High-pressure kinetics of oxidative copolymerization of styrene with alpha-methyl styrene

This is the first report on the study carried out on high-pressure free-radical initiated oxidated copolymerization of styrene (STY) with alpha-methylstyrene (AMS) at various temperatures (45-65degreesC) at constant pressure (100 psi) and then at various pressures (50-300 psi) keeping the temperature (50degreesC) constant. The compositions of the copolyperoxides obtained from the H-1 NMT spectra were utilized to determine the reactivity ratios of the monomers. The reactivity ratios indicate that STY forms an ideal copolyperoxide with AMS and the copolyperoxide is richer in AMS. The effect of temperature and oxygen pressure in the reactivity ratios of the monomers was studied. The rates of copolymerization (R-p) were used to determine the overall activation energies (E-a) and activation volume (DeltaV(#)) of copolymerization. The unusually higher values of the DeltaV(#) may be due to the pressurizing fluid oxygen which itself is a reactant in the copolymerization, the side reactions, and the chain-transfer reactions occuring during copolymerizations.

Surfaces of Bounded Mean Curvature In Riemannian Manifolds

Consider a sequence of closed, orientable surfaces of fixed genus g in a Riemannian manifold M with uniform upper bounds on the norm of mean curvature and area. We show that on passing to a subsequence, we can choose parametrisations of the surfaces by inclusion maps from a fixed surface of the same genus so that the distance functions corresponding to the pullback metrics converge to a pseudo-metric and the inclusion maps converge to a Lipschitz map. We show further that the limiting pseudo-metric has fractal dimension two. As a corollary, we obtain a purely geometric result. Namely, we show that bounds on the mean curvature, area and genus of a surface F subset of M, together with bounds on the geometry of M, give an upper bound on the diameter of F. Our proof is modelled on Gromov's compactness theorem for J-holomorphic curves.

Almost quarter-pinched Kähler metrics and Chern numbers

Given n is an element of Z(+) and epsilon > 0, we prove that there exists delta = delta(epsilon, n) > 0 such that the following holds: If (M(n),g) is a compact Kahler n-manifold whose sectional curvatures K satisfy -1 -delta <= K <= -1/4 and c(I)(M), c(J)(M) are any two Chern numbers of M, then |c(I)(M)/c(J)(M) - c(I)(0)/c(J)(0)| < epsilon, where c(I)(0), c(J)(0) are the corresponding characteristic numbers of a complex hyperbolic space form. It follows that the Mostow-Siu surfaces and the threefolds of Deraux do not admit Kahler metrics with pinching close to 1/4.

{C}^0$ penalty methods for the fully nonlinear Monge-Ampère equation

In this paper, we develop and analyze C(0) penalty methods for the fully nonlinear Monge-Ampere equation det(D(2)u) = f in two dimensions. The key idea in designing our methods is to build discretizations such that the resulting discrete linearizations are symmetric, stable, and consistent with the continuous linearization. We are then able to show the well-posedness of the penalty method as well as quasi-optimal error estimates using the Banach fixed-point theorem as our main tool. Numerical experiments are presented which support the theoretical results.

Dynamic Supply and Threshold Voltage Scaling for CMOS Digital Circuits Using In-Situ Power Monitor

A generalized power tracking algorithm that minimizes power consumption of digital circuits by dynamic control of supply voltage and the body bias is proposed. A direct power monitoring scheme is proposed that does not need any replica and hence can sense total power consumed by load circuit across process, voltage, and temperature corners. Design details and performance of power monitor and tracking algorithm are examined by a simulation framework developed using UMC 90-nm CMOS triple well process. The proposed algorithm with direct power monitor achieves a power savings of 42.2% for activity of 0.02 and 22.4% for activity of 0.04. Experimental results from test chip fabricated in AMS 350 nm process shows power savings of 46.3% and 65% for load circuit operating in super threshold and near sub-threshold region, respectively. Measured resolution of power monitor is around 0.25 mV and it has a power overhead of 2.2% of die power. Issues with loop convergence and design tradeoff for power monitor are also discussed in this paper.

Towards formal verification of analog mixed signal designs using SPICE circuit simulation traces

An extension to a formal verification approach of hybrid systems is proposed to verify analog and mixed signal (AMS) designs. AMS designs can be formally modeled as hybrid systems and therefore lend themselves to the formal analysis and verification techniques applied to hybrid systems. The proposed approach employs simulation traces obtained from an actual design implementation of AMS circuit blocks (for example, in the form of SPICE netlists) to carry out formal analysis and verification. This enables the same platform used for formally validating an abstract model of an AMS design, to be also used for validating its different refinements and design implementation; thereby, providing a simple route to formal verification at different levels of implementation. The feasibility of the proposed approach is demonstrated with a case study based on a tunnel diode oscillator. Since the device characteristic of a tunnel diode is highly non-linear with a negative resistance region, dynamic behavior of circuits in which it is employed as an element is difficult to model, analyze and verify within a general hybrid system formal verification tool. In the case study presented the formal model and the proposed computational techniques have been incorporated into CheckMate, a formal verification tool based on MATLAB and Simulink-Stateflow Framework from MathWorks.

Dynamic Supply and Threshold Voltage Scaling for CMOS Digital Circuits Using In-Situ Power Monitor

A generalized power tracking algorithm that minimizes power consumption of digital circuits by dynamic control of supply voltage and the body bias is proposed. A direct power monitoring scheme is proposed that does not need any replica and hence can sense total power consumed by load circuit across process, voltage, and temperature corners. Design details and performance of power monitor and tracking algorithm are examined by a simulation framework developed using UMC 90-nm CMOS triple well process. The proposed algorithm with direct power monitor achieves a power savings of 42.2% for activity of 0.02 and 22.4% for activity of 0.04. Experimental results from test chip fabricated in AMS 350 nm process shows power savings of 46.3% and 65% for load circuit operating in super threshold and near sub-threshold region, respectively. Measured resolution of power monitor is around 0.25 mV and it has a power overhead of 2.2% of die power. Issues with loop convergence and design tradeoff for power monitor are also discussed in this paper.

Badly approximable numbers and vectors in Cantor-like sets

We show that a large class of Cantor-like sets of R-d, d >= 1, contains uncountably many badly approximable numbers, respectively badly approximable vectors, when d >= 2. An analogous result is also proved for subsets of R-d arising in the study of geodesic flows corresponding to (d+1)-dimensional manifolds of constant negative curvature and finite volume, generalizing the set of badly approximable numbers in R. Furthermore, we describe a condition on sets, which is fulfilled by a large class, ensuring a large intersection with these Cantor-like sets.

Functions for rice RFL in vegetative axillary meristem specification and outgrowth

Roles for the transcription factor RFL in rice axillary meristem development were studied. Its regulatory effects on LAX1, CUC1, and OsPIN3 reveal its functions in axillary meristem specification and outgrowth.Axillary meristems (AMs) are secondary shoot meristems whose outgrowth determines plant architecture. In rice, AMs form tillers, and tillering mutants reveal an interplay between transcription factors and the phytohormones auxin and strigolactone as some factors that underpin this developmental process. Previous studies showed that knockdown of the transcription factor gene RFL reduced tillering and caused a very large decrease in panicle branching. Here, the relationship between RFL, AM initiation, and outgrowth was examined. We show that RFL promotes AM specification through its effects on LAX1 and CUC genes, as their expression was modulated on RFL knockdown, on induction of RFL:GR fusion protein, and by a repressive RFL-EAR fusion protein. Further, we report reduced expression of auxin transporter genes OsPIN1 and OsPIN3 in the culm of RFL knockdown transgenic plants. Additionally, subtle change in the spatial pattern of IR4 DR5:GFP auxin reporter was observed, which hints at compromised auxin transport on RFL knockdown. The relationship between RFL, strigolactone signalling, and bud outgrowth was studied by transcript analyses and by the tillering phenotype of transgenic plants knocked down for both RFL and D3. These data suggest indirect RFL-strigolactone links that may affect tillering. Further, we show expression modulation of the auxin transporter gene OsPIN3 upon RFL:GR protein induction and by the repressive RFL-EAR protein. These modified forms of RFL had only indirect effects on OsPIN1. Together, we have found that RFL regulates the LAX1 and CUC genes during AM specification, and positively influences the outgrowth of AMs though its effects on auxin transport.

Geometric multiplicity margin for a submatrix

AMS Classification: 15A18, 15A21, 15A60.

Studies of ambient and chamber aerosol composition using the aerosol mass spectrometer

This thesis presents composition measurements for atmospherically relevant inorganic and organic aerosol from laboratory and ambient measurements using the Aerodyne aerosol mass spectrometer. Studies include the oxidation of dodecane in the Caltech environmental chambers, and several aircraft- and ground-based field studies, which include the quantification of wildfire emissions off the coast of California, and Los Angeles urban emissions.

The oxidation of dodecane by OH under low NO conditions and the formation of secondary organic aerosol (SOA) was explored using a gas-phase chemical model, gas-phase CIMS measurements, and high molecular weight ion traces from particle- phase HR-TOF-AMS mass spectra. The combination of these measurements support the hypothesis that particle-phase chemistry leading to peroxyhemiacetal formation is important. Positive matrix factorization (PMF) was applied to the AMS mass spectra which revealed three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition.

Airborne measurements of biomass burning emissions from a chaparral fire on the central Californian coast were carried out in November 2009. Physical and chemical changes were reported for smoke ages 0 – 4 h old. CO₂ normalized ammonium, nitrate, and sulfate increased, whereas the normalized OA decreased sharply in the first 1.5 - 2 h, and then slowly increased for the remaining 2 h (net decrease in normalized OA). Comparison to wildfire samples from the Yucatan revealed that factors such as relative humidity, incident UV radiation, age of smoke, and concentration of emissions are important for wildfire evolution.

Ground-based aerosol composition is reported for Pasadena, CA during the summer of 2009. The OA component, which dominated the submicron aerosol mass, was deconvolved into hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low-volatility oxidized organic aerosol (LVOOA). The HOA/OA was only 0.08–0.23, indicating that most of Pasadena OA in the summer months is dominated by oxidized OA resulting from transported emissions that have undergone photochemistry and/or moisture-influenced processing, as apposed to only primary organic aerosol emissions. Airborne measurements and model predictions of aerosol composition are reported for the 2010 CalNex field campaign.

Field and Laboratory Studies of Atmospheric Organic Aerosol

This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation.

The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate.

Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f₄₂ and f₉₉) was found to coincide with periods of heavy (f₄₂ > 0.15; f₉₉ > 0.04), moderate (0.05 < f₄₂ < 0.15; 0.01 < f₉₉ < 0.04), and negligible (f₄₂ < 0.05; f₉₉ < 0.01) ship influence. Application of these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( < 1 hr) compared to the time needed for particles to become hygroscopic at sub-saturated humidity ( > 4 hr).

Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate.

Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.

Entre Petrônio e Longo: uma proposta da pedagogia erótica

A presente dissertação tem como corpus o romance erótico grego Pastoral ou Dáfnis e Cloé (III d.C.), do sofista Longo, e o romance erótico latino Satiricon(I d.C.), de Petrônio, arbitro da elegância do imperador Nero. O estudo objetiva descrever, em perspectiva comparada, como esses romancistas estão engajados com a técnica da cura sui, admitindo constituir essa prática uma espécie de paideia, ou seja, uma pedagogia erótica em prol de uma austeridade sexual, em nome da preservação da saúde do corpo e da elevação da alma. Busca, também, mostrar que o gênero romance surgiu muito antes do século XII da nossa era, ao contrário do que se afirma, bem como derrubar a falsa concepção, por parte do leitor moderno, de que a Antiguidade havia sido um verdadeiro paraíso da permissividade sexual. Tal percurso, também, permite-nos, ao fim, uma reflexão diferenciada acerca da situação social e política dos cidadãos livres e escravizados dos primeiros séculos da nossa era

Efeito magnetocalórico em sistemas ferrimagnéticos

Nesta tese, o efeito magnetocalórico é estudado teoricamente partindo de um hamiltoniano modelo que leva em conta uma rede magnética formada por diversas sub-redes magnéticas acopladas. No hamiltoniano são consideradas as interações de troca, Zeeman e magnetoelástica. Primeiramente, o hamiltoniano é apresentado em sua forma generalizada para R sub-redes magnéticas e a influência dos parâmetros do modelo na temperatura de Nèel e na temperatura de compensação é analisada no sistema com duas sub-redes magnéticas. Encontramos que, dependendo dos parâmetros de troca, arranjos ferrimagnético, antiferromagnético e ferromagnéticos podem ser obtidos. O efeito magnetocalórico foi sistematicamente estudado para diversos arranjos possíveis, posteriormente foi estudado em compostos reais do tipo R3Fe5O12 (RIG), sistema formado por três sub-redes magnéticas. Retornando ao sistema com duas sub-redes magnéticas foi analisada a influência da interação magnetoelástica no efeito magnetocalórico nos arranjos ferrimagnéticos obtidos previamente. Aplicando este modelo para uma estrutura cúbica do tipo perovskita, estudamos o efeito magnetocalórico nos compostos EuZrO3 e EuTiO3. Uma metodologia para a obtenção da magnetização de uma amostra policristalina foi apresentada e ainda estudamos o efeito magnetocalórico anisotrópico de natureza antiferromagnética.

In me tota ruens Venus: as leituras dos discursos misógino e feminista em Hipólito de Eurípides

In me tota ruens Venus Vênus derrubando-se inteira sobre mim, esse verso de Horácio representa claramente a posição dos personagens de Fedra e Hipólito na tragédia Hipólito de Eurípides. Em linhas gerais, Fedra, enfeitiçada por Afrodite, sofre de amor pelo seu enteado Hipólito, que a rejeita veementemente. Enfurecida pelo tratamento dispensado por Hipólito não só a ela, mas às mulheres em geral, Fedra acusa Hipólito de estupro, através de um bilhete e suicida-se logo em seguida. Teseu, pai de Hipólito, ao encontrar a esposa morta, exila o filho e providencia que ele seja morto. As tensões criadas pelos discursos de Fedra e Hipólito têm sido material de inúmeros debates críticos. A análise da fortuna crítica levanta mais perguntas que fornece respostas. De todas as linhas críticas, duas linhas antagônicas merecem ser ressaltadas. A leitura crítica do discurso misógino que irá defender que Eurípides não pregava a misoginia através dos seus textos, mas, muito pelo contrário, a combatia ao fazer mudanças no mito dando voz a personagens femininas tão fortes quanto Fedra. E a leitura do discurso feminista que irá defender que há um discurso misógino presente no texto de Eurípides, fruto de uma imposição ideológica vigente na Grécia do século V a.C.. O presente trabalho irá discutir ambos discursos e demonstrar, que a sua maneira, Eurípides não era misógino