O presente trabalho estuda a produção e modificações físico-químicas do grafeno frente a tratamentos térmicos. Em uma primeira etapa, foi investigada a síntese de grafeno pela técnica de Deposição Química a partir da fase Vapor (CVD) sobre fitas de cobre. Nós variamos quatro parâmetros que influenciam no crescimento de grafeno: fluxo de metano (CH4), fluxo de hidrogênio (H2), tempo de crescimento e grau de pureza do cobre. Usando as técnicas de caracterização de espectroscopia Raman e microscopia óptica, observamos que fluxo menor de H2 e fluxo intermediários de CH4 favorecem o crescimento de grafeno de alta qualidade. Além disso, vimos que 15 minutos de crescimento de grafeno é suficiente para cobertura do substrato de cobre com grafeno. Por fim, foi visto que o maior grau de pureza do cobre permite a produção de monocamadas de grafeno mais homogêneas. Numa segunda etapa, foi realizado um estudo com objetivo de entender a interação de hidrogênio com monocamadas de grafeno. Nós usamos amostras de grafeno depositadas em filmes de SiO2 (285 nm)/Si e tratadas termicamente em atmosfera controlada de deutério (99,8%) em temperaturas entre 200 e 800 °C. Nós também investigamos a dessorção de hidrogênio do grafeno usando amostras previamente tratadas em deutério a 600 °C e depois tratadas em atmosfera controlada de nitrogênio em temperaturas entre 200 e 800 °C. Após os tratamentos, análise por reação nuclear (NRA) foi realizada para quantificar o deutério, onde nós observamos uma grande incorporação de deutério no grafeno acima de 400 °C, tendo um aumento moderado até 800 °C. Nós também observamos que a dessorção do deutério do grafeno ocorre apenas em 800 °C, embora a dessorção de deutério do óxido de silício ocorra a partir de 600°C. Espectroscopia Raman também foi realizada após cada tratamento térmico. Os resultados mostram que os defeitos na estrutura do grafeno têm um grande aumento para as etapas de maior temperatura na incorporação de deutério. Análises realizadas com Espectroscopia de Fotoelétrons Induzidos por Raios X (XPS) mostraram que a incorporação de deutério para maiores temperaturas causa o "etching" do grafeno. Por fim, caracterizações usando Espectroscopia de Absorção de Raios X (NEXAFS) mostraram que o deutério liga-se ao grafeno sem orientação preferencial. / The present work studies the production and physical-chemical modifications of the graphene under thermal annealings. In a first study, the graphene synthesis by Chemical Vapor Deposition (CVD) on copper foils was investigated. We varied four parameters that influence the growth of graphene: methane flow (CH4), hydrogen flow (H2), growth time and copper purity. Using Raman spectroscopy and optical microscopy, we observed that lower flux of H2 and intermediate flux of CH4 leads to the growth of high quality graphene. In addition, we observed that 15 minutes growth of graphene is sufficient to cover the copper substrate. A higher copper purity allows the production of homogeneous graphene monolayers. In a second step, a study was carried out to understand the interaction of hydrogen with graphene monolayers. We used graphene samples deposited on SiO2 (285 nm)/Si films and annealed in a controlled atmosphere of deuterium (99.8%) at temperatures between 200 and 800 °C. We also investigated the hydrogen desorption of graphene using samples previously treated in deuterium at 600 °C and then annealed in a controlled atmosphere of nitrogen at temperatures between 200 and 800 °C. After the annealings, nuclear reaction analysis (NRA) was performed to quantify the deuterium, where we observed a large incorporation of deuterium in graphene above 400 °C, with a moderate increase up to 800 °C. We also observed that desorption of deuterium occurs only at 800 °C, although deuterium desorption from silicon oxide occurs at 600 °C. Raman spectroscopy was also performed after each annealing. The results show that defects in the structure of graphene have a large increase for deuterium incorporation. Analyzes carried out with X-ray Photoelectron Spectroscopy (XPS) showed that the deuterium incorporation at higher temperatures leads to graphene etching. Finally, characterizations using X-ray Absorption Spectroscopy (NEXAFS) showed that deuterium binds to graphene without preferential orientation.

Made available in DSpace on 2014-10-09T12:50:42Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:03Z (GMT). No. of bitstreams: 1 00385.pdf: 917455 bytes, checksum: 170691f120f1bd5b66fa48cba02fe1f6 (MD5) / Dissertacao (Mestrado) / IEA/D / Escola Politecnica, Universidade de Sao Paulo - POLI/USP

No description available.

Tritium is a radioisotope of hydrogen and a component of emissions from the nuclear industry. It is also a radioisotope of concern for human and environmental health. The near future could see an increase in tritium production as experimental fusion reactors initiate first plasma. The greatest risk pathway is human ingestion of edible plants grown near sites of tritium emissions as they can acquire high levels of organically bound tritium (OBT). Recent studies at a tritium Beta-light facility in Pembroke, Ontario, Canada characterized by tritiated hydrogen gas (HT) emissions have identified high OBT:HTO ratios that are not consistent with current tritium transfer models. This suggests that there is an unidentified physical, chemical, or biological mechanism generating OBT in plant tissue. Laboratory experiments have been undertaken using deuterium gas (D2) as an analogue for atmospheric HT in controlled plant exposure experiments, and compared the observations with short-term exposures at the SRBT facility. While the deuterium results did not uncover a hidden pathway or enrichment mechanism, the SRBT exposures showed elevated tissue free water tritium (TFWT) in stems and leaves in the presence of atmospheric HT, and lacking HTO in both soils and surrounding air. This study proposes that hydrogenase activity in microbial communities hosted within the laminar boundary layer on the leaf surface, are responsible for HT oxidation to HTO that contributes directly to leaf waters used in photosynthesis.

By using two electrospray emitters containing different solutions (“dual-spray”) we have recently conducted in-source hydrogen/deuterium exchange (HDX) reactions and synthesized organometallic species. For dual-spray HDX reactions, peptide and protein solutions were electrosprayed through one emitter and the deuterating agent D2O through the secondary electrospray emitter. Clear shifts in isotope distributions indicated hydrogen-deuterium exchange occurring within the ion source. By ion mobility, simultaneous deuterium exchange for two isobaric species, the oxytocin monomer and dimer, was observed. Lysozyme has a linear relation between the charge state and the average number of exchanges, indicating that lysozyme becomes increasingly unfolded as the charge state increases. Based on deuterium uptake data and the lack of a temperature dependence, the dual-spray HDX reaction is thought to occur mostly in the gas phase. Tris(2,2’-bipyridine)ruthenium(II) and similar complexes containing the 1,10-phenanthroline ligand were formed by spraying a ligand solution and the ruthenium trichloride solution through two independent ESI emitters. This was confirmed by comparing ion mobility drift time, mass spectra, and CID fragmentation with the reference standard compounds. Tris(2,2’-bipyridine)iron(II), tris(1,10-phenantroline)iron(II) and mixed ligand complexes of iron(II) formed by dual-spray showed two additional hydrogens bonded to the complex. By CID, these unique gas phase complexes showed similar initial ligand loss to the reference standards however the secondary ligand loss showed dissimilar dissociation channels and energetics. Using DFT calculations, geometry optimizations for the [Fe(phen)3 + 2H]2+ complex and its fragment ions were done. After the initial ligand loss, the additional hydrogens are believed to transfer to the central iron atom. The relative energy of the dissociation channels showed good agreement with experimental breakdown curves.

A central quest in biology is to understand the structure-function relationship of complex biological systems. The brain represents the ultimate complexity of a biological system: (1) the vertebrate brain contains 107-1011 neurons interconnected with glial cells; (2) over tens of diverse cell types are organized in a hierarchical way over an intricate landscape; (3) coordinated electrical and chemical activities of neuronal ensembles generate emergent properties and functions; and (4) each neuron can extend over large volumes with its spatial scales spanning 6 orders of magnitude. As a result, compared to other organ systems, our understanding of the brain remains primitive and obscure in terms of both its structures and its functions. Accordingly, many grand challenges endure in brain sciences, including comprehensively mapping neuronal wiring of the brain, an exhaustive taxonomy of cell types in the brain, and robust diagnostic and therapeutic strategies for brain diseases. These challenges are difficult to tackle with existing microscopy methods, because general trade-offs prevail between number of colors, imaging depth, spatial resolution, imaging throughput, sensitivity, and specificity. Therefore, the quest to understand the brain calls for advances and innovations on novel microscopy methods.The evolution of modern Raman microscopy is fundamentally driven by the development of novel spectroscopy methods. The advancement of molecular spectroscopy in turn pushes forward and benefits from, the progress in vibrational probes, labeling chemistry, and sample processing and transformation. In particular, stimulated Raman scattering (SRS) microscopy offers high sensitivity and fast acquisition for biomedical imaging, by harnessing accelerated vibrational transition from stimulated emission. Bio-orthogonal chemical imaging provides chemical specificity and minimal perturbation for visualizing metabolic dynamics of small molecules, by using tiny vibrational probes such as deuterium and alkyne. Electronic pre-resonance SRS (epr-SRS) microscopy further enhances the sensitivity to the nanomolar level for imaging specific proteins, by exploiting electronic pre-resonance of specially designed Raman dyes. Despite these notable innovations, the imaging depth of these Raman microscopy methods is limited to superficial layers of biological tissues (~100 μm) due to light scattering. This dissertation contributes to the development of advanced Raman microscopy methods for volumetric imaging with extended imaging depth in scattering tissues. For this purpose, we develop a set of tissue clearing strategies tailored to specific Raman imaging modalities. In addition, we develop image analysis methods to extract systems information from volumetric high-dimensional imaging datasets. Equipped with our volumetric imaging and analysis methods, we elucidate intricate structures and functions of the brain at both physiological and pathological conditions, providing implications for brain tumor metabolism and cerebellum development. Chapter 1 introduces an overview of Raman microscopy with particular emphasis on SRS and epr-SRS microscopies. Chapter 2 discusses the principles of tissue clearing with special focus on the basis of light scattering, the working mechanisms of different categories of tissue clearing methods, and the rationale underlying the development and evolution of these tissue clearing methods. Chapter 3 describes the development of volumetric chemical imaging, which brings label-free SRS microscopy, bio-orthogonal chemical imaging, and metabolic imaging to the realm of volumetric imaging with greater than 10-fold depth extension. Chapter 4 depicts the development of volumetric multiplex imaging, which generalizes epr-SRS microscopy to the territory of volumetric imaging. With this method we achieve one-shot imaging of more than 10 colors over millimeter-thick brain tissues, extending the imaging depth of multiplex protein imaging by 10~100 folds. Chapter 5 is a manuscript of an ongoing project on imaging nanocarriers for drug delivery across the blood-brain barrier (BBB). We develop a method of correlative multispectral SRS and fluorescence microscopy to image nanoparticles by SRS with multispectral information and particle counting capability and to image tissue context (especially cerebral vasculature) by fluorescence with high specificity. Using this method, we achieve direct imaging of nanocarriers that cross the BBB with definitive spectral evidence and single particle sensitivity. The preliminary results quantifying the proportion of nanoparticles that cross the BBB provide implications that challenge the current understanding of drug delivery to the brain.

<p>To achieving successfully commercial nuclear fusion energy, fully understanding of the interaction between plasma particles and plasma facing components is one of the essential issues. Tungsten, due to good thermal and mechanical properties such as high thermal conductivity and melting temperature, is one of the most promising candidates. However, the plasma facing components interacting with the extreme environmental conditions such as high temperature and radiation may lead to nanostructure formation, sputtering and erosion that will lead to material degradation. And these deformations may influence not only properties of plasma facing components but also might affect the plasma itself. For example, the contamination of plasma with a few amounts of tungsten, a high Z element, as a result of erosion or sputtering may cause core plasma cooling that results in loss of plasma confinement. Additionally, the retention of hydrogen isotopes, especially tritium, in tungsten is essential issue because of its radioactivity and market value.</p> In this study, deuterium trapping in tungsten is analyzed by molecular dynamics method and the effect of pre-irradiation on trapping is studied. Non-cumulative studies show that the increase in the energy of hydrogen isotopes rises the absorption rate, the initial implantation depth, and the average resting time for initial implantation. Additionally, the effect of implanted deuterium due to pre-irradiation on the hydrogen isotopes trapping is analyzed by combining both cumulative and non-cumulative simulations, and results indicate that while the increase in the pre-irradiation time raises the absorption rate of deuterium with higher energy than 80 eV, it causes a decrease the initial implantation depth and the average resting time for initial implantation because of deuterium-deuterium interactions. Additionally, the deuterium-deuterium interactions may transfer enough energy to implanted deuterium to start a motion which may lead to deeper implantation or escaping from the surface of tungsten. The escaping from surface as a result of deuterium-deuterium interaction could explain the decrease in accumulation rate of deuterium while absorption rate rises.

In dieser Arbeit wird beschrieben, wie sich die in situ-IR-Spektroskopie zur Charakterisierung von CVD-Prozessen einsetzen läßt. Es werden Modellreaktoren vorgestellt, deren Konstruktion an die spektroskopische Verfolgung thermisch aktivierter Gasphasenreaktionen angepaßt ist. Ausgehend von Referenzmessungen, mit deren Hilfe Möglichkeiten und Grenzen der FT-IR-Spektroskopie in Bezug auf die CVD-Prozeßanalytik aufgezeigt werden, können auftretende Species im untersuchten System sicher bestimmt werden. Im Mittelpunkt der Arbeit steht die Untersuchung der Gasphase bei der Thermolyse von Methyltrichlorsilan in Abhängigkeit von den Prozeßparametern Temperatur und Eduktgaszusammensetzung. Die gefundenen Korrelationen werden durch Thermolysen einzelner, nachgewiesener Verbindungen bestätigt. Eine weitere Absicherung der Ergebnisse erfolgt durch Isotopenmarkierung mit Deuterium. Untersuchungen zur Schichtbildung ergänzen die Gasphasenanalytik. Auf Grundlage der nachgewiesenen stabilen und instabilen Species und deren Abhängigkeit von den Prozeßparametern wird ein Mechanismus vorgeschlagen und diskutiert, der die Thermolyse von Methyltrichlorsilan zur Abscheidung von Siliciumcarbid vollständig beschreibt.

This work focuses on the effects of formulation and manufacturing as it effects protein structure and physical stability. Using common physical characterization techniques, X-ray photoelectron spectroscopy, and solid-state hydrogen/deuterium exchange with mass spectrometry, correlations are identified between these results and accelerated stability studies.

No description available.