Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals

Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths.  We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process.  We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.

Phenotypic profile of expanded NK cells in chronic lymphoproliferative disorders: a surrogate marker for NK-cell clonality

Currently, the lack of a universal and specific marker of clonality hampers the diagnosis and classification of chronic expansions of natural killer (NK) cells. Here we investigated the utility of flow cytometric detection of aberrant/altered NK-cell phenotypes as a surrogate marker for clonality, in the diagnostic work-up of chronic lymphoproliferative disorders of NK cells (CLPD-NK). For this purpose, a large panel of markers was evaluated by multiparametric flow cytometry on peripheral blood (PB) CD56(low) NK cells from 60 patients, including 23 subjects with predefined clonal (n = 9) and polyclonal (n = 14) CD56(low) NK-cell expansions, and 37 with CLPD-NK of undetermined clonality; also, PB samples from 10 healthy adults were included. Clonality was established using the human androgen receptor (HUMARA) assay. Clonal NK cells were found to show decreased expression of CD7, CD11b and CD38, and higher CD2, CD94 and HLADR levels vs. normal NK cells, together with a restricted repertoire of expression of the CD158a, CD158b and CD161 killer-associated receptors. In turn, NK cells from both clonal and polyclonal CLPD-NK showed similar/overlapping phenotypic profiles, except for high and more homogeneous expression of CD94 and HLADR, which was restricted to clonal CLPD-NK. We conclude that the CD94(hi)/HLADR+ phenotypic profile proved to be a useful surrogate marker for NK-cell clonality.

Abordagem rítmica probabilística aplicada em análises de fluxo e estabilidade de taludes

Tese (doutorado)—Universidade de Brasília, Faculdade de Tecnologia, Programa de Pós-Graduação em Geotecnia, 2015.

MINING AND VERIFICATION OF TEMPORAL EVENTS WITH APPLICATIONS IN COMPUTER MICRO-ARCHITECTURE RESEARCH

Computer simulation programs are essential tools for scientists and engineers to understand a particular system of interest. As expected, the complexity of the software increases with the depth of the model used. In addition to the exigent demands of software engineering, verification of simulation programs is especially challenging because the models represented are complex and ridden with unknowns that will be discovered by developers in an iterative process. To manage such complexity, advanced verification techniques for continually matching the intended model to the implemented model are necessary. Therefore, the main goal of this research work is to design a useful verification and validation framework that is able to identify model representation errors and is applicable to generic simulators. The framework that was developed and implemented consists of two parts. The first part is First-Order Logic Constraint Specification Language (FOLCSL) that enables users to specify the invariants of a model under consideration. From the first-order logic specification, the FOLCSL translator automatically synthesizes a verification program that reads the event trace generated by a simulator and signals whether all invariants are respected. The second part consists of mining the temporal flow of events using a newly developed representation called State Flow Temporal Analysis Graph (SFTAG). While the first part seeks an assurance of implementation correctness by checking that the model invariants hold, the second part derives an extended model of the implementation and hence enables a deeper understanding of what was implemented. The main application studied in this work is the validation of the timing behavior of micro-architecture simulators. The study includes SFTAGs generated for a wide set of benchmark programs and their analysis using several artificial intelligence algorithms. This work improves the computer architecture research and verification processes as shown by the case studies and experiments that have been conducted.

A REMOTE SENSING APPROACH TO CHARACTERIZE THE HYDROGEOLOGY OF MOUNTAINOUS AREAS: APPLICATION TO THE QUITO AQUIFER SYSTEM (QAS), ECUADOR

Climate change, intensive use, and population growth are threatening the availability of water resources. New sources of water, better knowledge of existing ones, and improved water management strategies are of paramount importance. Ground water is often considered as primary water source due to its advantages in terms of quantity, spatial distribution, and natural quality. Remote sensing techniques afford scientists a unique opportunity to characterize landscapes in order to assess groundwater resources, particularly in tectonically influenced areas. Aquifers in volcanic basins are considered the most productive aquifers in Latin America. Although topography is considered the primary driving force for groundwater flows in mountainous terrains, tectonic activity increases the complexity of these groundwater systems by altering the integrity of sedimentary rock units and the overlying drainage networks. Structural controls affect the primary hydraulic properties of the rock formations by developing barriers to flow in some cases and zones of preferential infiltration and subterranean in others. The study area focuses on the Quito Aquifer System (QAS) in Ecuador. The characterization of the hydrogeology started with a lineament analysis based on a combined remote sensing and digital terrain analysis approach. The application of classical tools for regional hydrogeological evaluation and shallow geophysical methods were useful to evaluate the impact of faulting and fracturing on the aquifer system. Given the spatial extension of the area and the complexity of the system, two levels of analysis were applied in this study. At the regional level, a lineament map was created for the QAS. Relationships between fractures, faults and lineaments and the configuration of the groundwater flow on the QAS were determined. At the local level, on the Plateaus region of the QAS, a detailed lineament map was obtained by using high-spatial-resolution satellite imagery and aspect map derived from a digital elevation model (DEM). This map was complemented by the analysis of morphotectonic indicators and shallow geophysics that characterize fracture patterns. The development of the groundwater flow system was studied, drawing upon data pertaining to the aquifer system physical characteristics and topography. Hydrochemistry was used to ascertain the groundwater evolution and verify the correspondence of the flow patterns proposed in the flow system analysis. Isotopic analysis was employed to verify the origin of groundwater. The results of this study show that tectonism plays a very important role for the hydrology of the QAS. The results also demonstrate that faults influence a great deal of the topographic characteristics of the QAS and subsequently the configuration of the groundwater flow. Moreover, for the Plateaus region, the results demonstrate that the aquifer flow systems are affected by secondary porosity. This is a new conceptualization of the functioning of the aquifers on the QAS that will significantly contribute to the development of better strategies for the management of this important water resource.

Calibration and operational analysis of variable speed limits for high flow condition

Variable Speed Limits (VSL) is a control tool of Intelligent Transportation Systems (ITS) which can enhance traffic safety and which has the potential to contribute to traffic efficiency. This study presents the results of a calibration and operational analysis of a candidate VSL algorithm for high flow conditions on an urban motorway of Queensland, Australia. The analysis was done using a framework consisting of a microscopic simulation model combined with runtime API and a proposed efficiency index. The operational analysis includes impacts on speed-flow curve, travel time, speed deviation, fuel consumption and emission.

Data flow analysis of embedded program expressions

Data flow analysis techniques can be used to help assess threats to data confidentiality and integrity in security critical program code. However, a fundamental weakness of static analysis techniques is that they overestimate the ways in which data may propagate at run time. Discounting large numbers of these false-positive data flow paths wastes an information security evaluator's time and effort. Here we show how to automatically eliminate some false-positive data flow paths by precisely modelling how classified data is blocked by certain expressions in embedded C code. We present a library of detailed data flow models of individual expression elements and an algorithm for introducing these components into conventional data flow graphs. The resulting models can be used to accurately trace byte-level or even bit-level data flow through expressions that are normally treated as atomic. This allows us to identify expressions that safely downgrade their classified inputs and thereby eliminate false-positive data flow paths from the security evaluation process. To validate the approach we have implemented and tested it in an existing data flow analysis toolkit.