U, FE, AND LI ISOTOPE RATIOS IN THE MINERALIZED AND BARREN AREAS OF THE KOMBOLGIE BASIN

The Paleo- to Meso-Proterozoic Jabiluka unconformity related uranium mine is located within the Alligator River Uranium Field, found in the Northern Territories, Australia. The uranium ore is hosted in the late middle Paleoproterozoic Cahill Formation, which is unconformably overlain by a group of unmetamorphosed conglomerates known as the Kombolgie subgroup. The Kombolgie subgroup provided the source for oxidized basinal brines, carrying U as the mobile form U(VI), which interacted with reducing lithologies in the Cahill formation, thus reducing U(VI) to the solid U(IV), and leading to the precipitation of uraninite (UO2). In order to characterize fluid interaction with the ore body and compare that to areas without mineralization, several isotopic tracers were studied on a series of clay samples from drill core at Jabiluka as well as in barren areas throughout the ARUF. Among the potential tracers, three were selected: U (redox sensitive and recent fluid mobilization), Fe (redox sensitive), and Li (fractionated by hydrothermal fluids and adsorption reactions). δ238U values were found to be closely linked to the mineralogy, with samples with higher K/Al ratios (indicating high illite and low chlorite concentrations) having higher δ238U values. This demonstrates that 235U preferentially absorbs onto the surface of chlorite during hydrothermal circulation. In addition, δ234U values lie far from secular equilibrium (δ234U of 30‰), indicating there was addition or removal of 234U from the surface of the samples from recent (<2.5Ma) interactions of mobile fluids. δ57Fe values were found to be related to lithology and spatially to known uranium deposits. Decreasing δ57Fe values were found with increasing depth to the unconformity in a drill hole directly above the ore zone, but not in drill holes in the barren area. Similarly to δ238U, δ7Li is found to correlate with mineralogy, with higher δ7Li values associated with samples with more chlorite. In addition, higher δ7Li values are found at greater depth throughout the basin, indicating that the direction of the mineralizing fluid circulation was upwards from the Cahill formation to the Kombolgie subgroup.

El periodismo deportivo condicionado por la gestión comunicativa de los clubes de fútbol: el caso del FC Barcelona

Las relaciones entre los gabinetes de Comunicación de los clubes de fútbol y los periodistas deportivos se enmarcan en el modelo de Gieber y Johnson (1961) por el que el hecho de que ambos compartan objetivos comunes, donde los gabinetes de Comunicación necesitan que los medios publiquen determinadas informaciones y los periodistas precisan de noticias que publicar, provoca una pérdida de independencia por parte de los periodistas, ya que necesitan a esos departamentos como fuentes. En la actualidad, los departamentos de Comunicación de los clubes de fútbol, como el del FC Barcelona, se han constituido en gatekeepers. Esto ha acentuado las históricas diferencias que existen entre los periodistas y los profesionales de la comunicación corporativa, incrementado por el control informativo de estos departamentos lo que provoca constantes tensiones entre ambos.

Scaling up online learning checklist: master version

This checklist highlights key questions for institutions that are considering their online learning provision and relates to all three of the Jisc Scaling up online learning guides.

Quantitative characterization of physico-chemical properties of the active layers of reverse osmosis and nanofiltration membranes, and their relation to membrane performance

The main objectives of this dissertation were: (i) to develop experimental and analytical procedures to quantify different physico-chemical properties of the ultra-thin (~ 100 nm) active layers of reverse osmosis (RO) and nanofiltration (NF) membranes and their interactions with contaminants; (ii) to use such procedures to evaluate the similarities and differences between the active layers of different RO/NF membranes; and (iii) to relate characterization results to membrane performance. Such objectives were motivated by the current limited understanding of the physico-chemical properties of active layers as a result of traditional characterization techniques having limitations associated with the nanometer-scale spatial resolution required to study these ultra-thin films. Functional groups were chosen as the main active layer property of interest. Specific accomplishments of this study include the development of procedures to quantify in active layers as a function of pH: (1) the concentration of both negatively and positively ionized functional groups; (2) the stoichiometry of association between ions (i.e., barium) and ionized functional groups (i.e., carboxylate and sulfonate); and (3) the steric effects experienced by ions (i.e., barium). Conceptual and mathematical models were developed to describe experimental results. The depth heterogeneity of the active layer physico-chemical properties and interactions with contaminants studied in this dissertation was also characterized. Additionally, measured concentrations of ionized functional groups in the polyamide active layers of several commercial RO/NF membranes were used as input in a simplified RO/NF transport model to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) at different pH values based on rejection results at one pH condition. The good agreement between predicted and experimental results showed that the characterization procedures developed in this study serve as useful tools in the advancement of the understanding of the properties and structure of the active layers of RO/NF membranes, and the mechanisms of contaminant transport through them.

What makes a successful online learner?

This report is based on a study into online learners and is part of a wider project investigating students’ expectations and experiences of the digital environment.

What makes a successful online learner?

Findings of the Digital Student Online learners’ expectations and experiences of the digital environment

ANTICANCER MECHANISM OF TOLFENAMIC ACID IN COLORECTAL CANCER

Colorectal cancer (CRC) is the third leading cause of cancer-related death in the United States. Chemopreventive therapies could be effective way to treat CRC. Tolfenamic acid, one of the NSAIDs, shows anti-cancer activities in several types of cancer. Aberrant Wnt/β-catenin regulation pathway is a major mechanism of colon tumorigenesis. Here, we sought to better define the mechanism by which tolfenamic acid suppresses colorectal tumorigenesis focusing on regulation of β-catenin pathway. Treatment of tolfenamic acid led to a down-regulation of β-catenin expression in dose dependent manner in human colon cancer cell lines without changing mRNA. MG132 inhibited tolfenamic acid-induced downregulation of β-catenin and exogenously overexpression β-catenin was stabilized in the presence of tolfenamic acid. Tolfenamic acid induced an ubiquitin-mediated proteasomal degradation of β-catenin. In addition, tolfenamic acid treatment decreased transcriptional activity of β-catenin and expression of Smad2 and Smad3 while overexpression of Smad 2 inhibited tolfenamic acid-stimulated transcriptional activity of β-catenin. Moreover, tolfenamic acid decreased β-catenin target gene such as vascular endothelial growth factor (VEGF) and cyclin D1. In summary, tolfenamic acid is a promising therapeutic drug targeting Smad 2-mediated downregulation of β-catenin in CRC.

Faithful Genres: Rhetorics of the Civil Rights Mass Meeting

“Faithful Genres” examines how African Americans adapted the genres of the black church during the civil rights movement. Civil rights mass meetings, as the movement’s so-called “energy machine” and “heartbeat,” serve as the project’s central site of inquiry for these meetings were themselves adaptations of the genre of the black church service. The mass meetings served as the space to draw people into the movement, encourage people toward further activism, and testify to anyone watching that the African American community was working toward desegregation, voting rights, and racial equality. In Martin Luther King, Jr.’s words, “Through these meetings we were able to generate the power and depth which finally galvanized the entire Negro community.” In these weekly or sometimes even nightly meetings, participants inhabited the familiar genres of the black church, song, prayer, and testimony. As they did, they remade these genres to respond directly to white supremacy and to enact the changes they sought to create. While scholars have studied the speeches men and women such as King, Ralph Abernathy, and Fannie Lou Hamer delivered at meetings (Wilson; Selby; Holmes; Brooks), scholars have yet to examine how civil rights mass meetings functioned through a range of genres and rhetors. My study addresses this absence and invigorates this discussion to demonstrate how the other meeting genres beyond the speech—song, prayer, and testimony—functioned to create energy, sustenance, and motivation for activists. Examining these collectively enacted genres, I show how rhetors adapted song, prayer, and testimony toward strategic interventions. I also examine how activists took these same genres up outside the meetings to circulate them in broader contexts for new audiences. By recovering and defining the mass meeting as a flexible repertoire of genres and then examining the redeployment of meeting genres outside the meeting, “Faithful Genres” contributes to histories of civil rights and African American rhetorics, genre studies, and histories of religious rhetorics.

Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work.

Heat dissipation from carbon nano-electronics

The incorporation of graphitic compounds such as carbon nanotubes (CNTs) and graphene into nano-electronic device packaging holds much promise for waste heat management given their high thermal conductivities. However, as these graphitic materials must be used in together with other semiconductor/insulator materials, it is not known how thermal transport is affected by the interaction. Using different simulation techniques, in this thesis, we evaluate the thermal transport properties - thermal boundary conductance (TBC) and thermal conductivity - of CNTs and single-layer graphene in contact with an amorphous SiO2 (a-SiO2) substrate. First, the theoretical methodologies and concepts used in our simulations are presented. In particular, two concepts are described in detail as they are necessary for the understanding of the subsequent chapters. The first is the linear response Green-Kubo (GK) theory of thermal boundary conductance (TBC), which we develop in this thesis, and the second is the spectral energy density method, which we use to directly compute the phonon lifetimes and thermal transport coefficients. After we set the conceptual foundations, the TBC of the CNT-SiO2 interface is computed using non- equilibrium molecular dynamics (MD) simulations and the new Green-Kubo method that we have developed. Its dependence on temperature, the strength of the interaction with the substrate, and tube diameter are evaluated. To gain further insight into the phonon dynamics in supported CNTs, the scattering rates are computed using the spectral energy density (SED) method. With this method, we are able to distinguish the different scattering mechanisms (boundary and CNT-substrate phonon-phonon) and rates. The phonon lifetimes in supported CNTs are found to be reduced by contact with the substrate and we use that lifetime reduction to determine the change in CNT thermal conductivity. Next, we examine thermal transport in graphene supported on SiO2. The phonon contribution to the TBC of the graphene-SiO2 interface is computed from MD simulations and found to agree well with experimentally measured values. We derive the theory of remote phonon scattering of graphene electrons and compute the heat transfer coefficient dependence on doping level and temperature. The thermal boundary conductance from remote phonon scattering is found to be an order of magnitude smaller than that of the phonon contribution. The in-plane thermal conductivity of supported graphene is calculated from MD simulations. The experimentally measured order of magnitude reduction in thermal conductivity is reproduced in our simulations. We show that this reduction is due to the damping of the flexural (ZA) modes. By varying the interaction between graphene and the substrate, the ZA modes hybridize with the substrate Rayleigh modes and the dispersion of the hybridized modes is found to linearize in the strong coupling limit, leading to an increased thermal conductance in the composite structure.

Technological, institutional and market structure changes as evolutionary processes: the case of the Port Wine sector (1680-1974).

Doutoramento em Economia.

Tribes under threat : the collective behavior of firms during the stock market crisis

Due to their unpredictable behavior, stock markets are examples of complex systems. Yet, the dominant analysis of these markets as- sumes simple stochastic variations, eventually tainted by short-lived memory. This paper proposes an alternative strategy, based on a stochastic geometry defining a robust index of the structural dynamics of the markets and based on notions of topology defining a new coef- ficient that identifies the structural changes occurring on the S&P500 set of stocks. The results demonstrate the consistency of the random hypothesis as applied to normal periods but they also show its in- adequacy as to the analysis of periods of turbulence, for which the emergence of collective behavior of sectoral clusters of firms is mea- sured. This behavior is identified as a meta-routine.

Identificação de alvos moleculares para o diagnóstico quantitativo da resistência a pesticidas organofosforados em populações do carrapato-dos-bovinos.

Os programas de controle direcionados aos parasitas ainda exigem a utilização de produtos químicos para maior estabilidade operacional das ações de controle e o uso de carrapaticidas químicos é a principal ferramenta de controle para as infestações do carrapato-dos-bovinos. A utilização de técnicas fenotípicas de avaliação in vitro da suscetibilidade de carrapatos às bases pesticidas são ainda o método mais prático e mais utilizados para o diagnóstico e mensuração do fator de resistência às bases carrapaticidas. Na atualidade, o desenvolvimento e o aprimoramento de provas diagnósticas moleculares de resistência aos diferentes grupos pesticidas devem ser consideradas como ações prioritárias de pesquisa e desenvolvimento dada a necessidade de disponibilização ao setor produtivo de ferramentas acuradas e de rápida execução que a médio prazo venham a substituir os bioensaios, os quais necessitam de aproximadamente 45 dias para obtenção dos resultados. A partir de uma população de Rhipicephalus microplus reconhecidamente resistente a pesticidas foram realizados os estudos que demonstram a atividade enzimática das estares no processo de detoxicação de organofosforados. Observou-se que na cepa de R. microplus resistente a organofosforados ocorreu o aumento na transcrição dos genes que codificam enzimas metabolizantes, possibilitando identificar os alvos moleculares aptos para serem utilizadas no desenvolvimento do ensaio diagnóstico molecular quantitativo para a resistência aos pesticidas organofosforados em populações do carrapato-dos-bovinos.