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Abstract available through American Astronomical Society.

The aim of the present study was to examine retention of spatial reference memory after 6 (Experiment I) and 15days (Experiment II) of binge-like drinking and during alcohol withdrawal in young adult Wistar rats. Prior to alcohol treatment, rats received Morris Water Maze (MWM) training. Afterwards, rats were intragastrically administered ethanol at the dose increasing from 4.5g-to-12g/kg. Intubation control groups (n=7 and n=10, respectively) received infusions of a sucrose solution without ethanol. Subsequently, all subjects were given a single probe trial in the MWM to test memory retention. In both experiments, there were three alcohol groups: A0 group (n=7) tested 4h after the last alcohol administration for acute effects of ethanol / A24 group (n=7) tested 24h after alcohol cessation, when acute ethanol effects disappear but withdrawal symptoms does not develop yet / A72 group (n=7) tested 72h after the last ethanol infusion for withdrawal effects. Finally, potential molecular changes in hippocampus were examined using Fourier Transform Infra-Red (FT-IR) spectroscopy. The blood alcohol concentration was 605.67&plusmn / 36mg/dl. In Experiment I, due to the low overall level of performance in the memory retention task the behavioral effects of ethanol could not be evaluated and no significant between&ndash / group differences were observed in Experiment II. In Experiment I, no significant changes in the molecular make-up of the hippocampus were noted. Conversely, in Experiment II, significant changes in protein, lipid, and nucleic acid profiles related to ethanol intake and withdrawal were found. They are linked to both development of tolerance to ethanol and adverse withdrawal effects.

Die Dissertation hat sich mit der Aufgabe befasst, durch Kombination von IR-Spektroskopie und chemometrischen Auswertungsalgorithmen eine Differenzierung und Klassifizierung von Hirnmetastasen-Dünnschnitten zu erreichen. Die Untersuchungen konzentrieren sich dabei auf jene fünf Primärtumoren, die besonders oft Metastasen im Gehirn bilden. Das sind kolorektale Karzinome, Mammakarzinome, maligne Melanome, Nierenzellkarzinome und Bronchialkarzinome. Metastasen tragen die molekularen Informationen der Gewebezellen des Primärtumors in sich. Die Anwendung von IR-spektroskopischen Methoden stellt deshalb einen innovativen Ansatz zur Identifikation des Primärtumors von Hirnmetastasen dar, da die Spektren einem molekularen Fingerabdruck entsprechen. Als Klassifizierungsalgorithmen wurden SIMCA (soft independent modeling of class analogies) und ANN (artificial neural networks) herangezogen. Die Entwicklung der Klassifizierungsverfahren gliederte sich in drei Teile. Im ersten Teil wurden Trainingsmodelle mit den ausgewählten homogenen Bereichen der Metastasengewebeschnitte erstellt und an unabhängigen Daten weiterer Proben bekannter und unbekannter Organherkunft getestet. Im zweiten Teil wurden die Modelle mit Hilfe homogener Tumorzelllinien optimiert und auf die Zuordnung der Hirnmetastasen zu den Primärtumoren angewandt. Eine zweistufige Klassifizierungsstrategie gewährleistet damit eine Genauigkeit der Klassifizierung von über 80%.

<p>U ovom radu kori&scaron;cen je spektroskopski, teorijski i hemometrijski pristup<br />proucavanju N-HO i N-H&middot;&middot;&middot; vodonicne veze koja se uspostavlja izmedu<br />amidnog protona i etarskog kiseonika tj aromaticnog sistema. U ovom radu<br />odredeni su parametri N-HO i N-H vodonicne veze za &scaron;esnaest Nsupstituisanih<br />amida sa tetrahidrofuranom i toluenom. Vecina ispitivanih amida do<br />sada nije bila izucavana sa stanovi&scaron;ta vodonicne veze. Uspostavljene su korelacije<br />izmedu spektorsopskih i teorijskih parametara. Izvr&scaron;eno je poredenje medu<br />osobinama vodonicno vezanih kompleksa za razlicite amide kao proton donore.<br />Svih 32 ispitivanih vodonicno vezanih kompleksa okarakterisano je<br />hemometrijskim metodama: Klaster analizom i analizom glavne komponente, na<br />osnovu spektroskopskih, teorijskih i Taftovih parametara</p> / <p> In this PhD thesis, N-H&times;&times;&times;O and N-H&middot;&middot;&middot; hydrogen bond beetwen the amide<br /> proton with ether oxygen and aromatic system has been investigated using the<br /> spectroscopic and theoretical approach. The study included sixteen N-substituted<br /> amides (formamides, acetamides, caproamides and benzamides) as well as<br /> tetrahydrofuran and toluene. The possibility of using chemometric methods was<br /> investigated in order to characterise N-H...O and N-H&middot;&middot;&middot; hydrgen bonded<br /> complexes. Hierarchial clustering and Principal Component Analysis (PCA) have<br /> been applied on infrared spectroscopic, PM3 theoretical and Taft parameters of 32 Nsubstituted<br /> amide complexes with tetrahydrofuran and toluene</p>

Nanosized SSZ-13 was synthesized hydrothermally by applying N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as a structure-directing agent. In the next step, the quantity of TMAdaOH in the initial synthesis mixture of SSZ-13 was reduced by half. Furthermore, we varied the sodium hydroxide concentration. After ion-exchange with copper ions (Cu2+ and Cu+), the Cu-SSZ-13 catalysts were characterized to explore their framework composition (XRD, solid-state NMR, ICP-OES), texture (N2-sorption, SEM) and acid/redox properties (FT-IR, TPR-H2, DR UV-Vis, EPR). Finally, the materials were tested in the selective catalytic reduction of NOx with ammonia (NH3-SCR). The main difference between the Cu-SSZ-13 catalysts was the number of Cu2+ in the double six-membered ring (6MRs). Such copper species contribute to a high NH3-SCR activity. Nevertheless, all materials show comparable activity in NH3-SCR up to 350 °C. Above 350 °C, NO conversion decreased for Cu-SSZ-13(2–4) due to side reaction of NH3 oxidation.

The main purpose for this paper is to study iron artefacts excavated in the Black Earth harbour district of Birka. This locale, positioned on the island Björkö in Adelsö par. Sweden, is one of the mayor sites in regard to the Scandinavian Viking age. The how and why of the corrosive process will be touched upon. Specifically how archaeological iron interacts with the soil in which it is found, and what can be done to prevent unnecessary decay after excavation. This, in turn, leads to an observation of how methods have changed in regard to the conservation of archaeological iron, from the processes used in the early days of the field, to the more present day with the method utilized in this study. The conservation of said artefacts is for this study accomplished through the use of a conventional chemical method called EDTA. The usability of this method with waterlogged metallic artefacts is tested. The product of the conservation work revealed the objects to be mostly, iron rivets, bolts or nails. Not too surprising when the articles came from an area widely believed to be a harbour. This specific chemical solution proved not to be a sufficient conservation method for the waterlogged metal objects examined in this paper. This was due to the notably hard crust that covered the objects and the structural fragility of the artefacts. Specific analyses of some of the artefacts were undertaken due to the emergence of substantial amounts of depositions in the final steps of the process. Using XRD, XRF and IR-spectroscopy, the depositions were analysed and the result showed that the depositions most likely consists of a blend of non-water-soluble iron phosphates.

Les minéraux nominalement anhydres du manteau terrestre (NAMs) contiennent de l’eau en faible quantité, dissoute sous forme de défauts ponctuels, et qui affecte de manière drastique les propriétés physico-chimiques du manteau supérieur terrestre. Afin de mieux comprendre cet effet, il est nécessaire d’estimer la capacité de stockage de l’eau des phases mantelliques et les mécanismes de solubilité. De nombreuses données expérimentales sur la solubilité de l’eau dans les NAMs tels que l’olivine, le pyroxène et le grenat, sont disponibles dans la littérature. Toutefois, la majorité de ces études ont été réalisées en système simple, et à des températures ou des pressions trop basses pour être représentatives du manteau supérieur terrestre. L’objectif de cette étude était de contraindre les effets combinés de la pression, de la température et de la composition sur la solubilité de l’eau dans l’olivine et le pyroxène dans les conditions du manteau supérieur terrestre. Les expériences ont été réalisées en condition de saturation en eau dans le système MSH enrichi en fer et en fer et aluminium, à 2,5 ; 5 ; 7,5 et 9 GPa, entre 1175 et 1400°C, à l’aide d’une presse multi-enclumes. Les teneurs en eau ont été mesurées par spectroscopie infrarouge en mode polarisé, à partir d’échantillons finement double polis, sur des cristaux orientés de manière aléatoire. Al est incorporé dans l’olivine et le pyroxène selon la réaction de type Tschermak, et diminue avec la pression dans les deux phases. L’ajout d’Al3+ dans le système favorise l’incorporation de H+ dans l’olivine et surtout dans le pyroxène, mais cet effet disparaît à mesure que la pression et la température augmentent. Dans ces conditions, la solubilité de l’eau dans les deux phases est contrôlée par l’activité de l’eau dans le liquide qui se charge de plus en plus en silicates. Le mécanisme majeur de l’incorporation de l’eau dans l’olivine se fait via le remplacement de sites métalliques par 2H+, impliquant que la solubilité de l’eau dans l’olivine est directement proportionnelle à la fugacité de l’eau dans le liquide. Le partage de l’eau entre pyroxène et olivine est toujours inférieur à 1, sauf à basse pression et basse température, quand Al aide à l’incorporation de l’eau dans le pyroxène par rapport à l’olivine. Dans les conditions du manteau convectif profond, l’eau va préférentiellement dans l’olivine. L’effet de la température sur le partage de l’eau entre les deux phases est négligeable. Ces données ont permis de construire un modèle de stockage de l’eau dans l’olivine à toutes pressions et toutes températures, dans le système MFASH. En combinant ce modèle au partage de l’eau entre pyroxène et olivine calculé dans notre étude, et aux données disponibles dans la littérature sur la solubilité de l’eau dans le clinopyroxène et le grenat, nous avons pu modéliser la capacité de stockage de l’eau dans le manteau supérieur terrestre. Ce modèle prédit que la couche de faible vitesse sismique, détectée à 350 km de profondeur par les observations sismiques, peut être expliquée par la fusion partielle de matériel hydraté provenant de la zone de transition et contenant initialement 750 ppm pds H2O. / Trace amounts of hydrogen dissolved as defects in nominally anhydrous minerals (NAMs) in the mantle are believed to play a key role in physical and chemical processes in the Earth’s upper mantle. Hence the estimation of water storage in mantle phases and solubility mechanisms are important in order to better understand the effect of water. Experimental data on water solubility in NAMs are available for upper mantle minerals such as olivine, pyroxenes and garnet. However, the majority of studies are based on single phases, and at temperatures or pressures that are too low for the Earth’s upper mantle. The aim of this study was to constrain the combined effects of pressure, temperature and composition on water solubility in olivine and pyroxene under upper mantle conditions. The solubility of water in coexisting pyroxene and olivine was investigated by simultaneously synthesising the two phases at high pressure and high temperature in a multi-anvil press. Experiments were performed under water-saturated conditions in the MSH systems with Fe and Al at 2.5, 5, 7.5 and 9 GPa and temperatures between 1175 and 1400°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on doubly-polished thin sections of randomly-oriented crystals. Al is incorporated in pyroxene and olivine via the Tschermak substitution and decreases rapidly as pressure increases in both phases. Addition of Al3+ into the system enhances water solubility notably in pyroxene and also in olivine. However, this effect tends to vanish as pressure and temperature increase. Under these conditions, water solubility in both phases is controlled by water activity in the fluid due to dissolution of silicate component. The main mechanism responsible for water incorporation in olivine is 2H+ substituting for metal sites, which indicates that water solubility in olivine is directly proportional to water fugacity. Water partitioning between pyroxene and olivine is always lower than unity except at low pressure and temperature, in which case Al favours water incorporation into pyroxene rather than into olivine. In the conditions of the deep convective mantle, water preferentially goes into olivine. The effect of temperature on water partitioning between the two phases is negligible. The newly collected data allowed the construction of a water storage capacity model in olivine at all pressures and temperatures in the MFASH system. Combining this model with the newly measured partitioning of water between olivine and pyroxene, as well as previous data on solubility in clinopyroxene and garnet, we are able to build a model of the water saturation curve in the upper mantle. This model predicts that the low velocity layer reported by seismic observations at a depth of 350 km depth can be explained by partial melting triggered by the rise of a hydrated mantle-transition-zone material containing 750 wt ppm H2O.

Os ionômeros de vidro vêm sendo utilizados largamente na odontologia com diversas funções. Suas formulações sofreram alterações durante os anos, como a incorporação de componentes resinosos, para a melhoria de suas propriedades físicas e aumento do tempo de trabalho. Com isso, o estudo teve como objetivo avaliar o grau de conversão e a microdureza Knoop dos cimentos de ionômero de vidro modificados por resina (Rely X Luting e Vitremer, ambos da 3M ESPE) de acordo a forma de polimerização (química ou fotopolimerável por lâmpada halógena Ultralux EL ? Gnatus e LED LEC 1000 ? MMOptics) e o tempo de armazenagem. Três espécimes de cada material, autopolimerizável e fotopolimerizável, e tipo de fotopolimerização (por luz halógena e LED) foram confeccionados para cada tempo experimental de 6 horas, 1, 2, 3, 5, 7 ,11 e 14 dias (n=72). Os espécimes foram armazenados em ambiente escuro a 37°C durante esses períodos. Os 72 espécimes foram analisados pela espectroscopia FT-IR para a medição do grau de conversão (GC). Três espécimes de cada material e tipo de polimerização (n=9) foram confeccionados para a medição da microdureza, com um penetrador diamantado piramidal, tipo Knoop, carga estática de 50 gramas por 30 segundos. Os resultados encontrados demonstraram que o material fotopolimerizado com LED apresentou os maiores valores do grau de conversão e da microdureza. O grau de conversão aumentou com o tempo de armazenagem enquanto a microdureza obteve os maiores resultados entre 24-48 horas. Os resultados permitiram concluir que para os cimentos de ionômero de vidro modificados por resina, Vitremer e Rely X Luting, o material fotopolimerizável onde se utilizou o LED apresentou os melhores resultados e que a microdureza Knoop foi ineficaz para predizer o grau de conversão. / Glass ionomer cement have been widely used for many functions. Over the years, some alterations have been made to improve some physico-mechanical properties and to prolong working time. The purpose of this study was to evaluate the relation of the degree of conversion (DC) and Knoop microhardness of resin modified glass ionomer cements (Rely X Luting and Vitremer - 3M ESPE) with polymerization type (chemical curing and light curing reactions, using halogen light or LED) and time of storage. Three specimens of each material, self-cured and light-cured, and light-curing type (halogen light or LED) were prepared for each period of time (n=72). Specimens were stored in dark and dry conditions, at 37oC, during 6 hours, 1, 2, 3, 5, 7, 11 and 14 days. All the specimens were analyzed by FT-IR spectroscopy to measure the DC. Three specimens of each material and polimeryzation type (n=9) were prepared for the microhardness determination, equipped with a Knoop indenter, 50g load for 30 seconds. Results showed that higher values of DC and Knoop microhardness were found on the LED light-cured material. DC values increased with storage time while the Knoop microhardness achieved its higher values between 24-48 hours. Results showed that the LED light-curing unit used to polymerize the resin modified glass ionomer cement Vitremer achieved better values of DC, between light and self-cured materials, and that the Knoop microhardness could not predict the DC.

Biochemische Prozesse treten in wässriger Umgebung auf und Wechselwirkungen der Wasserhülle mit Biomolekülen spielt eine Schlüsselrolle für deren Struktur und Funktion. In dieser Arbeit wird die Strukturdynamik der Wassermoleküle und Gegenionen in der umgebenden Wasserhülle der DNA mit der Methode der zweidimensionalen Infrarotspektroskopie (2D IR) sowie Anrege-Abfrage-Spektroskopie untersucht. Die Ergebnisse der vorliegenden Arbeit zeigt das starke Potenzial von Schwingungsmoden an Grenzflächen für die Abbildung und das Verständnis von Wechselwirkungen zwischen Biomolekülen und ihrer Wasserhülle. In Zukunft soll dieses Konzept auch auf andere Biomoleküle angewendet werden. / Biochemical processes occur in an aqueous environment and interactions of the water shell with biomolecules play a key role for their structure and function. In this thesis, the structural dynamics of water molecules and counterions in the hydration shell of DNA is investigated by two-dimensional infrared (2D IR) spectroscopy and pump-probe transient spectroscopy. 2D IR spectroscopy is a powerful technique that can track molecular couplings between different vibrational modes and structural fluctuations of the chemical environment on a femto- to picosecond time scale. In the present study, vibrational modes of the DNA backbone serve as probes located at the DNA-water interface. The results of this thesis demonstrate the strong potential of interfacial vibrational modes for mapping and understanding interactions between biomolecules and their water shell. In future, this concept will be applied to other biomolecular systems.