Orientador: Watson Loh / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-11T09:12:14Z (GMT). No. of bitstreams: 1 Angarten_RodrigoGiatte_M.pdf: 1395431 bytes, checksum: 0f52b58a143972707ace4bd85a873d30 (MD5) Previous issue date: 2007 / Resumo: Alquilglicosídeos (AG) são surfatantes não-iônicos totalmente provenientes de fontes naturais e renováveis, além de serem totalmente biodegradáveis e atóxicos. Neste trabalho estudou-se a termodinâmica de micelização desta classe de surfatantes através das técnicas de calorimetria diferencial de varredura (DSC) e titulação calorimétrica isotérmica (ITC), em função do número de átomos de carbono presentes em sua cadeia hidrofóbica e do número de unidades glicosídicas em sua parte polar. Estas propriedades foram determinadas em H2O e em D2O. Para um mesmo AG, o aumento de temperatura implica em uma energia de Gibbs, DmicG, mais favorável à micelização. Com o aumento de temperatura, a variação de entalpia, DmicH, passa de positiva para negativa e o termo entrópico, TDmicS, perde sua contribuição para a micelização. Quando comparados surfatantes de mesmo número de átomos de carbono na cadeia alquílica, mono e di-glicosídeos apresentam estritamente o mesmo comportamento termodinâmico. Heptilglicosídeo apresentou comportamento distinto dos demais surfatantes estudados, indicando que o ambiente químico no interior de sua micela é diferente. Estudos da micelização nos dois solventes mostraram que a maior energia coesiva de D2O, comparada a H2O, implica numa maior contribuição entrópica ao processo de micelização, mas não altera significativamente a energia de Gibbs / Abstract: Alkylglucosides (AG) are non-ionic surfactants obtained from natural raw materials, which are also totally biodegradable and non-toxic. This study investigated the thermodynamics of their micellization using the techniques of differential scanning calorimetry (DSC) and isothermal titration calorimetry (ITC), for a series of homologues varying their alkyl chain lengths and number of glucoside units (one or two). Some studies were conducted in D2O too, and compared with the results in H2O. As temperature increases, the micellization process becomes more favorable, as measured by a more negative DmicG. In parallel, the enthalpic contribution, DmicH, changes from positive to negative and the entropic term, TDmicS, reduces it positive value. These trends agree well with those reported for other families of surfactants. When AGs of the with the same alkyl chain length are compared, mono and diglucosides display the same thermodynamic functions for micellization. Only for the heptyl homologue of the monoglucoside family, results are slightly out of the general trend observed for the other AG, possibly due to different micelle structure being formed by this smaller surfactant. Comparison of results obtained in D2O with H2O confirmed that the greater cohesive energy of the former leads to a larger entropic contribution to micellization, but with no significant change in the Gibbs energy values / Mestrado / Físico-Química / Mestre em Química

Tritium generation presents a significant hazard during operation of nuclear reactors and necessitates safety precautions in the case of a combustion incident. Accurate kinetic models should inform these safety precautions, however, reliable tritium data do not exist to generate such models. This work focuses on laminar flame speed, which is an important component of kinetic models. Current estimates based on established kinetic theories and experimental measurements of the other isotopes of hydrogen predict tritium to have a flame speed approximately 70% that of standard protium over a broad range of stoichiometries at one atmosphere in air. These estimates are based solely on isotopic mass differences and do not account for radioactive decay, which, in the case of tritium, is energetic enough to cause significant radiolysis reactions and potentially alter the radical pool for combustion. Simulations of a protium flame present compelling evidence that hydrogen flames are controlled by preferential radical diffusion from the rigorous flame region towards the unburned gases and not by heat conduction and dissociation of stable molecules. These flames rely on very low radical concentrations at the initiation region of the flame and the chemistry may be altered by a slight increase in radicals due to radioactive decay. This work also presents an experimental method suitable for measuring these radioactivity effects on tritium flame speed utilizing direct measurements of a flame propagating through a transparent tube. Measurements of protium and deuterium flame speeds using this method have proven highly repeatable and consistent with literature values while consuming much less reactant than other potential methods.

In quantitative proteomics, many of the LC-MS based approaches employ stable isotopic labelling to provide relative quantitation of the proteome in different cell states. In a typical approach, peptides are first detected and identified by tandem MS scans prior to quantifying proteins. This provides the researcher with a large amount of data that are not useful for quantitation. It is desirable to improve the throughput of current approaches to make proteomics a more routine experiment with an enhanced capacity to detect differentially expressed proteins. This thesis reports the developments towards this goal, including an assessment of the viability of stable dimethyl labelling for comparative proteomic measurements and the evaluation of a dynamic algorithm called Parallel Isotopic Tag Screening (PITS) for the detection of isotopically labelled peptides for quantitative proteomics without the use of tandem MS scans.

In this work we generalize existing theory of low-energy collisions of atomic hydrogen with its anion. We extend the non-local resonance model for this system by adding new discrete state and two continua that are coupled with it. We calculate numerically cross sections for associative electron detachment process that is important for models of early universe. We add cross section for collision detachment and show spectra of outgoing electrons. We show how the isotopic effect is involved in studied collision. We also calculate charge transfer, elastic scattering cross sections, and reaction rates for hydrogen collisions with deuterium anion. We compare our results with recent experiments and we discuss their reliability. Powered by TCPDF (www.tcpdf.org)

Master of Science / Department of Physics / Brett D. Esry / The two-state field-aligned (1-D) model has been employed to investigate the dissociation dynamics of a hydrogen molecular ion and its isotopes under the Born-Oppenheimer approximation without rotation. The emphasis of this work was on the role of mass during the dynamical dissociation processes and on the laser-induced branching ratios between different photon pathways. Firstly, we have found that scaling the pulse duration of the laser pulse, applied to H[subscript]2+ and D[subscript]2+ , by the square root of the mass ratio of these isotopes will produce similar structure in the nuclear kinetic energy release (KER) spectra. In fact, the similarity of the spectra is enhanced by including some averaging that is necessary for comparison with experiment. For this to occur, the same broad initial vibrational distribution and a short pulse are preferred. Using this scaling idea, it is possible to produce effectively shorter laser pulses by studying heavier isotopes, like D[subscript]2+. Secondly, we have demonstrated analytically and numerically that there is a carrier-envelope phase effect in the total dissociation probability (TDP) of H[subscript]2+, and this effect grows with nuclear mass. We further show that under the same laser conditions, the CEP effect in the asymmetry between breakup channels decreases with mass. Our analytic expressions enhance the idea that CEP effects can be understood as an interference between different n-photon processes. Thirdly, the trends in the dissociation dynamics of H[subscript]2+ and D[subscript]2+ in a 800nm ultra short intense laser field were demonstrated by studying the dissociation branching ratios of multiphoton processes as a function of the laser peak intensity (from 8[times]10[superscript]9 to 10[superscript]14 W/cm[superscript]2) or pulse length (5fs-7.5fs). Based on the two-state approximation, an energy-analysis method (EAM) was employed to separate multiphoton processes. The results show that the one-photon dissociation process dominates over all other photon processes under all the laser conditions applied in the calculations and that the zero-photon process contributes to a surprisingly large fraction of the total dissociation. Two- and three- photon dissociation are weaker processes, but become more and more important as the laser peak intensity and pulse length increases. A two-state Floquet method was used to check the accuracy of the EAM, and good agreement between the two methods was found, demonstrating the reliability of the EAM. In comparison with H[subscript]2+, D[subscript]2+ displays stronger two and three photon branching ratios (above-threshold dissociation - ATD), which can be attributed to the late arrival of D[subscript]2+ to the critical distance for ATD to occur due to its heavier mass. Therefore, this "mass" effect can be used to steer the molecular dissociation pathways.