Graphene, first isolated in 2004 by Andre Geim and Konstantin Novoselov, is an atomically thin two-dimensional layer of hexagonal carbon that has been extensively studied due to its unique electronic, mechanical, thermal and optical properties. Its vast potential has led to the development of a wide variety of novel devices such as, transistors, solar cells, batteries and sensors that offer significant advantages over the conventional microelectronic ones. Although graphene-based devices show very promising performance characteristics, limited has been done in order to evaluate how these devices operate in a radiation harsh environment. Undesirable phenomena such as total dose effects, single event upsets, displacement damage and soft errors that silicon-based devices are prone to, can have a detrimental impact on performance and reliability. Similarly, the significant effects of irradiation on carbon nanotubes indicate the potential for related radiation induced defects in carbon-based materials, such as graphene. In this work, we fabricate graphene field effect transistors (GFETs) and systematically study the various effects of ionizing radiation on the material and device level. Graphene grown by chemical vapor deposition (CVD) along with standard lithographic and shadow masking techniques, was used for the transistor fabrication. GFETs were subjected to different radiation sources, such as, beta particles (electron radiation), gamma (photons) and ions (alpha, protons and Fe particles) under various radiation doses and energies. The effects on graphene’s crystal structure, transport properties and doping profile were examined by using a variety of characterization tools and techniques. We demonstrate not only the mechanisms of ionized charge build up in the substrate and displacement damage effects on GFET performance, but also that atmospheric adsorbents from the surrounding environment can have a significant impact on the radiation hardness of graphene. We developed different transistor structures that mitigate these effects and performed computer simulations to enhance even further our understanding of radiation damage. Our results show that devices using a passivation layer and a shielded gate structure were less prone to irradiation effects when compared to the standard back-gate GFETs, offering less performance degradation and enhanced stability over prolonged irradiation periods. This is an important step towards the development of radiation hard graphene-based devices, enabling operation in space, military, or other radiation sensitive environments.

O glioblastoma multiforme (GBM) é um tipo de câncer grave que acomete o sistema nervoso central (SNC), e a sobrevida dos pacientes é de aproximadamente 12 meses. O tratamento com o quimioterápico paclitaxel (PTX) reduz o GBM experimental e humano. No entanto, sua utilização é limitada pelas reações adversas graves que acarreta. A nanoemulsão rica em colesterol (LDE), a qual mimetiza a lipoproteína de baixa densidade, tem sido empregada como um sistema de entrega de fármacos eficiente em alguns casos de tumores. No presente trabalho visou-se avaliar a eficácia do oleato de PTX (OPTX), um derivado mais lipofílico do que o PTX, associado a LDE (LDE-OPTX) em ensaios in vitro e in vivo. Inicialmente, células tumorais da linhagem de glioblastoma murino GL261 foram incubadas com PTX em solução ou com LDE-OPTX, nas concentrações de 1 ou 10 µM. Os resultados obtidos mostraram que o tratamento in vitro com PTX e o LDE-OPTX causa toxicidade in vitro em células GL261 pela redução da proliferação e indução de apoptose, e que ainda reduz a secreção de MCP-1 (proteína quimiotáxica de monócitos). Os ensaios in vivo mostraram a toxicidade intensa do PTX comercial, uma vez que os animais com GBM não sobreviveram ao tratamento com 75mg/Kg, i.p., a cada 3 dias, e foram a óbito a partir do oitavo dia de tratamento. Diferentemente, os animais tratados com a mesma dose de LDE-OPTX sobreviveram ao tratamento, sem sinais de toxicidade, mas os dados obtidos mostraram que este protocolo de tratamento não foi eficaz para redução do volume tumoral. Assim, os animais com GBM passaram a ser tratados com doses diárias, i.p., de 15 mg/kg de PTX ou de 75mg/Kg de LDE-OPTX. Os resultados obtidos mostraram a ineficácia e eficácia dos tratamentos com PTX e LDE-OPTX, respectivamente, em reduzir o GBM; no entanto os animais tratados com LDE-OPTX apresentaram redução no peso corporal e no número de linfócitos circulantes. Em conjunto, os dados obtidos mostram a habilidade de preparação LDE-OPTX causar toxicidade in vitro nas células GL261 e sua eficácia terapêutica em dose elevada, em reduzir o GBM em modelo murino. / Glioblastoma multiforme (GBM) is a type of severe cancer that affects the central nervous system, and patient survival is about12 months. The treatment with the chemotherapeutic paclitaxel (PTX) reduces the experimental and human GBM, however, their use is limited by side effects. The lipid nanoemulsion (LDE), that is mimetic to low density protein, has been employed as an efficient drug nanocarrier to treat cancer. Therefore, the present study aimed to assess the effectiveness of the oleate PTX (OPTX), a more lipophilic derivative of PTX, associated to (LDE), in in vitro and in vivo studies. Initially, glioblastoma murine strain GL261 was incubated with commercial PTX solution or LDE-OPTX at concentrations of 1 or 10 µM. Data obtained showed that treatment with PTX or LDE-OPTX caused in vitro toxicity to GL261 cells, by reducing the proliferation and inducing apoptosis. Moreover, both treatments reduced the secretion of monocyte chemotacticprotein-1 (MCP-1). In vivo experiments showed the severe toxicity of commercial PTX, as mice with GBM did not survive to the treatment with 75mg/kg, i.p., each 3 days, and died after 8 days of treatment. Conversely, animals treated with the same schedule of treatment with LDE-OPTX survived until the end of treatment, without any toxicity signal. Nevertheless, the treatment was not effective to reduce the GBM volume. Hence, other sets of animals with GBM were treated with daily i.p. dose of 15mg/kg of PTX or 75mg/kg of LDE-OPTX. Data obtained showed the inefficacy and efficacy of PTX and LDE-OPTX treatments, respectively, to reduce the volume of GBM. Nevertheless, mice treated with LDE-OPTX lost weight and lower number of circulating lymphocytes. Together, our data show the ability of LDE-OPTX treatment cause in vitro toxicity on GL261 cells e the in vivo therapeutic efficacy of higher doses on GBM murine model.

A construção de sistemas metal-orgânicos supramoleculares através da exploração da conectividade de ligantes terpiridínicos e o desenvolvimento de suas aplicações em nanodispositivos, são tratados nesta tese. Foram desenvolvidos novos complexos de ferro e rutênio com ligantes terpiridínicos funcionalizados, capazes de gerar filmes finos e apresentar interações supramoleculares do tipo hóspede-hospedeiro. Esses complexos foram empregados na modificação de superfícies de dióxido de titânio, visando aplicações em sensores e dispositivos fotoeletroquímicos. Modificando-se o dióxido de titânio nanocristalino, com moléculas hospedeiras de carboxi-metil-β-ciclodextrina, foi possível gerar um sistema seletivo para fotodegradação de compostos aromáticos, como demonstrado para o complexo bis(4\'-(4-bromo-fenil)-2,2\':6\',2\'\'-terpiridina)ferro(II), cujo descoramento foi observado efetuando-se a fotoirradiação no ultravioleta. Esse sistema foi aprimorado para gerar um dosímetro de UV, com base nesse princípio. Além disso, foram feitos estudos de eletropolimerização desse complexo e sobre a capacidade dos filmes moleculares gerados, de atuarem em sensores amperométricos na detecção de espécies químicas relevantes, como os íons nitrito. Outro complexo sintetizado foi o [Ru(c-ph-terpy)(Q)(NCS)], em que c-ph-terpy é a 4\'-(4-carboxi-fenil)-2,2\':6\',2\'\'-terpiridina e Q é o ligante 8-oxiquinolinato. Esse complexo terpiridínico foi desenvolvido para ser utilizado como fotossensibilizador em células solares do tipo Grätzel, tanto na forma direta, como após a modificação da superfície de dióxido de titânio com a carboxi-metil-β-ciclodextrina. Demonstrou-se que através da sua inclusão na cavidade supramolecular, o fotossensibilizador aumenta a eficácia da fotoconversão de energia. Finalmente, foi sintetizada uma nova supermolécula a partir da auto-montagem coordenativa entre a tetra-piridilporfirina e complexos de rutênio(II) coordenados com ligantes oxalato e 4-cloro-2,2\':6\',2\'\'-terpiridina. Foi observado que essa supermolécula apresenta atividade catalítica de oxidação de substratos orgânicos, associada aos grupos periféricos. Os vários sistemas estudados possibilitaram avançar nas estratégias de engenharia supramolecular, através da construção de novos conectores, blocos de montagem e filmes moleculares, bem como avaliar algumas de suas aplicações nanotecnológicas. / This thesis deals with the development of new metal-organic supramolecular systems based on functionalized terpyridine compounds, including their application in nanotechnological devices. New iron and ruthenium coordination compounds incorporating terpyridine ligands have been obtained, and their ability to generate thin films and participate in host-guest interactions has been conveniently explored. Such complexes have been employed in the modification of titanium dioxide surfaces, for applications in sensors and photoeletrochemical cells. By combining nanocrystalline titanium dioxide with carboxy-methyl-β-cyclodextrin, a novel, efficient strategy has been devised for photodegradation of aromatic compounds, and successfully demonstrated after anchoring the bis(4\'-(4-bromophenyl)-2,2\':6\'2\'\'-terpyridine)iron(II) complex and monitoring its bleaching by exposing to UV radiation. In this way, this system has been successfully employed in the design of a novel, versatile UV dosimeter. Electropolymerization studies have also been carried out on this complex, in order to generate molecular films for use in amperometric sensors, capable of probing relevant species, such as the nitrite ions. Another compound dealt with in this work was [Ru(c-ph-terpy)(Q)(NCS)], where c-ph-terpy = 4\'-(4-carboxy-pheny)-2,2\':6\',2\'\'-terpyridine, and Q = 8-oxyquinolinate ligand. This terpyridine complex has been designed as fotosensitizer in Grätzel\'s photoelectrochemical cells, by its direct coating on the titanium dioxide nanoparticles or by performing their previous treatment with carboxi-methyl-β-cyclodextrin. It has been shown that the inclusion into the cyclodextrin cavity improves the performance of the photosensitizer for energy conversion. Finally, a new supermolecule encompassing a central tetrapyridylporphyrin unity attached to four chloro(oxalate)(4-chloro-2,2\':6\',2\'\'-terpyridine)ruthenium(II) complexes, has been synthesized. This species exhibits catalytic activity in the oxidation of organic compounds. The reported study, involving several systems, has contributed to the available molecular engineering strategies, through the building up of new connecting groups and molecular films, and has also allowed the exploitation of some of their possible nanotechnological applications

Single-molecule carbon nanotube-based field-effect transistors are promising all-electronic devices for probing interactions of various biological and chemical molecules at the single- molecule level. Such devices consist of point-functionalized carbon nanotubes which are charge sensitive in the vicinity of a generated defect on the nanotube sidewall. Of particular interest is the characterization of the kinetic rates and thermodynamics of DNA duplex formation through repeated association (hybridization) and dissociation (melting) events on timescales unmatched by conventional single-molecule methods. In this work, we study the kinetics and thermodynamics of DNA duplex formation with two types of single-walled nanotubes: CVD-grown and solution-processed. In both assessments, we are able to extract kinetic and thermodynamic parameters governing the hybridization and melting of DNA oligonucleotides. In the latter case, devices are spun onto a wafer surface from an organic suspension, revealing consistent electrical characteristics. Significant effort is made to expand this work to wafer-level, in an effort to make the fabrication manufacturable.

Animals have evolved diverse strategies to control solar and thermal radiations so that they can better adapt to their natural habitats. Structured materials utilized by these animals to control electromagnetic waves often surpass analogous man-made optical materials in both sophistication and efficiency. Understanding the physical mechanism behind these structured materials of nature inspires one to create novel materials and technologies. Our optical and thermodynamic measurements of insects (Saharan silver ants and cocoons of the Madagascar comet moth) living in harsh thermal environments showed their unique ability to simultaneously enhance solar reflectivity and thermal emissivity, and to maintain a cool body temperature. Saharan silver ants, Cataglyphis bombycina, forage on the desert surface during the middle of the day. The ants’ conspicuous silvery glance is caused by a coating of hairs with unique triangular cross-sections. The hair coating enhances not only the reflectivity of the ant’s body surface in the visible and near-infrared range of the spectrum, where solar radiation culminates, but also the emissivity of the ant in the mid-infrared. The latter effect enables the animals to efficiently dissipate heat back to the surroundings via blackbody radiation under full daylight conditions. The fibers produced by the wild comet moth, Argema mittrei, are populated with a high density of air voids that have a random distribution in the fiber cross-section but are invariant along the fiber. These filamentary air voids strongly back-scatter light in the solar spectrum, which, in combination with the fibers’ intrinsic high emissivity in the mid-infrared, enables the cocoon to function as an efficient radiative-cooling device, preventing the pupa inside from overheating. The reduced dimensionality of the random voids leads to strong optical scattering in the transverse direction of the cocoon fibers. This enables tightly confined optical modes to propagate along the fibers via transverse Anderson localization. We made the first observation of transverse Anderson localization in a natural fiber and further demonstrated light focusing and image transport in the fibers. This discovery opens up the possibility to use wild silk fibers as a biocompatible and bioresorbable material for transporting optical signals and images. Drawing inspirations from these discoveries, we designed and developed high-throughput fabrication processes to create coatings and fibers with passive radiative-cooling properties. The radiative-cooling coatings consist of various nanoparticles imbedded within a silicone thin film. The sizes and materials of the nanoparticles were chosen to provide simultaneously high solar reflectivity and thermal emissivity. The coating has been implemented in two site studies on real roofs and has demonstrated reduced roof temperature by up to 30oC in the summer and associated reduction of electricity usage by up to 30%. We also made biomimetic fibers from regenerated silk fibroin and a thermoplastic using wet spinning. Spectroscopic measurements showed that these man-made fibers exhibit exceptional optical properties for radiative-cooling applications.

Two dimensional (2D) materials have unique properties that make them exciting candidates for various optical and electronic applications. Materials such as graphene and transition metal dichalcogenides (TMDCs) have been intensively studied recently with researchers racing to show advances in 2D device performance while developing a better understanding of the material properties. Despite recent advances,there are still significant roadblocks facing the use of 2D materials for real-world applications. The ability to make reliable, low-resistance electrical contact to TMDCs such as molybdeum disulfide (MoS22) has been a challenge that many researchers have sought to overcome with novel solutions. The work laid out in this dissertation uses novel techniques for addressing these issues through the use of improved device fabrication and with a clean, and potentially scalable doping method to tune 2D material properties.A high-performance field-effect transistor (FET) was fabricated using a new device platform that combined graphene leads with dielectric encapsulation leading to the highest reported value for electron mobility in MoS2. Device fabrication techniques were also investigated and a new, commercially available lithography tool (NanoFrazor) was used to pattern contacts directly onto monolayer MoS2. Through a series of control experiments with conventional lithography, a clear improvement in contact resistance was observed with the use of the NanoFrazor. Plasma-doping, a dry and clean process, was investigated as an alternative to traditional wet-chemistry doping techniques. In addition to developing doping parameters with a chlorine plasma treatment of graphene, a series of experiments on doped graphene were conducted to study its effect on optical properties. Whereas previous studies used electrostatic gating to modify graphene’s optical properties, this work with plasma-doped graphene showed the ability to tune absorbence and plasmon wavelength without the need for an applied bias opening the door to the potential for low-power applications. This work is a just small contribution to the larger body of research in this field but hopefully represents a meaningful step towards a greater understanding of 2D materials and the realization of functional applications.

This thesis is concerned with academics' behaviour when organising research aimed at being relevant. More specifically, this study combines a sociological approach and an extensive bibliometric analysis, investigating the relationships between scientists' perceptions of relevance, their research behaviours and their publishing activities in terms of organising nanomaterials research in Taiwan. By introducing a resource-based concept of the notion of relevance from a scientist's perspective, it contributes to intellectual debates on changes to knowledge production and the relationship between scientific excellence and socio-economic relevance. The study finds that the ways nanomaterials scientists perceive and organise their research, specifically in terms of research orientation, industry involvement and interdisciplinary collaboration, are not entirely oriented towards socio-economic concerns. Scientists tend to adapt to the demand for relevance by demonstrating potential research applications and forming interdisciplinary collaborations. Nevertheless, they are more persistent in terms of not having industry involved in the research process. Balancing adaptation and persistence reflects scientists' concerns with securing financial, intellectual and symbolic resources in order to establish their academic credibility. The bibliometric analysis broadly confirms the qualitative results findings, showing an increasing trend towards publishing in applied and targeted basic journals, and towards interdisciplinary collaboration. Yet, the proportion of university-industry papers has been rather stable over time. While our interviews suggest that senior scientists tend to consider interdisciplinary collaboration as a way to facilitate application, the bibliometric analysis shows that interdisciplinary co-authored papers tend to be more basic and receive more citations. The analysis also finds that junior scientists tend to feel more pressure to achieve a strong academic performance, thereby pushing them away from activities concerning achieving the envisioned socio-economic relevance of their research. Given the ambiguous notion of relevance and the inconsistency of policy practices, this thesis suggests that the real pressure is more to do with the demand for excellence than for relevance.

Physical factors in the environment of a cell regulate cell function and behavior and are involved in the formation and maintenance of tissue. There is strong evidence that substrate rigidity plays a key role in determining cell response in culture. Previous studies have demonstrated the importance of rigidity in numerous cellular processes including migration and adhesion and stem cell differentiation. Immune cells have been shown to respond differently to surfaces having different rigidities. Atypical response to rigidity is also a characteristic of cancerous cells. Understanding the mechanisms that support cellular rigidity sensing can lead to new tissue engineering strategies and potential new therapies based on rigidity modulation. A new technique was developed for the creation of biomimetic surfaces comprising regions of heterogeneous rigidity on the micro- and nanoscale. The surfaces are formed by exposing an elastomeric film of polydimethylsiloxane (PDMS) to a focused electron beam to form patterned regions of micro- and nanoscale spots. This thesis involves the formation of theses surfaces, characterization of their physical and chemical properties as a consequence of the electron beam exposure and investigation of how cells behave when plated on these surfaces. Cellular response to different patterns of heterogeneous rigidity is performed for several cell types. Human mesenchymal stem cells plated upon electron beam-exposed PDMS in a pattern of spots with diameters ranging from 2 µm to 100 nm display differential focal adhesion co-localization to the exposed features, depending on both rigidity and feature size. This behavior persists as the area of the exposed regions is reduced below ~1 µm. On spots with diameters of ~ 250 nm and smaller, focal adhesion co-localization is lost. This supports the notion that there is a length scale for cellular rigidity sensing, with the critical length in the range of a few hundred nanometers. When the heterogeneous rigidity surfaces are applied to CD4+ T cells, accumulations of proteins including TCR and pCasL on the exposed features are observed as a function of feature size. The pCasL appeared to significantly accumulate on 2 µm spots; For spots ~ 1 µm and below, cells appeared unable to identify the rigid regions. Further, Ca2+ release, a functional indicator of immunoresponse, is significantly enhanced on mixed-rigidity patterned PDMS relative to both soft and hard PDMS. Possible signaling pathways of TCR activation have been verified on e-beam exposed PDMS substrates with heterogeneous rigidity. These results are suggestive of possible new approaches to adoptive immunotherapy based on rigidity modulation. Studies on breast cancer cells indicate that on patterned substrates, sub-cellular processes are also significantly modulated. Integrin recruitment is enhanced on the rigid regions. Understanding the role of geometry in cellular rigidity response will point the way toward revealing its functional response and will shed light on the mechanistic underpinnings of this process.

The development and characterization of lithographically patterned dielectric superlattice systems are presented, which have enabled the first clear realization of fully developed fractal mini-gaps owing to the interplay between a quantizing magnetic field and a lithographically defined spatial superlattice potential. Following a history of lateral superlattice gating on 2-D electron gas systems, we present patterned dielectric superlattice graphene systems of unmatched quality, allowing for the characterization of Hofstadter fractal band structure under triangular and square lattice geometries. Hexagonal boron nitride, graphene heterostructures are uniquely suited to integration with patterned gating structures, due to their high mobility and thin encapsulating dielectric environment. These systems have already been utilized for the observation of Hofstadter’s fractal spectrum through the moiré superlattice effect, but such systems are limited in their tunability. The patterned dielectric superlattice allows for control of the superlattice geometry, polarity, and strength. Utilizing this control, we compare the resultant fractal spectra from both triangular and square superlattice potentials, which confer unique gap structures in agreement with their lattice symmetry. More generally, patterned dielectric superlattices can be used to generate a variety of spatially dependent scalar potentials onto van der Waals heterostructures with length scales of order 10nm, while maintaining low disorder.

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No intervalo de potencial -0,2 a +0,5 V vs. Ag/AgCl/KCl (3,0 mol L-1), utilizando voltametria de pulso diferencial (DPV), observou-se um processo em +0,1 V e este corresponde a dimerização dos produtos de oxidação eletroquímica da tiolcolina, formando ditio-bis-colina. O biossensor desenvolvido foi avaliado utilizando DPV na análise do pesticida carbaril, o qual inibe a ação da enzima AChE. Os melhores resultados obtidos foram com as seguintes condições otimizadas: 75 mV amplitude de pulso, incremento de potencial de 4 mV, e uma solução tampão fosfato (PBS) 0,2 mol L-1 pH 6,0. Usando tais parâmetros observou-se uma resposta linear para o carbaril no intervalo de 0,1 a 0,5 mol L-1, com um limite de detecção de 11,6 nmolL-1 (2,3 µg/kg), que é um limite adequado para determinar carbaril nas culturas em que este pesticida é aplicado considerando o limite máximo de resíduo permitido pelas legislações brasileiras. O biossensor proposto, Pt/rGO/PPy/AChE, foi aplicado com sucesso na determinação de carbaril em amostras de tomate e repolho. / A new biosensor was developed by a simple electrocodeposition of reduced graphene oxide (rGO), polypyrrole (PPy) and the enzyme acetylcholinesterase (AChE) on surface of platinum (Pt) electrode. In potential range of -0.2 to +0.5 V vs. Ag/AgCl/KCl (3.0 mol L-1), using differential pulse voltammetry (DPV), it was observed a process in + 0.1 V and this corresponds to the dimerization of electrochemical oxidation products of thiocholine, resulting in ditio-bis-choline. The biosensor developed was evaluated using DPV in the analysis of carbaryl, which inhibits the AChE enzyme action. The best results achieved were with the followings optimized conditions: 75 mV pulse amplitude, step potential of 4 mV, and a phosphate buffer solution (PBS) 0.2 mol L-1 and pH 6.0. Using these parameters was observed a linear response to carbaryl in a range of 0.1 to 0.5 µmol L-1, with a detection limit of 11.6 nmol L-1 (2.3 µg/kg), which is an appropriate limit for determination of carbaryl in the cultures which these pesticide is applied, considering the maximum reside limit allowed by Brazilian legislation. The biosensor proposed, Pt/rGO/PPy/AChE, was applied successfully in the determination of carbaryl in samples of cabbage and tomato. / FAPESP: 2015/02136-2