Neste trabalho foi investigado o efeito exercido por microambientes sobre a estabilidade química e fotoquímica de corantes. Em particular, estudaram-se os fatores responsáveis pelo aumento da estabilidade química e fotoquímica de índigo quando em interação com paligorsquita, que compõem o pigmento histórico Azul Maia, sobre o qual ainda havia controvérsias na literatura. Os corantes investigados foram índigo, dehidroíndigo, alizarina, purpurina, luteolina e β-caroteno; os microambientes foram proporcionados pelas argilas paligorsquita, sepiolita, montmorilonita, laponita e HDL de Al3+ e Mg2+ (3:1). Paligorsquita e a sepiolita são as únicas argilas que apresentam microporos em sua estrutura. As técnicas de caracterização empregadas neste trabalho foram: espectroscopia vibracional (Raman e absorção no infravermelho), espectroscopia de absorção no UV-VIS, difratometria de raios X, análise térmica (TG e DSC), CG-MS, HLPC-MS, medidas de área superficial por isoterma de adsorção de N2 e SEM. Duas técnicas com resolução temporal em escala de sub-picosegundos (absorção de transiente e infravermelho resolvido no tempo) foram utilizadas. O sistema índigo+paligorsquita corresponde à mistura dos dois sólidos, seguida de aquecimento, sendo que a partir de 70 °C a coloração da mistura adquire tonalidade esverdeada e também apresenta maior estabilidade química e fotoquímica. Essa estabilidade e também a alteração na cor aumentam com a temperatura de aquecimento da mistura e o intervalo considerado engloba as temperaturas de perda de água zeolítica (70 - 150 °C) e coordenada (170 - 280 °C) da estrutura da argila. Os resultados de espectroscopia vibracional e eletrônica dos simulantes de Azul Maia indicam que o índigo interage através de ligações de hidrogênio com as moléculas de água coordenada. Essa interação, entretanto, só é possível com a remoção da água zeolítica, o que ocorre a partir de 70 °C. Com aquecimento em temperaturas acima de 170 °C o comportamento do espectro eletrônico e vibracional se altera, indicando a formação direta de complexos com os metais presentes nas bordas internas dos microporos. Os resultados de espectroscopia Raman indicam que com a interação por ligação de hidrogênio a simetria molecular do índigo diminua. Os estudos por espectroscopia com resolução temporal mostraram que o índigo apresenta transferência de próton no estado excitado (ESIPT) de um dos amino grupos para a carbonila adjacente; após esta transferência, há a formação da espécie mono-enol a qual relaxa ao estado fundamental após 120 ps, através de intersecção cônica, o que explica a alta fotoestabilidade do corante. No caso da mistura aquecida a 130 °C os resultados, obtidos pela primeira vez para uma molécula imobilizada em argila, confirmam que o índigo encontra-se em um ambiente hidrofílico, considerando o tempo de vida de decaimento do estado excitado (3,0 ps), comparável ao do índigo carmim em solução aquosa (2,7 ps). O tempo de vida também é muito curto, comparado ao em solução de DMSO (120 ps) o que pode explicar a alta estabilidade do corante quando dentro do microcanal da argila. Finalmente, constatou-se que o dehidroíndigo não é responsável pela coloração de simulantes de Azul Maia, a qual resulta de alterações no espectro de absorção no visível do corante que ocorrem com a interação com a argila / In this work, the role played by the microenvironment on the chemical and photochemical stability of dyes was investigated. The factors responsible for the enhanced stability of indigo when interacting with palygorskite were detailed studied; the indigo and palygorskite system constitutes a simulant of Maya Blue, a historical pigment with properties which are controversially described in the literature. The dyes here investigated were indigo, dehydroindigo, alizarin, purpurin, luteolin and β-carotene; the microenvironment was provided by palygorskite, sepiolite, montmorillonite, laponite and a layered double hydroxide (Al3+ e Mg2+, 3:1). Palygorskite and sepiolite are the only clays with micropores in their structure. Several characterization techniques were employed, namely vibrational spectroscopy (Raman and infrared), UV-VIS electronic absorption spectroscopy, X-ray diffractometry, thermal analysis (TG and DSC), CG-MS, HPLC-MS, surface area and porosity determination (N2 isotherm adsorption) and scanning electron microscopy. Two sub-picosecond time resolved techniques (transient absorption and infrared absorption) were also used. The indigo+palygorskite system corresponds to the intimate mixture of both solids, followed by heating; from 70 °C the mixture attains a greenish hue and an enhanced chemical and photochemical stability. Both stability and color change increase with the heating temperature, which also leads to loss of zeolitic and coordinated water (70 to 150 °C and 170 to 280 °C, respectively). Vibrational and electronic spectroscopies indicate that, in the Maya Blue simulants, the dye interacts with the clay through hydrogen bonds with the coordinated water molecules. Such interaction, however, is only possible with the removal of the zeolitic water, which starts at 70 °C. At temperatures above 170 °C, both vibrational and electronic spectral profiles change, indicating that the interaction is now proceeding directly with the metals that are at the internal borders of the micropores. Results from Raman spectroscopy suggest that with the hydrogen bond and metal interaction a symmetry lowering occurs. Time resolved spectroscopy results show that indigo present an excited state intramolecular proton transfer from one of the NH to the adjacent carbonyl group, originating a mono-enol species, which decays to the ground state after 120 ps through a conical intersection. Such fast decay explains the high photochemical stability of indigo. In the case of the ind+paly mixture heated at 130 °C, the time resolved data obtained for the first time for a dye+clay system confirms that indigo is in a hydrophilic environment, taking into account the excited state lifetime (3.0 ps), comparable to indigo carmine in aqueous solution (2.7 ps). The excited state lifetime of indigo in the clay is also very short when compared to the experimental data for the dye in DMSO solution (120 ps), which is possibly an explanation for the dye high stability when inside the clay micropores. Finally, dehydroindigo was not found to be responsible for the color of Maya Blue simulants, which results from the spectral changes in the dye absorption spectrum originated by the interaction with the clay.

The methods used to create visual effects for feature film production are quickly evolving. Cutting edge techniques are constantly being improved upon, and the capability to solve unique problems is paramount in real world production. I present a creative project which utilizes novel applications of common techniques, such as projection mapping, multi-tile UV workflows, procedural texture generation, normal mapping, and image based lighting.

The purpose of this study was to use soil physical and chemical analyses to better understand the ancient agricultural landscape around the ancient Maya cities of Rio Amarillo and Piedras Negras, two tributary sites to Copan, Honduras. Our primary objective was to determine whether a mass erosion event around 800 A.D. occurred which could have caused crop failure and famine or if stable soil conditions persisted during the collapse of these city-states. Stable carbon isotope analysis of the humin fraction of the soils showed that much of this valley was used anciently for agriculture, including hillslopes and hilltops; however, there is no evidence of mass erosion in the soil profiles. Soil horizon development and texture is consistent with stable soil conditions in this area. The demise of these city-states was likely caused by a variety of factors including warfare and political unrest, and not solely by environmental degradation as postulated in previous studies of the valley.

Stable carbon isotope analyses of the humin fraction of the soil organic matter were conducted on more than 160 soil profiles from Tikal, Guatemala. The profiles were collected from near areas associated with the earthworks of Tikal; an ancient ditch and parapet construction hypothesized to have formed ancient boundaries of the polity. In addition to the isotope analyses, the physical and chemical characteristics of the horizons were determined. Maize, a C4 plant, formed an integral part of the ancient Maya diet and is the only known C4 plant cultivated by the Maya. Prior to and subsequent to the ancient Maya occupation of Tikal, the landscape was dominated by C3 forest vegetation. Over the centuries C4 plant biomass including rhizodeposition decomposed to form soil organic matter that contains a distinct C4 signature reflecting the vegetation history of the area. Forested areas anciently cleared for agriculture were identified through interpretation of significant isotopic shifts that signaled past vegetation changes. Buried horizons were encountered in the upland depressions and bajo wetlands. The aggraded soil deposits were likely the result of increased human activity related to settlement and agriculture. The buried horizons and the overlying sediments exhibited stable carbon isotope shifts associated with forest clearance and maize agriculture. Geospatial analysis of the stable carbon isotope ratios indicated that ancient Maya agriculture was focused on deeper footslope and toeslope soils in both bajos and upland depressions. Some evidence of infield agriculture or food processing was also encountered in connection with ancient settlement at upland locations. The soil data provide insight into ancient land use and sustainability that could potentially contribute to subsistence and population reconstruction models.

The main focus of this project is to chronicle whether or not social inequality increased among households and community-level interactions in Ucanha, Yucatan, Mexico, at the time it was physically integrated with a larger regional polity headed by Ucí around the Terminal Preclassic/Early Classic (50 BCE – CE 400) transition. My research seeks to identify how social distinctions emerged during the early moments of social inequality and how these distinctions did or did not become a threat to social cohesion, as seen in the Early Classic “collapse” in some areas. Using a relational theoretical perspective, I argue that political authority and economic practices are embedded in moral expectations of a household quality of life that is negotiated by all actors. Trenching and broad-scale horizontal excavations document five variables of social distinction—architectural energetics, feasting, diversity of household assemblage, caching/burial practices, and the use of space—at three dwellings. Gini scores that calculate the distribution of fancy ceramics and labor investments in architecture also contribute to measuring household wellbeing at Ucanha. Results highlight differential, yet relatively high, quality of life during the Late Preclassic and then greater inequality and an overall decreased quality of life by the middle of the Early Classic (CE 400/450 – 600). Excavations from contexts associated with monumental architecture indicate vast labor inputs into Ucanha’s built landscape around the time of broader regional integration. Excavations and multi-elemental chemical analyses from the Central Plaza suggest this large public space was built during the Late Preclassic and was used for a variety of rituals that incorporated the populace through processions and performances. By the first few centuries into the Early Classic, however, the Central Plaza was walled off and access became limited and more tightly controlled. Thus, it appears emergent leaders at Ucanha, as evidenced by the presence of iconography related to centralized decision-making and possibly kingship, were successful in providing a high quality of life for their citizenry in exchange for labor and devoted followers during regional integration. Yet, during the Early Classic, household quality of life diminished, access to fancy ceramics became highly curtailed, and many residential platforms were abandoned likely as a result of leaders failing to meet the expectations of their followers.

This project is concerned with obstetric complications and cesarean births in a Yucatec Maya community that has recently began interacting with global market economies and Western biomedicine. ​This research engages with maternal health, reproductive biology, colonial histories, and the global trend of increasing cesarean births. The Yucatec Maya are a short statured population [average adult female height 2010 = 143.2 cm] with historically low obstetric complications and maternal mortality. In the last 30 years, CS rates have risen to account for 25% of all births in this community. Because extreme short stature for population has been linked to obstructed labor and birth complications, this project was designed to determine if stature is impacting the rising rate of CS. Reproductive outcomes and obstetric complications were modeled against height in 3 age cohorts of mothers using one-way ANOVA with a Bonferroni-post hoc test and univariate general linear models. No statistical evidence was found to indicate that stature is related to reproductive outcomes or obstetric complications; however, there is an association between short stature and likelihood of cesarean birth. The dramatic change in birth mode in this population may be attributed to increased availability of biomedical resources, doctor-driven perceptions of indigenous women, and low capacity of rural public hospitals to serve numerous patients in labor.

Par l'association d'une molécule organique colorée avec une matrice inorganique incolore, les composés hybrides sont une solution appropriée pour l'obtention de pigments stables. Ces composés sont en effet capables de résister au temps et aux conditions du milieu les environnant : la stabilité de la couleur est assurée après fixation ou encapsulation de la molécule organique à la surface d'un minéral ou dans une matrice microporeuse. Dans ce travail, nous étudions la diffusion et le processus de physisorption de l'indigo à l'intérieur des cavités et canaux d'alumino-silicates ordonnés tels que les zéolithes. Nous obtenons un complexe hybride, dont la couleur et la stabilité se rapprochent de celles du pigment Bleu Maya archéologique. Le processus physico-chimique à l'origine de la stabilité remarquable du Bleu Maya est encore très controversé. L'élaboration et l'étude du composé archéomimétique ouvre alors de nouvelles perspectives sur la compréhension des caractéristiques spectroscopiques et structurales du Bleu Maya. Les composés analogues sont caractérisés en combinant spectroscopies optiques et vibrationnelles, diffraction des rayons X sur poudre et monocristaux, et diffusion quasi-élastique des neutrons. Nous montrons que l'indigo diffuse sous la forme de monomères dans le réseau de canaux de certaines zéolithes, et se localise en stabilisant le minéral dans un état métastable. Ce travail sur les pigments hybrides anciens et leurs analogues modernes est le premier exemple sur la façon dont les matériaux anciens peuvent être une source d'inspiration dans la conception de matériaux fonctionnels modernes.

<p>Fluid simulation is today a hot topic in computer graphics. New highly optimized algorithms have allowed complex systems to be simulated in high speed. This master thesis describes how the graphics processing unit, found in most computer workstations, can be used to optimize the rendering of volumetric fluids. The main aim of the work has been to develop a software that is capable of rendering fluids in high quality and with high performance using OpenGL. The software was developed at Filmgate, a digital effects company in Göteborg, and much time was spent making the interface and the workflow easy to use for people familiar with Autodesk Maya. The project resulted in a standalone rendering application, together with a set of plugins to exchange data between Maya and our renderer.</p><p>Most of the goals have been reached when it comes to rendering features. The performance bottleneck turned out to be reading data from disc and this is an area suitable for future development of the software.</p>

<p>In 3D and 2D animations walk cycles of characters appear very frequently and are an important way of expressing various aspects of the story told. However walk cycles are tedious and time consuming to animate. In this work an Autodesk MAYA plug-in has been developed, that aims at automating this process. The walk cycle plug-in can be highly beneficial for animators when creating convincing walk cycles in a fast and simple way. The plug-in calculates the right values for each phase in the walk cycle. The GUI of the plug-in makes it easy to provide the required input parameters. In addition, the plug-in allows the animation of a character to walk along a chosen path.</p>

<p>Stereoscopy is a technique that can create an illusion of depth in a flat image. There are many different methods to do this, and here is explained some of the most common and popular ways, with a bigger focus on the anaglyphic method. Since stereoscopy is an old technique, the discovery of it by Charles Wheatstone is explained briefly. In Autodesk Maya 2009, a new stereoscopic plug-in was included which makes the creation of stereoscopic imagery easier. An animated project is made during the course of this research which takes advantage of and tests the functions of the new plug-in. The main purpose of the project is to create a stereoscopic movie which utilized the anaglyph stereoscopic technique. The result is rendered stereoscopic material that is edited with Adobe Premiere Pro to create anaglyphic imagery and a full color alternative using the Infitec technique.</p>