysis of double labeling OT/p65 on PVN and SON revealed a weak immunoreactivity for oxytocin on SL4 and SL4 + Dexa groups, when compared to control and Control + Dexa groups. Was observed expression of p65 subunit of NF-κB in all hypothalamic studied areas, with predominant cytoplasmic imunoreactivity in all groups. These data demonstrate that p65 subunit of NF-κB are present in oxytocinergic neurons from the most important hypothalamic areas that integrates the stress axis (HPA) and hidroelectrolyte balance (SHNH). More studies are necessary to clarify the real participation of NF-κB intracellular pathway evoked by intracellular dehydration on endocrines and behavioral hidroelectrolyte adjustments. / O sistema hipotálamo neuro-hipofisário (SHNH) é o principal sistema pelo qual o cérebro mantém a homeostase dos líquidos corporais. Especificamente, os núcleos supra-óptico (SON) e paraventricular (PVN) do hipotálamo estão diretamente envolvidos com o controle do balanço hidroeletrolítico e são especializados na síntese e secreção de vasopressina (AVP) e ocitocina (OT). Alterações no milieu intérieur são vistas como estressoras pelo sistema nervoso central (SNC) e moduladas pelo eixo hipotálamo-hipófise-adrenal (HHA). O fator de transcrição nuclear kappa B (NF-κB) é conhecido por mediar os efeitos imunossupressores e anti-inflamatórios dos glicocorticoides. Sendo assim, o objetivo do presente estudo foi verificar o perfil de expressão do componente p65 da via clássica do NF-κB em neurônios ocitocinérgicos do PVN e SON, em resposta à desidratação crônica, associada, ou não, ao tratamento com glicocorticoides. Métodos: Ratos wistar (250-300 g) foram mantidos em ambiente com temperatura (23 ± 2ºC) e luminosidade, ciclo claro-escuro de 12 horas (luz das 6 às 18 horas), controladas, com água e ração específica para roedores (Labina®- Purina) ad libitum até o início dos experimentos. Todos os procedimentos foram aprovados pelo Comitê de Ética em Pesquisa com Animais da UFS (Protocolo # 60/2012). Os animais foram divididos de modo a constituir os grupos Controle (ratos com acesso à água ad libitum, durante quatro dias, n = 6 - 7); Controle + Dexa (ratos com acesso à água ad libitum, durante quatro dias, e tratados com dexametasona, n = 6 - 7); SL4 (ratos com acesso à sobrecarga salina ad libitum, solução de NaCl 1,8%, durante quatro dias, n = 6 - 7); SL4 + Dexa (ratos com acesso à sobrecarga salina ad libitum, NaCl 1,8%, durante quatro dias e tratados com dexametasona, n = 6 - 7). A dexametasona (10 mg / kg, i.p.) foi administrada apenas no 4º dia, 12h e 2 h antes da perfusão para coleta do cérebro e realização da dupla imunofluorescência OT/p65 ou eutanásia para coleta de sangue do tronco e posterior dosagem de angiotensina II (ANGII). Os dados comportamentais e de dosagem hormonal obtidos foram submetidos ao teste ANOVA de duas vias e pós-teste Bonferroni. Os resultados obtidos da imuno-histoquímica, para a marcação de neurônios expressando ocitocina e/ou p65, foram submetidos à avaliação qualitativa. Verificou-se que os animais SL4 ingeriram mais fluido que seus controles, no segundo (p < 0,01), terceiro (p < 0,001) e quarto (p < 0,001) dia experimental. A SL4 elevou a concentração plasmática de ANGII (p < 0,01). A análise qualitativa da dupla imunofluorescência OT/p65 no PVN e SON revelou uma fraca imunorreatividade à ocitocina nos grupos SL4 e SL4 + Dexa, quando comparados aos grupos Controle e Controle + Dexa. Observou-se expressão da subunidade p65 do NF-κB em todas áreas hipotalâmicas estudadas, com imunorreatividade predominantemente citoplasmática em todos os grupos. Estes dados mostram que a subunidade p65 do NF-κB está presente em neurônios ocitocinérgicos das principais áreas hipotalâmicas que integram os eixos do estresse (HHA) e do equilíbrio hidroeletrolítico (SHNH). Mais estudos são necessários a fim de esclarecer sobre a real participação da via intracelular do NF-κB evocada pela desidratação intracelular, nos ajustes hidroeletrolíticos endócrinos e comportamentais.
90

Synthèse et fonctionnalisation des nanoparticules d'or et caractérisation de leurs interactions avec des molécules biologiques

Doyen, Matthieu 22 January 2016 (has links)
Le développement et l’utilisation des nanomatériaux, matériaux constitués d’éléments dont au moins une dimension est comprise entre 0.2 nm et 100 nm, suivent une croissance exponentielle. L’intérêt pour ces nouveaux matériaux s’explique par le développement de nouvelles propriétés modulables en fonction de la taille et la forme des nanocomposants. Dans le cadre de ce travail, le mécanisme de formation de nanoparticules d’or, l’étude de leurs interactions avec des acides aminés et l’élaboration de supra-réseaux de nanoparticules d’or fonctionnalisées avec des oligonucléotides ont été investigués.L’étude, par spectroscopie d’absorption UV-Visible et par Résonance Magnétique Nucléaire (RMN), de la synthèse des nanoparticules d’or via la méthode dite de Turkevich a permis de clarifier le rôle du citrate durant la nucléation et la croissance des nanoparticules ainsi que l’effet du pH du milieu réactionnel sur le déroulement de la réaction. Nous avons montré que, pour obtenir une distribution de taille étroite, le pH de la solution doit être contrôlé de façon à ce que le citrate soit polydéprotonné et que les complexes d’Au(III) ne se trouvent pas sous une forme polyhydroxylé. Grâce au suivi in operando de la synthèse par RMN 1H, et plus précisément par la mesure du coefficient de diffusion (DOSY) des espèces présentes en solution, nous avons pu mettre en évidence la formation d’assemblages supramoléculaires lors de la nucléation des particules. Ces assemblages sont composés de molécules de citrates et d’atomes d’Au(I) ou Au(0). Nous avons donc pu démontrer que le citrate n’est pas seulement, comme décrit dans la littérature, un agent réducteur de l’Au(III) en Au(0) et un agent protecteur permettant d’éviter l’agrégation des nanoparticules, mais qu’il joue surtout le rôle crucial d’agent de nucléation.Nous nous sommes également intéressés à l’interaction entre des nanoparticules d’or et des acides aminés. Plusieurs études rapportées dans la littérature mettent en avant l’apparition d’une seconde bande d’absorption plasmon lorsque des acides aminés sont ajoutés à des colloïdes d’or ainsi que l’agrégation des particules sous forme de structures linéaires. Deux hypothèses sont émises pour expliquer la formation de ces structures. La première suggère que les acides aminés s’adsorbent à la surface des particules de manière anisotrope suite à l’interaction favorable entre leurs têtes zwitterioniques. Cette anisotropie créerait un dipôle électrique à travers des particules et mènerait à leur alignement. La seconde hypothèse propose que certains acides aminés interagissent spécifiquement via leur chaîne latérale avec la surface des particules. Leurs têtes zwitterioniques formeraient des liens hydrogènes avec celles d’acides aminés adsorbés sur une autre particule ce qui provoquerait l’agrégation des nanoparticules en structures linéaires. Nous avons étudié les interactions entre des nanoparticules d’or et certains acides aminés par spectroscopie d’absorption UV-Visible, par diffusion dynamique de la lumière (DLS), par mesure de potentiel zêta et par microscopie électronique à transmission (TEM). Nos expériences ont mis en évidence que les interactions entre têtes zwitterioniques ne seraient pas à l’origine de l’agrégation des nanoparticules. Nos résultats montrent que le régime d’agrégation des colloïdes est limité par la diffusion (DLCA) et que deux paramètres contrôlent cette agrégation. Le premier est la charge globale de l’acide aminé qui influence directement la force ionique de la solution ;le second est la facilité avec laquelle la molécule est capable d’interagir avec la surface des nanoparticules et modifier son potentiel de surface. Le calcul du potentiel total d’interaction entre nanoparticules à l’aide de la théorie de Derjaguin, Landau, Verwey et Overbeek (DLVO) a confirmé les paramètres clés mis en évidence par les expériences. Notre dernière étude a porté sur une approche Bottom-Up pour élaborer des supra-réseaux à partir de nanoparticules d’or fonctionnalisées avec des oligonucléotides. La méthode investiguée consiste à mélanger deux lots de nanoparticules d’or fonctionnalisées au préalable à l’aide d’oligonucléotides complémentaires. Cette approche bioinspirée a été adoptée car elle permet un contrôle précis de la structure grâce à l’appariement hautement spécifique entre oligonucléotides complémentaires. L’influence de différents paramètres sur la stabilité thermique des assemblages a été observée. Nous avons pu démontrer que plus la distance interparticulaire est importante, plus les assemblages sont stables et que la stabilité augmente aussi avec le nombre de bases complémentaires. La fonctionnalisation de nanoparticules d’or à l’aide d’oligonucléotides de tailles différentes a également permis de mettre en exergue la coopérativité du processus d’assemblage. Nos résultats ont établi que les appariements les plus longs gouvernent le processus d’assemblage et ce, quel que soit leur nombre sur les particules. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

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