Submitted by MARCIA ROVADOSCHI (marciar@unifra.br) on 2018-08-16T12:53:12Z No. of bitstreams: 2 Dissertacao_RafaeliOlequesPires.pdf: 1220663 bytes, checksum: 54cb1e137bd526bbde3fe44c848329e7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-08-16T12:53:12Z (GMT). No. of bitstreams: 2 Dissertacao_RafaeliOlequesPires.pdf: 1220663 bytes, checksum: 54cb1e137bd526bbde3fe44c848329e7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2011-03-29 / From the 60s, a debate about a new and promising world-wide technologies started, and it was called nanotechnology. Together with the global growth, many fields of research had started to use in their studies, for example, in the pharmaceutical area. Among these innovations, we can include the discovery of new composites, biodegradable products and the development of carries in nanoscale. Among the most used nanocarries there are nanosphere and nanocapsules, showing controlled release compared to conventional drug delivery systems. The release process was studied by some authors that described this process using mathematical equations, one for each use. However, actually, there is no mathematical equation that represents the behavior of the nanocarries, emphasizing the factors relevant at nanoscale. Then, the present study analyzed a specific carrier - nanocapsule - to develop a mathematical equation that represents the behavior of the drug release from polymeric nanocapsules. For the construction of the mathematical model, we used mathematical modeling as methodology. We proved there isn’t change in particle size during the release process, when used poly ( -caprolactone). After that, we noticed that the parameters that interfere in the release process were drug solubility in the oil core of nanocapsule and the encapsulation efficiency. Based in these two parameters, the mathematical model was constructed and then validated, showing to be an good model to describe the drug release profiles from nanocapsules. / A partir da década de 60, iniciou-se o debate sobre uma das mais novas e promissoras tecnologias mundiais, a nanotecnologia. Juntamente com o crescimento mundial, vários campos de pesquisa começaram a utilizá-la em seus estudos, como por exemplo, as inovações na área farmacêutica. Entre estas inovações destacam-se a descoberta de novos compostos, produtos biodegradáveis e o desenvolvimento de carreadores em escala nanométrica: os nanocarreadores. Estes, os mais utilizados são as nanoesferas e nanocápulas, por apresentarem uma liberação sustentada e controlada de fármaco comparada a formulações convencionais. À medida que os anos foram passando, o processo de liberação de fármaco foi sendo explicado e representado por equações matemáticas distintas, cada uma com suas aplicações e peculiaridades. Mas, atualmente, não existe nenhuma equação matemática que represente o comportamento dos nanocarreadores, dando ênfase aos fatores relevantes na nanoescala. Assim, o presente trabalho analisou um carreador específico – nanocápsula – para modelar uma equação matemática que represente o comportamento da liberação de fármacos a partir do mesmo. Para a construção do modelo matemático, foi utilizada a modelagem matemática como metodologia. Foi comprovado que não ocorre modificação no tamanho de partícula durante o processo de liberação, quando utilizado o polímero poli( -caprolactona). Depois disso, percebeu-se que o parâmetro que influencia no processo de liberação é a solubilidade do fármaco no núcleo oleoso da nanocápsula e a taxa de associação às naopartículas. Baseado nestas duas variáveis, foi construído o modelo matemático, que quando validado, mostrou-se ser um excelente modelo para descrever os perfis de liberação de fármacos através das nanocápsulas.

A combination of magnetic sensors with magnetic nanoparticles offers a promising approach for highly sensitive, simple, and rapid detection of cancer cells and biomolecules. The challenge facing the field of magnetic biosensing is the development of low-cost devices capable of superconducting quantum interference device (SQUID)-like field sensitivity at room temperature. In another area of interest, improving the sensitivity of existing electromagnetic field sensors for microwave energy sensing applications is an important and challenging task. In this dissertation, we have explored the excellent magnetoimpedance and microwave absorption responses of soft ferromagnetic amorphous ribbons and microwires for the development of high-performance magnetic biodetectors and microwave energy sensors. We have developed the effective approaches to improve the magnetoimpedance response of Co65Fe4Ni2Si15B14 amorphous ribbons by tuning their dimension and/or coating them with thin layers of CoFe2O4. Coating amorphous and crystalline CoFe2O4 films on the ribbon surface have opposite impacts on the magnetoimpedance response. Pulsed laser deposition (PLD) is shown to be a novel in-situ annealing and coating method for improving the magnetoimpedance response of the soft ferromagnetic amorphous ribbons for advanced sensor applications. The magnetoimpedance responses are also enhanced in multi-microwire systems relative to their single microwires. We have introduced a new method of combining the magnetoresistance (MR), magnetoreactance (MX), and magnetoimpedance (MI) effects of a soft ferromagnetic amorphous ribbon to develop an integrated biosensor with enhanced sensitivity and tunable frequency. While existing MI biosensors have limited sensitivities, we show that by exploiting the MR and MX effects it is possible to improve the sensitivity of the biosensor by up to 50% and 100%, respectively. The MX-based approach shows the most sensitive detection of superparamagnetic (Fe3O4) nanoparticles at low concentrations, demonstrating a sensitivity level comparable to that of a SQUID-based biosensor. Unlike a SQUID, however, the proposed MX technique is cryogen-free and operates at room temperature, providing a promising avenue to the development of low-cost highly sensitive biosensors. We have further improved the detection sensitivity of the MI and MX biosensors by patterning the sensing (ribbon) surface with nano/micro-sized holes, using the etching or focused ion beam (FIB) technique. These biosensors have been successfully employed to detect and quantify various bioanalytes, such as Curcumin-type anticancer drugs, bovine serum albumen (BSA) proteins, and Lewis lung carcinoma (LLC) cancer cells that have taken up the surface-functionalized Fe3O4 nanoparticles. Since Fe3O4 nanoparticles are widely used as magnetic resonance imaging (MRI) contrast agents, our biosensing technique can also be used as a new, low-cost, fast and easy pre-detection method before MRI. Finally, we have developed a new method of using a soft ferromagnetic glass-coated amorphous microwire as a microwave absorber for fabrication of a fiber Bragg grating-based microwave energy sensor with improved sensitivity and less perturbation of the microwave field. As compared to a similar approach that uses gold to absorb electromagnetic radiation, the microwire yields a device with greater sensitivity (~10 times at f = 3.25 GHz) relative to the perturbation of the microwave field. A correlation between the magnetic softness and microwave absorption in the microwires has been established, paving the way to improve the performance of the microwave energy sensor by tailoring their soft magnetic properties.

In this dissertation, I present the results of a systematic study on novel multifunctional nanostructure systems for magnetic hyperthermia applications. All the samples have been synthesized, structurally/magnetically characterized, and tested for magnetic hyperthermia treatment at the Functional Materials Laboratory of the University South Florida. This work includes studies on four different systems: (i) Core/shell Fe/γ-Fe2O3 nanoparticles; (ii) Spherical and cubic exchange coupled FeO/Fe3O4 nanoparticles; (iii) Fe3O4 nano-octopods with different sizes; (iv) High aspect ratio FeCo nanowires and Fe3O4 nanorods. In particular, we demonstrated the enhancement of the heating efficiency of these nanostructures by creating monodisperse and highly crystalline nanoparticles, and tuning their magnetic properties, mainly their saturation magnetization (MS) and effective anisotropy, in controlled ways. In addition, we studied the influence of other parameters, such as the size and concentration of the nanoparticles, the magnitude of the applied AC magnetic field, or different media (agar vs. water), on the final heating efficiency of these nanoparticles. For the core/shell Fe/γ-Fe2O3 nanoparticles, a modest heating efficiency has been obtained, resulting mainly from the strong reduction in MS caused by the shrinkage of the core with time. However, for sizes above 14 nm, the shrinkage process is much slower and the obtained heating efficiency is better than the one exhibited by conventional solid nanoparticles of the same size. In the case of the exchange-coupled FeO/Fe3O4 nanoparticles, we successfully created two sets of comparable particles: spheres with 1.5 times larger MS than the cubes, and cubes with 1.5 times larger effective anisotropy than the spheres, while keeping the other parameters the same. Our results show that increasing the effective anisotropy of the nanoparticles gives rise to a greater heating efficiency than increasing their MS. The Fe3O4 nano-octopods, with enhanced surface anisotropy, present better heating efficiency than their spherical and cubic nanoparticles, especially in the high field region, and we have shown that by tuning their size and the effective anisotropy, we can optimize their heating response to the applied AC magnetic field. For magnetic fields, smaller than 300−400 Oe we found that the smallest nano-octopods give the best heating efficiency. Yet if we increase the AC field value, the bigger octopods show an increased heating efficiency and become more effective. Finally, the FeCo nanowires and Fe3O4 nanorods exhibit enhanced heating efficiency with increasing aspect ratio when aligned in the direction of the applied AC magnetic field, due to the combined effect of shape anisotropy and dipolar interactions. Of all the studied systems, these 1D high aspect ratio nanostructures have displayed the highest heating rates. All of these findings point toward an important fact that tuning the structural and magnetic parameters in general, and the effective anisotropy in particular, of the nanoparticles is a very promising approach for improving the heating efficiency of magnetic nanostructures for enhanced hyperthermia.

Crystal symmetry and elemental composition play a critical role in determining the physical properties of materials. In layered van der Waals (vdW) heterostructures, a two-dimensional (2D) material layer can be influenced by interactions between adjacent layers, dictating that the measured properties of the combined system will be in part derived from the geometric structure within the active layers. This thesis examines active crystal symmetry tuning in composite heterostructures of two-dimensional (2D) materials, engineered via nanomechanically assisted twist angle control, and designed by careful consideration of lowest energy stacking configurations. The material systems, devices, and experimental setups described in this thesis constitute a platform featuring highly programmable properties that are on-demand and reversible. Two prototypical systems are discussed in detail. The first is graphene encapsulated between boron nitride (BN) crystals, wherein the alignment state between the three layers is controlled. The second is the same system, but with no graphene between the encapsulating BN layers. In both systems, a long-wavelength geometric interference pattern, also known as a moiré pattern, forms between the adjacent crystals as a consequence of lattice-constant mismatch and twist angle. The moiré pattern caries its own symmetry properties that are also demonstrated to be tunable, and can be thought of as an artificially constructed superlattice of periodic potential with wavelength much greater than the lattice constants of the constituent layers. In the BN-encapsulated graphene system we show drastic tunability of band gaps at primary and secondary Dirac points (PDP and SDPs) indicating reversible on-demand inversion symmetry breaking, as well as evidence of dual coexisting moiré superlattices and additional higher-order interference patterns that form between them. The all-BN system shows substantial enhancement and suppression of second harmonic generation (SHG) response from the vdW interface between the BN crystals when the quadrupole component of the SHG response is engineered to be minimal, by controlling for total layer number and layer number parity. Changes in the physical properties of each composite system are measured with a combination of electronic transport measurements, and optical measurements (Raman and SHG), as well as piezo-force microscopy (PFM) measurements that give direct imaging of the moiré pattern. A number of invented and adapted fabrication and actuation techniques for controlling the twist angle of a bulk vdW crystal are discussed, and in the latter portion of this thesis these techniques are extended to include actuation of monolayer flakes of 2D crystals. In this discussion several case studies are discussed, including twist angle control for a single sample monolayer tungsten diselenide on monolayer molybdenum diselenide, as well as twist angle control for twisted bilayer graphene and graphene on BN. Additionally, a novel in-plane bending mode for graphene on BN is demonstrated using similar techniques. Further discussion of actuation via traditional electrostatic MEMS techniques is also included, illustrating complete on-chip control for on-demand nanomechanical actuation of 2D materials in vdW heterostructures.

Owing to their increasing application and potential toxicity, engineered nanoparticles (ENPs) have been considered as a potential agricultural contaminant that may pose unknown risk to human beings. However, many techniques require invasive and complicated sample preparation procedures to detect and characterize engineered nanomaterials in complex matrices. In the first part of this thesis, we present a non-destructive and label-free approach based on surface enhanced Raman spectroscopic (SERS) mapping technique to qualitatively detect and characterize gold nanoparticles (AuNPs), on and in spinach leaves in situ. We were able to detect the clearly enhanced signals from AuNPs at 15 to 125 nm on and in spinach leaves. Peak characterizations revealed the aggregation status of Au NPs and their interactions with plant biomolecules, such as chlorophylls and carotenoids. This developed approach will open a new analytical platform for various researches on studying ENPs' adhesion and accumulation. The second part focuses on investigating the interaction between AgNPs and plant leaves using surface enhanced Raman spectroscopy. AgNPs of different surface coating (citrate, CIT and polyvinylpyrrolidone, PVP) and size (40 and 100 nm), were deposited onto spinach leaves. SERS signals produced from all kinds of AgNPs exhibited a unique C-S stretching peak at 650-680 cm-1. In vitro study indicates this peak may originate from the interaction between AgNPs and cysteine-like compounds based on the peak pattern recognition. The interaction between AgNPs and the cysteine-like compounds happened as soon as 0.5 h after AgNPs exposure. The in situ replacement of the CIT with the cysteine-like compounds on the AgNP surfaces was faster compared to that of the PVP. Based on the mapping of the highest C-S peak, we observed the CIT-AgNPs penetrated faster in spinach leaves than the PVP-AgNPs, although the penetration profile for both of them is similar after 48 h (P ˂ 0.05). The 40 nm CIT-AgNPs was able to penetrate deeper (to the depth of 183 ± 38 µm) than the 100 nm CIT-AgNPs (to the depth of 90 ± 51 µm) after 48 h. The results obtained here demonstrate the size of AgNPs is the main factor that affects the penetration depth, and the surface coating mainly affects the initial speed of interaction and penetration. This study helps us to better understand the distribution and biotransformation of AgNPs in plants. In the third part, the removal efficiency of postharvest washing on AgNPs that had accumulated on fresh produce was evaluated. Ten µL commercially available 40 nm citrate coated AgNPs (0.4 mg L-1) were dropped to a (1×1 cm2) spot on spinach leaves, followed by washing with deionized water (DI water), Tsunami® 100 (80 mg L-1) or Clorox® bleach (200 mg L-1). Then, AgNPs removal efficiency of the three treatments was evaluated by surface enhanced Raman spectroscopy (SERS), scanning electron microscopy (SEM)-energy dispersive spectrometer (EDS), and inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS results showed that deionized water removed statistically insignificant amounts of total Ag, whereas Tsunami® 100 and Clorox® bleach yielded 21% and 10% decreases in total Ag, respectively (P < 0.05). The increased removal efficiency resulted from Ag NPs dissolution and Ag+ release upon contact with the oxidizing agents in Tsunami® 100 (peroxyacetic acid, hydrogen peroxide) and Clorox® bleach (sodium hypochlorite). According to the SERS results, the deionized water and Tsunami® 100 treatments removed nonsignificant amounts of AgNPs. Clorox® bleach decreased Ag NPs by more than 90% (P < 0.05), however, SEM-EDS images revealed the formation of large silver chloride (AgCl) crystals (162 ± 51 nm) on the leaf, which explained low total Ag removal from ICP-MS. This study indicates current factory washing methods for fresh produce may not be effective in reducing AgNPs (by water and Tsunami® 100) and total Ag (by all three means). This highlights the necessity to develop an efficient washing method for NP removal from food surfaces in the future.

Nanofluidics is an emerging field with many science and engineering applications. The physics of material transport through nanochannels are of interest in filtration, sensing, device miniaturization, and biomimetics. To address such ambitions with nanofluidic tools will require advancements in our understanding and control over nanofluidic systems. This work contributes to electrokinetic phenomena, characterization techniques, and applications in nanofluidics. Ion transport data through nanopipettes are used to validate a finite element model for nonlinear electrokinetic flows. With the model, we conclude that asymmetric surfaces induce fluid vortices and provide insight into supporting mathematical techniques. We then establish nanobubble-plugged nanopipettes as promising ionic devices due to the electrokinetic effects of three-phase interfaces. Using cryogenic transmission electron microscopy, ion current measurements, and extensive physical modeling, we conclude that nanobubble plugs are metastable, slow-growing, and induce strong current rectification and enhancement. All these insights let us study microbial surfaces using electrokinetic phenomena detected by a scanned nanopipette. Over immobilized Pseudomonas aerugonsa cells and Δphz-type biofilms, we detect topographic and surface charge properties due to voltage-dependent signals through a scanned nanopipette probe. Our efforts establish a fast hopping probe scanning ion conductance microscopy technique for long-range surface charge detection. Finally, we use an integrated carbon nanotube channel to demonstrate how solid-state charge can drive electrokinetic flows through Coulomb drag coupling.

>Magister Scientiae - MSc / TiO2 nanoparticle films are important electron transport layers (ETLs) in photovoltaics such as dye-sensitised, perovskite and polymer hetero-junction solar cells. These films, however, have significant electron trap-sites as a result of the large density of oxygen vacancies present in nanosized TiO2. These trap-sites cause electron-hole recombination and ultimately lower photon-tocurrent conversion efficiency of the underlying cell during operation. Doping the TiO2 lattice with low atomic number elements such as nitrogen is a proven method to overcoming the charge transport inefficiency of TiO2 ETLs; another is the use of one-dimensional (1D) nanowires (NWs), instead of nanoparticles. Modification of TiO2 with non-metals leads to optical bandgap narrowing, improvement in electron conductivity and increased electron lifetime in the ETL layer. However, a lot of scope exists in understanding and fully quantifying the relationship between optical property, for example light transmission and bandgap modification, versus the doping concentration and type. Most doping approaches are in-situ and involve the addition of a dopant precursor (usually a salt) during the synthesis of TiO2 nanostructures – this invariably leads to uncontrolled doping levels, anion contamination and poor-quality materials – a need thus exists to develop simple, controllable doping approaches. One such approach, which forms the basis of this study, is ex-situ doping by means of plasma generated species in a controlled environment. This field of study is fairly novel and not widely studied, requiring more research to understand the doping mechanisms and influence on the optical and electronic properties of the underlying nanomaterials. In particular, controlled doping of TiO2 with nitrogen using radio-frequency generated (RF) plasma requires vigorous experimentation and characterisation. Inaccuracy of the deposition parameters during exposure remains a common drawback for this approach in addition to a lack of understanding of the surface interaction between the N2 species and specimen during irradiation.

In this research, some fundamental aspects of surface growth processes are investigated through in-situ synchrotron based x-ray techniques, including a new coherent x-ray technique developed as part of this work, as well as ex-situ Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and simulation. The first part of this dissertation focuses on careful examination of early-time kinetics of indium (In) island growth via real-time Grazing Incidence Small Angle X-ray Scattering (GISAXS) since it is a good example of simple growth systems allowing the results to be directly compared to surface growth theories and also because of its technical relevance for III–V semiconductor deposition. The results are compared with Family-Meakin (FM) droplet growth and coalescence theory through Monte Carlo simulations. In addition, room temperature deposition of amorphous silicon (a-Si) through DC magnetron sputtering onto a silicon (Si) substrate has been investigated via real-time GISAXS. The deposition conditions are optimized to create an idealized growth environment so that the results can be directly compared to surface growth models. Performing the deposition at room temperature results in adatoms having limited surface mobility, which causes formation of correlated mound-like structures on the surface at the early stages of the growth. The correlation distance between the mount-like structures is found to grow linearly with time. The results are compared to a ballistic deposition model including self-shadowing and desorption effects. The second half of this study focuses on investigation of the kinetic roughening dynamics of thin film growth, where the local dynamics are measured after the overall kinetic evolution of the surface roughness reach a steady-state saturation. Coherent X-ray GISAXS (Co-GISAXS) has been developed as a new approach to investigate surface dynamics during thin film deposition. Room temperature deposition of a-Si and amorphous tungsten disilicide (a-WSi2) through DC magnetron sputtering onto respectively Si and SiO2 substrates has been examined. The overall dynamics are complex, but power law behavior is observed for the structure factor and correlation times at the most surface sensitive section of the data. This research demonstrated that Co-GISAXS is a powerful new approach to investigate the correlated dynamics between surface and sub-surface structures. / 2016-10-27T00:00:00Z

Emission of electromagnetic radiation due to the temperature of a body is an inherent property in nature. Electromagnetic radiation sources relying on thermal emission are critical in application of energy harvesting, lighting, spectroscopy and sensing. However, many of these sources, typically made of several hundreds of microns thick bulk objects, are inefficient and radiate much less power than an ideal blackbody. In the first part of this work, we demonstrate an efficient thermal emitter based on material films that are nanometers thin. Nano-film based thermal sources are generally poor emitters, but have received much interest lately since they require significantly lower heating power compared to their bulk counterparts. We show a novel approach for realizing thin-film based blackbody emitters by placing them inside an external optical cavity, engineered to provide enhancement of thermal emission while maintaining a constant temperature. Our approach is independent of the emitter material and can be tuned to operate at any temperature since the optical elements and the emitter are physically disconnected. The work opens new avenues for realizing blackbody-type thermal sources consuming significantly lower heating power than the current state-of-art, thus suggesting direct applications in lighting, spectroscopy and energy harvesting. Furthermore, we utilize the nano-film broadband emitters for demonstrating heat transfer that beats conventional blackbody limit at deep-subwavelength distances. We demonstrate the first of its kind, fully integrated and re-configurable thermo-photovoltaic on silicon platform. We report over an order of magnitude increase in generated electrical power by electro-statically tuning the distance between a suspended hot emitter TE ~ 880 K) and an underlying detector (maintained at TD ~ 300 K) from ~500 nm to ~100 nm. We believe this demonstration will be influential for the fields of active energy harvesting as well as in realizing integrated thermal control systems. In the third part of this work, we shift our focus away from broadband emitters, towards spectrally narrow band thermal emitters and propose a novel technique for long-distance transport of thermal radiation. In order to do so, we rely on enhanced near-field heat transfer over blackbody limits aided by surface plasmon polaritions (SPP). We then show that a dispersion engineered sub-wavelength waveguide can allow required states for SPP aided electromagnetic emission to propagate. We show computational analysis of the a composite structure using the open-source electromagnetic solvers SCUFF-EM that captures the effects of surface current distribution induced electromagnetic field effects inside and outside the emitter. We furthermore show a prototype structure of the proposed thermal-waveguide with doped silicon emitters that support SPP. We discuss the measurement technique and present preliminary results of thermal transport over a waveguide that is ~34 μm long. We believe that our proposed approach shown here could advance the field towards development of novel devices for thermal control.

This report considers both contributions and adverse consequences, uncertainties, and unknownrelationships that are potentially involved in the advances of techno-economic and humanisticinterests towards the advances in Nanosciences and Nanotechnologies (N&amp;N). Because of thedistinctive physical and chemical properties of materials at nanoscales, which have not beenunderstood deeply yet, besides the huge potentials to benefit many areas of research andapplication, it is recognized that application of N&amp;N may raise new ecological, health and safety,socio-economic, and regulatory challenges that will require scientific, techno-economic, andsocietal considerations. A comprehensive literature survey of peer reviewed journals, books, andother authoritative sources indicate that there have been very few studies on these fundamentalaspects and the research investments are mainly sponsored for market purposes, rather than forpure scientific structure-function discoveries or sustainability attitudes. The overarching issue ofimportance in this study is to consider the high level of uncertainties and lack of knowledge inN&amp;N, and the great potential threats and impacts of engineered nanoproducts that can be eitherin form of known-unknowns or even unknown-unknowns. Moreover, measures of improvementto govern N&amp;N developments to become sustainable, including public communication, call forpure and high quality non-prescribed research on unknown characteristics of N&amp;N, health and environmental friendliness based on a life cycle approach, and the industrial ecology approach,together with implementation of the related results in practice have been suggested. / www.ima.kth.se