abstract: Water affinity and condensation on Si-based surfaces is investigated to address the problem of fogging on silicone intraocular lenses (IOL) during cataract surgery, using Si(100), silica (SiO2) and polydimethylsiloxane (PDMS) silicone (SiOC2H6)n. Condensation is described by two step nucleation and growth where roughness controls heterogeneous nucleation of droplets followed by Ostwald ripening. Wetting on hydrophilic surfaces consists of continuous aqueous films while hydrophobic surfaces exhibit fogging with discrete droplets. Si-based surfaces with wavelength above 200 nm exhibit fogging during condensation. Below 200 nm, surfaces are found to wet during condensation. Water affinity of Si-based surfaces is quantified via the surface free energy (SFE) using Sessile drop contact angle analysis, the Young-Dupré equation, and Van Oss theory. Topography is analyzed using tapping mode atomic force microscopy (TMAFM). Polymer adsorption and ion beam modification of materials (IBMM) can modify surface topography, composition, and SFE, and alter water affinity of the Si-based surfaces we studied. Wet adsorption of hydroxypropyl methylcellulose (HPMC) C32H60O19 with areal densities ranging from 1018 atom/cm2 to 1019 atom/cm2 characterized via Rutherford backscattering spectrometry (RBS), allows for the substrate to adopt the topography of the HPMC film and its hydrophilic properties. The HPMC surface composition maintains a bulk stoichiometric ratio as confirmed by 4.265 MeV 12C(α, α)12C and 3.045 MeV 16O(α, α)16O, and 2.8 MeV He++ elastic recoil detection (ERD) of hydrogen. Both PIXE and RBS methods give comparable areal density results of polymer films on Si(100), silica, and PDMS silicone substrates. The SFE and topography of PDMS silicone polymers used for IOLs can also be modified by IBMM. IBMM of HPMC cellulose occurs during IBA as well. Damage curves and ERD are shown to characterize surface desorption accurately during IBMM so that ion beam damage can be accounted for during analysis of polymer areal density and composition. IBMM of Si(100)-SiO2 ordered interfaces also induces changes of SFE, as ions disorder surface atoms. The SFE converges for all surfaces, hydrophobic and hydrophilic, as ions alter electrochemical properties of the surface via atomic and electronic displacements. / Dissertation/Thesis / Ph.D. Physics 2011

L'objectif fondamental de cette thèse est de développer et de mettre en oeuvre un outil interactif desimulation des techniques de micromanipulation biologiques de cellules. Au moyen de cet outil, l'opérateurpourra se former, s'entraîner et améliorer sa maîtrise en développant une gestuelle proche de celle exécutéeen réalité. La conception d'un tel environnement de simulation en temps-réel nécessite de trouver uncompromis entre le réalisme des modèles de comportement biomécanique utilisés, la précision et la stabilitédes algorithmes des méthodes de résolution et de rendu haptique utilisées ainsi que la vitesse de calcul. Lamodélisation mécanique retenue repose sur l'utilisation du modèle hyperélastique de St Venant-Kirchhoff etune formulation dynamique explicite éléments-finis du type masses-tenseurs. Le bien-fondé de cettemodélisation est vérifié sur des essais de microindentation par Microscopie à Force Atomique (AFM) decellules souches embryonnaires de souris et de microinjection d'ovocytes. Nous avons développé etimplémenté des modèles d'interaction en temps-réel qui s'articulent autour de la détection et la gestionrapide des collisions entre outil/cellule.La synthèse du rendu haptique fourni à l'opérateur est également proposée par l'intermédiaire d'un couplagevirtuel. Pour chaque application, nous avons justifié nos choix méthodologiques et Algorithmiques qui sontguidés par les contraintes de "réalisme+précision" "temps-réel". Les différents modèles proposés ont étéintégrés dans le simulateur SIMIC que nous avons développé pendant cette thèse. Ce dernier est dédié à lasimulation interactive pour l'aide à l'apprentissage du geste de microinjection et de nanoindentationcellulaire. / The fundamental objective of this thesis is to develop and implementing an interactive simulation techniquesfor micromanipulation biological cells. Using this tool, the operator can form, train and improve its control bydeveloping a gesture similar to that performed in reality. The design of such a simulation environment in realtime requires a compromise between the realism of biomechanical models used the accuracy and stability ofalgorithms and solution methods used haptic rendering and computational speed. Modeling Mechanicalrestraint involves the use of hyperelastic model of St Venant-Kirchhoff formulation and explicit dynamic finiteelement-type mass tensors. The validity of this model is tested on microindentation tests by Atomic ForceMicroscopy (AFM) of mouse embryonic stem cells and microinjection of oocytes. We have developed andimplemented models of real-time interaction that revolve around the detection and management of rapidcollisions between tool / cell.The synthesis of the haptic feedback provided to the operator is also available through a virtual coupling. Foreach application, we have justified our methodological choices and Algorithms that are guided by theconstraints of realism + precision "" real time ". The various proposed models have been integrated into thesimulator SIMIC that we developed during this thesis. This is dedicated to interactive simulation to supportlearning of gesture microinjection and cell nanoindentation.

ALENCAR, Luciana Magalhães Rebêlo. Estudo da viscoelasticidade de células de câncer renal por microscopia de força atômica. 2010. 155 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2010. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-05-22T18:40:21Z No. of bitstreams: 1 2010_tese_lmralencar.pdf: 15264548 bytes, checksum: e3df53eb49036e78f623d089ab7e0995 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-05-22T18:42:17Z (GMT) No. of bitstreams: 1 2010_tese_lmralencar.pdf: 15264548 bytes, checksum: e3df53eb49036e78f623d089ab7e0995 (MD5) / Made available in DSpace on 2015-05-22T18:42:17Z (GMT). No. of bitstreams: 1 2010_tese_lmralencar.pdf: 15264548 bytes, checksum: e3df53eb49036e78f623d089ab7e0995 (MD5) Previous issue date: 2010 / The mechanical properties of living cells have a crucial role in the accomplishment of their physiological functions. However, our knowledge on this subject is still limited. Is not fully understood how a cell responds structurally and mechanically to an external pressure or as the elasticity of cells is altered in diseased organisms compared to healthy ones. Recently, the biomechanics of cancer cells, in particular the elasticity or stiffness, has been identified as an important factor that is related to function, adhesion, motility, invasion and transformation of the neoplastic cells. Studies in vivo show that cancerous transformations introduce significant changes in the structure and behavior of cells. These differences can cause changes in mechanical properties, often leading to greater cell deformability. Quantifying the change of elasticity using mechanical tests in conjunction with a microscopic examination, can become a powerful method for the diagnosis of cancer, and open new routes for treatments. In this context, Atomic Force Microscopy (AFM) is presented as an ideal tool for cell research due to its high resolution capability for surface nano-manipulation, ability to work in fluids and for being a noninvasive and nondestructive technique. This study investigates the mechanical response of cancer cells (lines A-498 and ACHN), compared to normal cells (RC-124). Using an AFM and its components as a morphological tool of high resolution characterization and characterization of the cells mechanical properties using the AFM probe as a nano-indenter, and from the strength data obtained by the microscope, and appropriate theoretical models to interpret these data to obtain qualitative and quantitative values of the elastic response these cells. / As propriedades mecânicas de células vivas possuem um papel crucial no bom desempenho de suas funções fisiológicas. Porém, nosso conhecimento nesse assunto ainda é limitado. Não é totalmente compreendido como uma célula responde, estrutural e mecanicamente, a uma tensão externa ou como a elasticidade das células altera-se em organismos doentes em comparação a organismos sadios. Recentemente, a biomecânica de células do câncer (em particular, a elasticidade ou rigidez) tem sido apontada como um fator importante que está relacionado à função, adesão, motilidade, transformação e invasão da célula neoplásica. Estudos in vivo mostram que transformações cancerosas introduzem alterações significativas na estrutura e comportamento celular. Essas diferenças também podem causar alterações nas propriedades mecânicas, geralmente levando a uma maior deformabilidade da célula. A quantificação da alteração de elasticidade, utilizando ensaios mecânicos em conjunto com um exame microscópico, pode tornar-se um poderoso diagnóstico do câncer e abrir caminhos para novos tratamentos. Neste contexto, a Microscopia de Força Atômica (AFM) se apresenta como uma ferramenta ideal para a investigação de células por sua alta resolução, capacidade de nano-manipulação de superfícies, possibilidade de trabalhar em meios líquidos e por ser uma técnica não destrutiva. Neste trabalho, propõe-se a investigação da resposta mecânica de células cancerígenas (linhagens A-498 e ACHN), comparando-se com células normais (RC-124), utilizando-se um Microscópio de Força Atômica e seus componentes como ferramentas de caracterização morfológica de alta resolução e caracterização das propriedades mecânicas dessas células. Utilizando a sonda de AFM como nano-indentador e a partir dos dados de força obtidos pelo microscópio, analisados por meio de modelos teóricos adequados, temos por objetivo obter valores qualitativos e quantitativos da resposta elástica dessas células.

DNA double-strand breaks (DSBs), where both strands of the DNA duplex are simultaneously fractured, are considered the most lethal type of DNA damage. The conserved Mre11-Rad50 DNA repair complex enables the catalytic activities of the Mre11 nuclease and the Rad50 ATPase to function together to coordinate the recognition and processing of DSBs prior to the recruitment of long-range end-resection machinery required to trigger the DSB repair by the homologous recombination (HR) pathway. Fast-scan atomic force microscopy (AFM) in fluid conditions was primarily used to explore the architectural arrangement, DNA binding and processing machinery of the Mre11-Rad50 complex from the thermophilic crenarchaeote Sulfolobus acidocaldarius. The structural analysis identified four distinct architectural arrangements and demonstrates the key role of the Rad50 zinc hooks in the oligomerisation of the complex. AFM imaging showed a dynamic and Velcro-like interplay between Mre11-Rad50 protein complexes and the DNA double-helix using the Rad50 coiled-coils in a novel mode of DNA binding. The complex appears to use the Rad50 zinc hook region to bind to and track along dsDNA for broken DNA-terminals. Furthermore, the present study shows that this archaeal complex can drive extensive ATP-dependent unwinding of DNA templates. It is the first time that such unwinding has been observed in a single molecule study. These observations reveal novel activities leading to the proposal of a new model for Mre11-Rad50 action during DSB repair. AFM was also used to visualise the structure and activity of the HerA-NurA protein complex, which has been predicted to combine the activity of the NurA nuclease and hexameric HerA-translocase to generate long single-stranded DNA overhangs essential for DSB repair by HR in archaea. The present data verify and clarify the presumed biological role of this complex. Overall, the present study provides new insights into the initial steps of DNA DSB repair by the HR pathway and, most importantly, the detection of the broken ends.

Une analyse détaillée des propriétés physico-chimiques des nanoparticules (NP) anthropogéniques est nécessaire pour comprendre à un niveau mécanistique leurs interactions/toxicité potentielle avec/envers les composants biotiques des systèmes aquatiques naturels. Une telle analyse est également requise pour réaliser une évaluation complète et une optimisation de la performance des méthodes d’(ultra)filtration développées pour circonscrire le relargage des NPs dans les milieux aquatiques. Dans ce contexte, l'objectif de cette thèse de doctorat était de déchiffrer les processus physico-chimiques fondamentaux régissant la capture de nanodendrimères carboxylés (PAMAM-COOH) - utilisés fréquemment dans des applications biomédicales – par des films multicouches du type (poly(diallyldiméthylammonium)chlorure-poly(acide acrylique))n ((PDADMAC-PAA)n) assemblés par déposition séquentielle des composantes polymériques cationique et anionique. À cette fin, une étude systématique des propriétés électrohydrodynamiques des NPs PAMAM-COOH a d'abord été effectuée en fonction du pH et de la concentration en sel monovalent du milieu. Sur la base de la théorie électrocinétique de particules molles ayant une fonctionnalité zwitterionique, il est démontré que les caractéristiques électriques interfaciales des NPs considérées sont déterminées à la fois par des contributions électrostatiques de surface et volumique des nanoparticules, lesquelles dependent de l’extension intraparticulaire de la double couche électrique. L’existence de ces deux types de contributions conduit à un changement remarquable de signe de la mobilité des NPs en modifiant la concentration du sel monovalent en solution et à une dépendance prononcé du point de zéro mobilité des NPs avec la concentration de l’électrolyte. En outre, une confrontation quantitative entre résultats expérimentaux et théorie souligne comment les modifications structurales des NPs induites par des changements de pH et de salinité affectent les caractéristiques électrocinétiques des dendrimères. Dans une deuxième partie, la structure, la morphologie et les propriétés mécaniques des films PDADMAC-PAA et leur évolution temporelle dans des conditions de vieillissement naturel ou après traitement thermique ont été déterminées par microscopie à force atomique (AFM) et analyses microspectroscopie Raman. Les résultats démontrent que les films multicouches PDADMAC-PAA de type exponentiel présentent des caractéristiques mécaniques et structurelles typiques de films polyélectrolytes multicouches à croissance linéaire. En particulier, leur relaxation lente vers un état d’équilibre est accélérée après traitement thermique à 60°C et se révèle être intimement liée à l'instabilité de domaines de films riches en PDADMAC, épuisés en eau (faits confirmés par la théorie de la fonctionnelle de la densité) et marqués par la présence de structures caractéristiques en forme de ‘donuts’. Dans une dernière partie, des résultats préliminaires sont donnés pour la dépendance de l'élasticité des films multicouches PDADMAC-PAA avec la concentration en solution de nanodendrimères. Les résultats suggèrent que ces films multicouches complexes constituent une option prometteuse pour la capture et l'élimination de nanodendrimères carboxylés présents en milieux aqueux / A detailed analysis of the physicochemical properties of engineered nanoparticles (NPs) is required to understand on a mechanistic level their interactions/potential toxicity with/towards biotic components of fresh water systems. Such an analysis is further mandatory to achieve a comprehensive evaluation and optimisation of the performance of (ultra)filtration methods developed to prevent NPs release into aquatic media. Within this context, the aim of this PhD thesis was to decipher the basic physico-chemical processes governing the loading of carboxylated-poly(amidoamine) (PAMAM-COOH) nanodendrimers -commonly employed in biomedical applications- into layer-by-layer assembled (poly(diallyl dimethyl ammonium) chloride-poly(acrylic acid))n ((PDADMAC-PAA)n) multilayer films. For that purpose, a systematic investigation of the electrohydrodynamic properties of PAMAM-COOH NPs was first performed as a function of pH and monovalent salt concentration in solution. On the basis of advanced electrokinetic theory for soft particles with zwitterionic functionality, it is demonstrated that the interfacial electrostatic features of the considered NPs are determined both by surface and bulk particle contributions to an extent that depends on electrolyte concentration. This leads to a remarkable NPs mobility reversal with changing monovalent salt concentration and to a marked dependence of the point of zero NPs mobility on electrolyte content. In addition, confrontation between experiments and theory further highlights how pH- and salt-mediated modifications of the NP particle structure affect dendrimer electrokinetic features at large pH and/or low salt concentrations. In a second part, the structure, morphology and mechanical properties of PDADMAC-PAA films, and their evolution over time under natural aging conditions or after thermal treatment, were addressed from atomic force microscopy (AFM) and Raman microspectroscopy analyses. Results evidence that PDADMAC-PAA multilayer films of exponential type exhibit mechanical and structural features that are typical for polyelectrolyte multilayer films with linear growth. In particular, their slow relaxation to equilibrium is accelerated after heating treatment at 60°C and, in line with density functional theory computation, this relaxation dynamics is shown to be intimately connected to instability of film domains rich in PDADMAC, depleted in water and marked by the presence of characteristic donut-like structures. In a final part, the reported dependence of PDADMAC-PAA multilayer films elasticity on concentration of nanodendrimers in bulk solution suggests that these complex multilayer films constitute a promising option to be further investigated for the loading and removal of carboxylated nanodendrimers from aqueous environments

This thesis presents work based on the interactions of water soluble caboxylated zinc phthalocyanines (Pcs) and coreshell quantum dots (QDs). The Pcs are ZnPc(COOH)₈ and ZnPc(COOH)₄ and coreshell QDs are CdTe@ZnS-GSH. GSH = L-glutathione. Characterization and photophysical studies of conjugates were carried out. The approach of coordinating Pcs to QDs was achieved using an organic cross linker, N-N’-dicyclohexylcarbodiimide (DCC) at pH 10 at room temperature. Employing atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman, infrared and X-ray photoelectron spectroscopies, the formation of the conjugates was confirmed. Upon conjugation with Pc derivatives, the fluorescence quantum yield of CdTe@ZnS-GSH decreased due to energy transfer from the QDs to the Pc. The average fluorescence lifetime of the CdTe@ZnS-GSH QD also decreased upon conjugation. The föster resonance energy transfer (FRET) behaviour of CdTe@ZnS-GSH-ZnPc(COOH)₄ conjugates was compared to that of CdTe@ZnS-GSH-ZnPc(COOH)₈. Higher FRET efficiencies were observed for CdTe@ZnS-GSH-ZnPc(COOH)₄-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₄-linked compared to the corresponding CdTe@ZnS-GSH-ZnPc(COOH)₈-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₈-linked. Triplet quantum yield (ΦT) and lifetime (ΤT) of ZnPc(COOH)₈ were found to increase in the presence of coreshell QDs. Though the singlet quantum yield (ΦΔ) value of ZnPc(COOH)8 was lower than ΦT , there was a slight upsurge in the ΦT in the presence of QDs. / Microsoft� Word 2010 / Adobe Acrobat 9.53 Paper Capture Plug-in

Les travaux de cette thèse se situent dans un contexte de miniaturisation des transducteurs ultrasonores micro-usinés (cMUTs). Ce type de dispositifs est utilisé depuis plusieurs décades dans le domaine de l'imagerie par échographie allant du contrôle non-destructif de structures jusqu'au domaine médical. La quête d'une imagerie hautement résolue nécessite l'utilisation de cMUTs de fréquence de résonance de l'ordre du GHz et de taille micrométrique. L'élément actif de ces cMUts est une membrane suspendue de surface micrométrique. Une étude analytique, basée sur le comportement mécanique des plaques minces, a permis de dimensionner les membranes suspendues et de souligner l'importance d'avoir une épaisseur nanométrique pour avoir un signal émis détectable électriquement. Plusieurs matériaux; à savoir des nanotubes de carbone, du graphène, du graphène oxydé, du DLC (diamond like carbon) et du silicium, ont été mis en œuvre dans la cadre de cette étude pour réaliser des membranes suspendues de taille micrométrique et d'épaisseur nanométrique. Des procédés technologiques propres à chacun de ces matériaux ont été conçus et des membranes d'épaisseurs variant de 2 à 15 nm et de largeurs variant de 1 à 2 µm ont été fabriquées. Une méthode de caractérisation innovante a été mise en place afin d'évaluer les propriétés mécaniques des différentes membranes réalisées. Un protocole de mesure a été développé pour mesurer l'amplitude de déplacement des membranes suspendues sous l'action d'une force électrostatique. Des amplitudes qui atteignent la dizaine de nanomètres ont été mesurées, amplitudes qui correspondent à des variations de capacités électriquement détectables. Plus généralement, ces travaux constituent une preuve solide de la faisabilité des nano-membranes suspendues de taille micrométrique avec un déplacement détectable. / This thesis concerns a context of miniaturization of micromachined ultrasonic transducers (cMUTs). This type of device has been used for decades in the field of ultrasound imaging for the non-destructive testing of structures for example. The quest of a highly resolved imaging requires the use of cMUTs with a resonance frequency in the order of GHz and with a micrometer size. The main part of these cMUts is a suspended membrane with a micrometric surface. An analytical study, based on the mechanical behavior of thin plates, is used for the design of the suspended membranes. This study emphasizes the importance of having a nanometric thickness to obtain a detectable electrical signal. Several materials, namely carbon nanotubes, graphene, graphene oxide, DLC (diamond like carbon ) and silicon have been implemented in this study to make a micron size suspended membranes with a nanometric thickness . Technological processes specific to each of these materials have been designed. Suspended membranes with thicknesses ranging from 2 to 15 nm and widths ranging from 1 to 2 microns were made. A novel method of characterization has been established to evaluate the mechanical properties of our membranes. A measurement protocol has been developed to measure the of displacement of the suspended membrane under the an electrostatic field . Amplitudes reaching ten nanometers were measured. More generally , this study provides a strong proof of the feasibility of suspended micrometer-sized membranes with an electrically detectable signal.

Neste trabalho, se pretende caracterizar a morfologia de filmes finos poliméricos por meio de técnicas de processamento de imagens, utilizando principalmente a geometria computacional e técnicas de classificação de padrões. Os objetivos principais foram quantificar as grandezas geométricas das estruturas observadas nos filmes finos e descrever padrões de superfície formados nestes filmes. Foram estudadas imagens obtidas por microscopia de força atômica (AFM) de amostras de filmes finos SEBS [poliestireno-poli(etileno-co-butileno)-poliestireno], depositados sobre um substrato de mica por técnicas de imersão. Os filmes finos SEBS são considerados de grande interesse devido à formação de estruturas auto-organizadas na escala nanométrica. A caracterização e a obtenção da morfometria dos filmes são de relevância neste trabalho, pois contribuem para o entendimento da dinâmica de formação destes padrões nas nanoestruturas estudadas. Foram analisadas diferentes morfologias, como forma de gotículas com anéis concêntricos e forma de tiras e pontos regularmente espaçados. Os resultados obtidos permitem caracterizar os padrões observados. / In this work, we intend to characterize the morphology of polymer thin films by techniques of image processing, mainly using computational geometry and pattern classification. The main objectives were to quantify the geometrical structures observed in thin films and describe surface patterns formed in these films. Were studied images obtained by atomic force microscopy (AFM) of SEBS [polystyrene-poly(ethylene-co-butylene)-polystyrene] thin films samples, deposited on a mica substrate by dip-coating technique . SEBS thin film polymers have great interest due to the formation of self-organized structures on the nanometer scale. The characterization and obtaining measurements of the morphology of the thin films are of relevance in this work, because they contribute to the understanding of the formation dynamics of these patterns in nanostructures studied. We analyzed different morphologies, such as droplets form with concentric rings and stripe and regularly spaced points forms. The results allow to characterize the observed patterns.

Orientador: Gilberto Medeiros Ribeiro / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-09T22:37:22Z (GMT). No. of bitstreams: 1 Leite_MarinaSoares_D.pdf: 10910248 bytes, checksum: 5dc120ade30e376360bb05f29092999a (MD5) Previous issue date: 2007 / Resumo: As propriedades estruturais e eletrônicas dos materiais em escala nanométrica dependem fortemente de sua composição química, assim como seu tamanho e forma. Uma variedade de morfologias distintas pode ser formada controlando-se as condições experimentais durante o crescimento epitaxial de Ge sobre um substrato de Si(001). Em particular, ilhas tridimensionais com tamanho e forma bem definidos são formadas para minimizar a energia total do sistema. O trabalho apresentado nesta tese de doutorado consiste no estudo da formação de ligas em ilhas de GeSi:Si(001) cristalinas obtidas via crescimento epitaxial tanto no regime cinético quanto no de quasi-equilíbrio, através da determinação da composição química e dos campos de deformação dessas nanoestruturas. No regime cinético de crescimento investigou-se as moléculas de pontos quânticos (QDMs, do inglês Quantum Dot Molecules), estruturas compostas por uma depressão central com facetas 105 e quatro ilhas alongadas, também com facetas 105 , ao seu redor, formadas a partir de um processo conhecido como nucleação cooperativa. As QDMs foram obtidas por epitaxia de feixe molecular para condições bastante específicas de crescimento: Si0,7 Ge0,3, 550 C e taxa de deposição de 1,0 A/s. A estreita distribuição de tamanhos desse conjunto de ilhas permitiu o mapeamento de sua composição e deformação através da difração de raios-x em incidência rasante (GIXRD, do inglês Grazing Incidence X-Ray Diffraction), apesar da simetria complexa envolvida. A concentração de Ge varia significativamente nessas nanoestruturas e difere consideravelmente da sua composição nominal, atingindo quase 100 % no topo das ilhas, indicando uma redistribuição atômica significativa durante o crescimento, associada a processos de difusão na superfície. Regiões comprimidas e tencionadas foram encontradas nas QDMs e no substrato, em acordo com cálculos de elementos finitos para a relaxação da rede. A formação das ligas em ilhas de GeSi e a influência dos diferentes mecanismos envolvidos foram investigadas para morfologias correspondentes ao regime de quasi-equilíbrio. As forças generalizadas que governam a formação dessas ligas, tensão e gradiente do potencial químico, bem como os potencias termodinâmicos, entalpia, entropia de mistura e energia livre de Gibbs, foram quantitativamente avaliados para um conjunto de amostras de domos obtido por deposição via química. Tratamentos térmicos pós-crescimento em ambientes de H2e de PH3 foram utilizados para fazer-se uma analogia com um sistema aberto e outro fechado do ponto de vista termodinâmico, respectivamente. A entropia de mistura tem uma contribuição bastante significativa para a energia total desses sistemas, prevalecendo sobre a entalpia, associada µas deformações do filme. Há essencialmente três mecanismos envolvidos na formação das ligas de GeSi: a troca de átomos Si/Ge que acontece durante o crescimento, a difusão na superfície e a difusão intra-ilha. A importância relativa entre cada mecanismo foi avaliada através da determinação do perfil de composição para ilhas de Ge:Si(001) em formato de domos mediante um conjunto de ataques químicos seletivos e medidas de GIXRD. Para amostras crescidas a mais alta taxa de deposição a interdifusão foi reduzida. A difusão na superfície do Si dominou durante o tratamento térmico em H2 (sistema aberto), enquanto a difusão do Ge e a difusão intra-ilha prevaleceram durante o tratamento térmico em um ambiente de PH3(sistema fechado no que concerne o Si). Ainda no regime de equilíbrio local, estudou-se a formação de misturas em superdomos: ilhas formadas a partir dos domos, com facetas bem definidas e planos de discordâncias que aliviam as tensões do filme. Essas estruturas desenvolvem-se através do processo de amadurecimento de Ostwald, no qual as ilhas maiores crescem ainda mais µas custas das menores. Em resumo, investigou-se a composição química de diversas morfologias de nanoestruturas de GeSi crescidas epitaxialmente sobre Si(001). Os processos de formação destas ligas foram avaliados experimentalmente. Finalmente, pôde-se investigar em detalhes a termodinâmica de sistemas nanométricos / Abstract: The structural and electronic properties of nanoscale materials strongly depend on the chemical composition, as well as their size and shape. A big variety of morphologies can be achieved by controlling the experimental conditions during the epitaxial growth of Ge on a Si(001) substrate. In particular, three-dimensional islands with well defined size and shape are formed in order to minimize the system's total energy. The work presented in this thesis consist in the study of the alloying in GeSi:Si(001) crystalline islands obtained by epitaxial growth methods in the kinetically-limited and the quasi-equilibrium regimes, beyond the chemical composition and strain ¯elds determination of these nanostructures. In the kinetically-limited regime the Quantum Dot Molecules (QDMs) were investigated. These nanostructures are composed by a central f 105 g faceted pit and four elongated islands, also 105 faceted, at the pit surrounding, and formed by a cooperative nucleation process. The QDMs were obtained by molecular beam epitaxy for speci¯c growth conditions: Si0:7Ge0:3, substrate temperature of 550 C and deposition rate of 1.0 º A/s. The narrow size distribution of the ensemble of islands allowed the chemical composition and strain fields maps by Grazing Incidence Anomalous X-Ray Diffraction (GIXRD), besides the complex symmetry involved. The Ge concentration was found to vary significantly from the nominal composition, it is almost 100 % at the islands top, indicating a strong atomic redistribution during the film growth, associated to surface diffusion processes. Compressed and tensile regions were found to co-exist inside the QDMs and the Si substrate, in agreement with finite element calculations performed for the same morphologies for the lattice relaxation. The alloying issue in GeSi islands and the mechanisms influence were investigated for different morphologies corresponding to the quasi-equilibrium regime. The driving forces for alloying - stress and the chemical potential gradient - and the thermodynamical potentials - enthalpy, mixing entropy and the Gibbs free energy - were quantitatively evaluated for an ensemble of samples of dome shaped islands obtained by chemical vapor deposition. Pos-growth annealing in H2 and PH3 environments were used in analogy with an open and closed systems from the thermodynamical point of view, respectively. The mixing entropy was found to have a strong contribution to the total energy, prevailing from the enthalpy, associated with the strain. The are essentially three different mechanisms involved in the alloying of epitaxial nanocrystals: intermixing between Si/Ge atoms during growth, surface diffusion, and intraisland diffusion. The relative importance of each mechanism was evaluated in determining a particular composition profile for dome-shaped Ge:Si (001) islands using a selective chemical etching and GIXRD measurements. For samples grown at a faster rate, intermixing during growth was reduced. Si surface diffusion dominates during H2 annealing (opened system), whereas Ge surface diffusion and intraisland diffusion prevail during annealing in a PH3 environment (closed system concerning Si). Also in the quasi-equilibrium regime, the superdomes (SDs) formation were studies. These islands, with well defined facets, are formed trough the dome-shaped ones and present dislocation which relieves the strain. These nanostructures are formed due to Ostwald ripening process, where the larger islands growth by consuming the smaller ones. Summarizing, the chemical composition were investigated in SiGe:Si(001) epitaxial nanostructures with different morphologies. The alloying processes were experimentally evaluated. Finally, the thermodynamical potentials were investigated in detail for nanoscale systems / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Biofilmes são aglomerados complexos de células microbianas que crescem na superfície de um material sólido, como um metal. As superfícies metálicas são amplamente utilizadas em dispositivos biomédicos cirúrgicos e em superfícies de mobiliário intra-hospitalares as quais podem ser infectadas por bactérias epidemiologicamente importantes e permitir o desenvolvimento de um biofilme. O objetivo desse trabalho foi avaliar a superfície topográfica dos metais puros, incluindo: chumbo, cromo, estanho, ferro e níquel, avaliar a aderência bacteriana nestas superfícies, com a consequente formação de biofilme e a potencial citotoxicidade dos metais por meio de microscopia de força atômica (MFA), microscopia óptica e microscopia eletrônica de varredura (MEV). A metodologia constou de observações microscópicas e procedimentos bacteriológicos. A aderência bacteriana foi verificada por meio de MEV e a viabilidade celular bacteriana por contagem de Unidades Formadoras de Colônia (UFC). A citotoxicidade dos metais foi avaliada frente a células CHO-K1 por ensaio XTT. As bactérias selecionadas foram: Escherichia coli, Pseudomonas aeruginosa (gram-negativos); Staphylococcus epidermidis e Staphylococcus aureus (gram-positivos) Para realizar o estudo, foram preparados corpos de prova dos metais puros e colocados em contato com cada uma das bactérias (da ordem 108 UFC/mL). Os resultados mostraram a formação de biofilme em cada um dos corpos de prova. A contagem das células viáveis demonstrou a recuperação de 105 UFC/mL para Escherichia coli, Pseudomonas aeruginosa e Staphylococcus aureus após contato com os metais chumbo, cromo, estanho, ferro e níquel, e para Staphylococcus epidermidis após contato com chumbo, níquel e cromo houve uma redução bacteriana de 103 UFC/mL. Para Staphylococcus epidermidis após contato com estanho foram recuperadas 1,14 x 102 UFC/mL e para o ferro, houve recuperação de 1,3 x 103 UFC/mL. A MEV demonstrou nestas superfícies metálicas, os bacilos e cocos aderidos e agrupados em uma massa amorfa formando biofilme. Os resultados da rugosidade (Ra) de cada uma destas superfícies obtidos por MFA em varredura em 2 microns da superfície, mostram que o Ra do chumbo foi de 38.258 &#956m; estanho 13.481 &#956m; níquel 3.929 &#956m; ferro 3.689 &#956m e cromo 2.097 &#956m. Os resultados do teste XTT, após contato com as células CHO-K1, mostram que o ferro foi citotóxico para estas células (p<0,05) diferença estatisticamente significante em relação ao controle negativo. Os metais puros avaliados nas condições experimentais do estudo mostram que as superfícies dos metais puros não impedem a aderência bacteriana e formação de biofilme das bactérias selecionadas. / Biofilms are complex microbial cell clusters that are growing on the solid material surface, as a metal. The metalic surfaces are widely used in surgical biomedical devices and hospital furniture surfaces which can be infected by important bacteria and to allow biofilm development. The aim of this work was to evaluate the topographic surface of the lead, chromium, tin, iron and nickel pure metals, evaluate bacterial adhesion in these surfaces with subsequent biofilm formation and the potential cytotoxicity of metals through force microscopy atomic (AFM), optical microscopy and scanning electron microscopy (SEM). The methodology consisted of microscopic observations and bacteriological procedures. Bacterial adherence was observed by SEM and the bacterial cell viability by colony forming units colony counts (CFU). The cytotoxicity of metals was evaluated using CHO-K1 cells by XTT assay.The isolated bacteria were: Escherichia coli, Pseudomonas aeruginosa (gram-negative), and Staphylococcus epidermidis and Staphylococcus aureus (gram positive). In order to realize this study, samples of pure metals were prepared and put in touch with each bacteria (in 108 CFU/mL). The results show biofilm formation in each of the specimens. The counting of viable cells demonstrated a recovery 105 CFU/mL for Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus after contact with lead, chromium, tin, iron and nickel metals and Staphylococcus epidermidis after contact with lead, nickel and chromium there was a bacterial reduction of 103 CFU/mL. For Staphylococcus epidermidis after contact with tin were recovered 1.14 x 102 CFU / mL and the iron, there was a recovery of 1.3 x103 CFU/mL. The data show that there was a bacterial reduction of 103 CFU/mL viable cells. Staphylococcus epidermidis on contact with tin were recovered 1,14 x 102 and the iron recovery was 1,3 x 103 UFC/mL. SEM showed the metal surfaces, bacilli and coccus adhered and grouped in an amorphous mass forming biofilm. The results of the roughness (Ra) of each of the surfaces obtained by AFM scan of 2 microns from the surface, show that the RA lead was 38,258 uM; Tin 13,481 uM; Nickel 3,929 uM; iron 3,689 &#956m and chrome 2,097 &#956m. The results of XTT, after contact with the CHO-K1 cells, show that iron was cytotoxic to these cells (p <0.05) statistically significant difference compared to the negative control. Pure metals evaluated in the experimental conditions of the study show that the surfaces of pure metals do not prevent bacterial adherence and biofilm formation of the bacteria selected.