Effect of cycling on the magnetization of ion exchanged magnetic nanocomposite based on polystyrene

Magnetic nanocomposites containing iron oxide particles embedded in a polymer matrix have been synthesized using the method of ion exchange. They have been characterized by using low temperature and room temperature magnetic measurements and Mo¨ ssbauer spectroscopy. The iron content in these samples has also been determined. The results have been analysed and explained. The physical and chemical properties of these nanocomposite materials are different from those of the bulk. Some of the unique properties of these materials find application in information storage, color imaging, ferrofluids and magnetic refrigeration

Nutrient dynamics in the two lakes of Kerala, India

Distribution and chemistry of major inorganic forms of nutrients along with physico-chemical parameters were investigated. Surface sediments and overlying waters of the Ashtamudi and Vembanad Lakes were taken for the study, which is situated in the southwest coast of India. High concentrations of dissolved nitrogen and phosphorus compounds carried by the river leads to oxygen depletion in the water column. A concurrent increase in the bottom waters along with decrease in dissolved oxygen was noticed. This support to nitrification process operating in the sediment-water interface of the Ashtamudi and Vembanad Lake. Estuarine sediments are clayey sand to silty sand both in Ashtamudi and Vembanad in January and May. Present study indicates that the sediment texture is the major controlling factor in the distribution of these nutrient forms. For water samples nitrite, inorganic phosphate was high in Vembanad in January and May compared to Ashtamudi. For sediments, enhanced level of inorganic phosphate and nitrite was found in Vembanad during January and May. It had been observed that the level of N and P is more in sediments. A comparative assessment of the Ashtamudi and Vembanad Lake reveals that the Vembanad wetland is more deteriorated compared to the Ashtamudi wetland system

Sedimentology and Geochemistry of core sediments from the Ashtamudi estuary and the adjoining coastal plain,central Kerala,India

The evolution of coast through geological time scale is dependent on the transgression-regression event subsequent to the rise or fall of sea level. This event is accounted by investigation of the vertical sediment deposition patterns and their interrelationship for paleo-enviornmental reconstruction. Different methods like sedimentological (grain size and micro-morphological) and geochemical (elemental relationship) analyses as well as radiocarbon dating are generally used to decipher the sea level changes and paleoclimatic conditions of the Quaternary sediment sequence. For the Indian coast with a coastline length of about 7500 km, studies on geological and geomorphological signatures of sea level changes during the Quaternary were reported in general by researchers during the last two decades. However, for the southwest coast of India particularily Kerala which is famous for its coastal landforms comprising of estuaries, lagoons, backwaters, coastal plains, cliffs and barrier beaches, studies pertaining to the marine transgression-regression events in the southern region are limited. The Neendakara-Kayamkulam coastal stretch in central Kerala where the coast is manifested with shore parallel Kayamkulam Lagoon on one side and shore perpendicular Ashtamudi Estuary on the other side indicating existence of an uplifted prograded coastal margin followed by barrier beaches, backwater channels, ridge and runnel topography is an ideal site for studying such events. Hence the present study has been taken up in this context to address the gap area. The location for collection of core samples representing coastal plain, estuarylagoon and offshore regions have been identified based on published literature and available sedimentary records. The objectives of the research work are:  To study the lithological variations and depositional environments of sediment cores along the coastal plain, estuary-lagoon and offshore regions between Kollam and Kayamkulam in the central Kerala coast  To study the transportation and diagenetic history of sediments in the area  To investigate the geochemical characterization of sediments and to elucidate the source-sink relationship  To understand the marine transgression-regression events and to propose a conceptual model for the region The thesis comprises of 8 chapters. The first chapter embodies the preamble for the selection and significance of this research work. The study area is introduced with details on its physiographical, geological, geomorphological, rainfall and climate information. A review of literature, compiling the research on different aspects such as physico-chemical, geomorphological, tectonics, transgression-regression events are presented in the second chapter and they are broadly classified into three viz:- International, National and Kerala. The field data collection and laboratory analyses adopted in the research work are discussed in the third chapter. For collection of sediment core samples from the coastal plains, rotary drilling method was employed whereas for the estuary-lagoon and offshore locations the gravity/piston corer method was adopted. The collected subsurficial samples were analysed for texture, surface micro-texture, elemental analysis, XRD and radiocarbon dating techniques for age determination. The fourth chapter deals with the textural analysis of the core samples collected from various predefined locations of the study area. The result reveals that the Ashtamudi Estuary is composed of silty clay to clayey type of sediments whereas offshore cores are carpeted with silty clay to relict sand. Investigation of the source of sediments deposited in the coastal plain located on either side of the estuary indicates the dominance of terrigenous to marine origin in the southern region whereas it is predominantly of marine origin towards the north. Further the hydrodynamic conditions as well as the depositional enviornment of the sediment cores are elucidated based on statistical parameters that decipher the deposition pattern at various locations viz., coastal plain (open to closed basin), Ashtamudi Estuary (partially open to restricted estuary to closed basin) and offshore (open channel). The intensity of clay minerals is also discussed. From the results of radiocarbon dating the sediment depositional environments were deciphered.The results of the microtextural study of sediment samples (quartz grains) using Scanning Electron Microscope (SEM) are presented in the fifth chapter. These results throw light on the processes of transport and diagenetic history of the detrital sediments. Based on the lithological variations, selected quartz grains of different environments were also analysed. The study indicates that the southern coastal plain sediments were transported and deposited mechanically under fluvial environment followed by diagenesis under prolonged marine incursion. But in the case of the northern coastal plain, the sediments were transported and deposited under littoral environment indicating the dominance of marine incursion through mechanical as well as chemical processes. The quartz grains of the Ashtamudi Estuary indicate fluvial origin. The surface texture features of the offshore sediments suggest that the quartz grains are of littoral origin and represent the relict beach deposits. The geochemical characterisation of sediment cores based on geochemical classification, sediment maturity, palaeo-weathering and provenance in different environments are discussed in the sixth chapter. In the seventh chapter the integration of multiproxies data along with radiocarbon dates are presented and finally evolution and depositional history based on transgression–regression events is deciphered. The eighth chapter summarizes the major findings and conclusions of the study with recommendation for future work.

Adsorption of element 112 on a Au surface

Während der letzten 20 Jahre hat sich das Periodensystem bis zu den Elementen 114 und 116 erweitert. Diese sind kernphysikalisch nachgewiesen, so dass jetzt die chemische Untersuchung an erster Selle steht. Nachdem sich das Periodensystem bis zum Element 108 so verhält, wie man es dem Periodensystem nach annimmt, wird in dieser Arbeit die Chemie des Elements 112 untersucht. Dabei geht es um die Adsorptionsenergie auf einer Gold-Ober fläche, weil dies der physikalisch/chemische Prozess ist, der bei der Analyse angewandt wird. Die Methode, die in dieser Arbeit angwandt wird, ist die relativistische Dichtefunktionalmethode. Im ersten Teil wird das Vielkörperproblem in allgemeiner Form behandelt, und im zweiten die grundlegenden Eigenschaften und Formulierungen der Dichtefunktionaltheorie. Die Arbeit beschreibt zwei prinzipiell unterschiedliche Ansätze, wie die Adsorptionsenergie berechnet werden kann. Zum einen ist es die sogenannte Clustermethode, bei der ein Atom auf ein relativ kleines Cluster aufgebracht und dessen Adsorptionsenergie berechnet wird. Wenn es gelingt, die Konvergenz mit der Größe des Clusters zu erreichen, sollte dies zu einem Wert für die Adsorptionsenergie führen. Leider zeigt sich in den Rechnungen, dass aufgrund des zeitlichen Aufwandes die Konvergenz für die Clusterrechnungen nicht erreicht wird. Es werden sehr ausführlich die drei verschiedenen Adsorptionsplätze, die Top-, die Brücken- und die Muldenposition, berechnet. Sehr viel mehr Erfolg erzielt man mit der Einbettungsmethode, bei der ein kleiner Cluster von vielen weiteren Atomen an den Positionen, die sie im Festkörpers auf die Adsorptionsenergie soweit sichergestellt ist, dass physikalisch-chemisch gute Ergebnisse erzielt werden. Alle hier gennanten Rechnungen sowohl mit der Cluster- wie mit der Einbettungsmethode verlangen sehr, sehr lange Rechenzeiten, die, wie oben bereits erwähnt, nicht zu einer Konvergenz für die Clusterrechnungen ausreichten. In der Arbeit wird bei allen Rechnungen sehr detailliert auf die Abhängigkeit von den möglichen Basissätzen eingegangen, die ebenfalls in entscheidender Weise zur Länge und Qualität der Rechnungen beitragen. Die auskonvergierten Rechnungen werden in der Form von Potentialkurven, Density of States (DOS), Overlap Populations sowie Partial Crystal Overlap Populations analysiert. Im Ergebnis zeigt sich, dass die Adsoptionsenergie für das Element 112 auf einer Goldoberfläche ca. 0.2 eV niedriger ist als die Adsorption von Quecksilber auf der gleichen Ober fläche. Mit diesem Ergebnis haben die experimentellen Kernchemiker einen Wert an der Hand, mit dem sie eine Anhaltspunkt haben, wo sie bei den Messungen die wenigen zu erwartenden Ereignisse finden können.

Growth and yield of groundnut, sesame and roselle in an Acacia senegal agroforestry system in North Kordofan, Sudan

A field experiment was conducted under rainfed conditions in western Sudan at El-Obeid Research Farm and Eldemokeya Forest Reserve, North Kordofan State, during the growing seasons 2004/05 and 2005/06. The main objective was to investigate the soil physical and chemical properties and yield of groundnut (Arachis hypogea), sesame (Sesamum indicum) and roselle (Hibiscus sabdariffa) of an Acacia senegal agroforestry system in comparison with the sole cropping system. Data were recorded for soil physical and chemical properties, soil moisture content, number of pods per plant, fresh weight (kg ha^−1) and crop yield (kg ha^−1). The treatments were arranged in Randomized Complete Block Design (RCBD) and replicated four times. Significant differences (P < 0.05) were obtained for sand and silt content on both sites, while clay content was not significantly different on both sites. The nitrogen (N) and organic carbon were significantly (P < 0.05) higher in the intercropping system in Eldemokeya Forest Reserve compared with sole cropping. Soil organic carbon, N and pH were not significant on El-Obeid site. Yet the level of organic carbon, N, P and pH was higher in the intercropping system. Fresh weight was significantly different on both sites. The highest fresh weight was found in the intercropping system. Dry weights were significantly different for sesame and roselle on both sites, while groundnut was not significantly different. On both sites intercropping systems reduced groundnut, sesame and roselle yields by 26.3, 12 and 20.2%, respectively. The reduction in yield in intercropping plots could be attributed to high tree density, which resulted in water and light competition between trees and the associated crops.

Untersuchung der Adsorptionskinetik photoschaltbarer azobenzolfunktionalisierter selbstorganisierter Monolagen mit optischer Frequenzverdopplung

In dieser Arbeit wurde das Adsorptionsverhalten zweier azobenzolfunktionalisierter Liganden auf Goldoberflächen untersucht. Diese Liganden zeichnen sich dadurch aus, dass sie mithilfe von Licht bestimmter Wellenlängen zwischen zwei Isomerisierungszuständen – sowohl in Lösung als auch in den auf der Oberfläche resultierenden Monolage – hin und her geschaltet werden können. Somit ist es möglich, Oberflächen herzustellen, deren physikalische und chemische Eigenschaften zwischen zwei Zuständen variiert werden können. Die Messungen des Adsorptionsverhaltens wurden mittels optischer Frequenzverdopplung durchgeführt. Diese Messmethode ist höchst grenzflächensensitiv und ermöglicht es somit die Adsorption der Liganden in situ und ich Echtzeit zu verfolgen. Neben den Adsorptionsmessungen wurde auch die Phase des frequenzverdoppelten Signals über eine Interferenzmethode gemessen. Die Ergebnisse dieser Phasenmessungen ermöglichen es, eine Aussage über eine mögliche Nichtlinearität der untersuchten Moleküle zu treffen. An die in den Adsorptionsmessungen gewonnenen Messdaten wurden drei kinetische Standardmodelle angepasst. Beschreibt eines dieser Modelle den im Experiment bestimmten Adsorptionsverlauf, kann eine Aussage über die zugrunde liegenden Prozesse des Adsorptionsvorganges getroffen werden. Die Ergebnisse der Adsorptionsmessungen zeigen einen deutlichen Einfluss des Isomerisierungszustandes der Liganden auf den Verlauf der Adsorption. Liegen die Moleküle im geschalteten Zustand vor, so verläuft die Adsorption langsamer. Weiterhin konnte gezeigt werden, dass ebenso intermolekulare Wechselwirkungen über Wasserstoffbrückenbindungen einen verlangsamenden Einfluss auf die Adsorption der Liganden haben. In den durchgeführten Phasenmessungen zeigte sich darüber hinaus, dass Liganden, die über an die Azobenzolgruppe angebundene Amidgruppen verfügen, eine Nichtlinearität aufweisen. Diese Nichtlinearität ist zudem vom Isomerisierungszustand der Liganden abhängig. In den kinetischen Untersuchungen konnte darüber hinaus gezeigt werden, dass sich die Adsorption der Liganden bis auf eine Ausnahme durch die Langmuirkinetik 2. Ordnung beschreiben lässt. Somit handelt es ich bei der Adsorption der untersuchten Liganden um eine Reaktion, der eine Bindungsspaltung voran geht. Dieser Befund konnte durch Vergleich mit weiteren Experimenten bestätigt werden.

Biochar improves fertility of a clay soil in the Brazilian Savannah: short term effects and impact on rice yield

The objective of this study was to report single season effects of wood biochar (char) application coupled with N fertilization on soil chemical properties, aerobic rice growth and grain yield in a clayey Rhodic Ferralsol in the Brazilian Savannah. Char application effected an increase in soil pH, K, Ca, Mg, CEC, Mn and nitrate while decreasing Al content and potential acidity of soils. No distinct effect of char application on grain yield of aerobic rice was observed. We believe that soil properties impacted by char application were inconsequential for rice yields because neither water, low pH, nor the availability of K or P were limiting factors for rice production. Rate of char above 16 Mg ha^(−1) reduced leaf area index and total shoot dry matter by 72 days after sowing. The number of panicles infected by rice blast decreased with increasing char rate. Increased dry matter beyond the remobilization capacity of the crop, and high number of panicles infected by rice blast were the likely cause of the lower grain yield observed when more than 60 kg N ha^(−1) was applied. The optimal rate of N was 46 kg ha^(−1) and resulted in a rice grain yield above 3 Mg ha^(−1).

Teoría de restricciones aplicada a la cadena de suministros en un operador logístico de productos farmacéuticos

En las instituciones hospitalarias es fundamental el tema relacionado con los medicamentos y dispositivos médicos para la atención del paciente, por lo tanto el mecanismo de adquisición y disponibilidad de éstos productos, ha llevado a la participación masiva de operadores logísticos (Outsoursing) interviniendo áreas de la cadena de suministros, desde el punto de fabricación con el producto terminado hasta la dispensación del medicamento o dispositivo médico, para que ser usado o administrado al paciente. Los operadores logísticos han emprendido una búsqueda de soluciones por medio de diferentes metodologías y estrategias que permitan entregar a tiempo en las farmacias hospitalarias, conservando las propiedades físicas y químicas de los medicamentos y dispositivos médicos, garantizando así la calidad de los productos. En ésta tesis se plantea una nueva alternativa de gestión de medicamentos y dispositivos médicos en un operador logístico de productos farmacéuticos a través de la teoría de restricciones (TOC), para emprender acciones que permitan analizar el sistema bajo esta metodología, intervenir de manera oportuna, impactar y estimular al personal a trabajar en la búsqueda del mejoramiento , aumentando a su vez la velocidad del flujo de operación en toda la cadena de suministros, basada no en el mejoramiento de los óptimos locales o de los subprocesos sino en la identificación de la verdadera restricción del sistema, permitiendo realizar un análisis más a fondo encontrando el conflicto raíz para mejorar el sistema a nivel global.

Estudi fonamental i aplicat de l'etapa d'eliminació de tinta per flotació

La tesi realitza un estudi detallat dels principals processos que tenen lloc durant l'eliminació de tinta tòner per flotació. L'estudi del procés d'adhesió de tinta a la superfície de bombolles d'aire s'ha realitzat mitjançant visió artificial. Els resultats obtinguts han mostrat que un excés de tensioactiu provoca una disminució de la quantitat de tinta unida a la bombolla d'aire i per tant una disminució de l'eficàcia del procés de flotació. La caracterització de les bombolles d'aire presents en una cel·la de flotació ha posat de manifest que tant el cabal d'aire com la velocitat de l'agitador configuren la distribució de diàmetres final. L'estudi del procés d'eliminació de tinta per flotació en absència de fibres cel·lulòsiques ha mostrat que les variables físico-químiques estudiades són les que tenen una major influència en el procés d'eliminació de tinta tòner per flotació. Finalment s'han addicionat fibres cel·lulòsiques a la suspensió. S'ha pogut comprovar que s'aconsegueix una bona eliminació de tinta sempre i quan les condicions hidrodinàmiques siguin les adequades.

Bioinspired iron and manganese catalysts for the effective and selective oxidation of alkanes and alkenes

La gran eficiència, selectivitat i les condicions suaus exhibides per les reaccions que tenen lloc al centre actiu de les metal·looxigenases són la font d'inspiració per la present dissertació. Amb l'objectiu de dissenyar catalitzadors d'oxidació eficients hem fet ús de dues estratègies: la primera consisteix en el disseny de complexos amb baix pes molecular inspirats en aspectes estructurals de la primera esfera de coordinació del centre metàl·lic d'enzims de ferro i de manganès. Aquests complexos s'han estudiat com a catalitzadors en l'oxidació selectiva d'alcans i d'alquens fent servir oxidants "verds" com ara l'H2O2. La segona estratègia està basada en l'ús de la química supramolecular per tal de desenvolupar estructures moleculars auto-acoblades amb la forma i les propietats químiques desitjades. Concretament, la construcció de nanocontenidors amb un catalitzador d'oxidació incrustat a la seva estructura ens permetria dur a terme reaccions més selectives, tal com passa en les reaccions catalitzades per enzims.

Single and multiple addition to C60. A computational chemistry study

Des del seu descobriment, a la molècula C60 se li coneixen una varietat de derivats segons el tipus de funcionalització amb propietats fisicoquímiques específiques de gran interès científic. Una sel·lecció de derivats corresponents a addicions simple o múltiple al C60 s'ha considerat en aquest treball d'investigació. L'estudi a nivell de química computacional de diversos tipus d'addició al C60 s'han portat a terme per tal de poder donar resposta a aspectes que experimentalment no s'entenen o són poc clars. Els sistemes estudiats en referència a l'addició simple al C60 han estat en primer lloc els monoiminoful·lerens, C60NR, (de les dues vies proposades per la seva síntesi, anàlisis cinètic i termodinàmic han ajudat a explicar els mecanismes de formació i justificar l'addició a enllaços tipus [5,6]), i en segon lloc els metanoful·lerens i els hidroful·lerens substituits, C60CHR i C60HR, (raons geomètriques, electròniques, energètiques i magnètiques justifiquen el diferent caràcter àcid ente ambdós derivats tenint en compte una sèrie de substituents R amb diferent caràcter electrònic donor/acceptor). Els fluoroful·lerens, C60Fn, i els epoxid ful·lerens, C60On, (anàlisi sistemàtic dels seus patrons d'addició en base a poder justificar la força que els governa han aportat dades complementàries a les poques que existeixen experimentalment al respecte).

Theoretical studies of the exohedral reactivity of fullerene compounds

Des del descobriment del buckminster ful.lerè el 1985, s'ha despertat un interés enorme per entendre la reactivitat química així com les propietats d'aquests compostos. La funcionalització exoèdrica del ful.lerè més abundant, el C60, està força ben establerta. Tanmateix, la investigació en aquest camp encara continua oberta ja que s'han sintetitzat una gran varietat de derivats molt prometedors donades les seves futures aplicacions. La tesi comprèn quinze capítols que contenen set publicacions relacionades. Els primers dos estudis es basen en la reacció Diels-Alder sobre els anomenats metal.loful.lerens endoèdrics TNT X3N@C78, X= Sc, Y. Aquest projecte de investigació està motivat pel desconeixament existent sobre les possibles conseqüències de l'encapsulació del grup X3N. El tercer estudi descriu minuciosament els canvis detectats en la funcionalització exoèdrica un cop s'ha produït l'encapsulació dels diferents gasos nobles. En aquesta tesi s'estudia en detall l'ús de l'aproximació ONIOM per a estudiar reaccions de cicloaddició en compostos ful.lerènics. Els resultats d'aquest projecte són d'alt interès per a la realització dels estudis posteriors sobre la reacció de Diels-Alder i la 1,3-dipolar en ful.lerens i derivats. Finalment, l'última part d'aquesta tesi es basa en les propietats antioxidants de determinats ful.lerens. A l'últim treball inclòs en aquesta tesi s'estudia en detall el mecanismo de reacció per a la eliminació del ió superòxid en presència de ful.lerens.

Fate of prions in soil: Longevity and migration of recPrP in soil columns

Research into transmissible spongiform encephalopathy (TSE) diseases has become a high priority worldwide in recent years yet remarkably little is known about the behaviour of TSE infectivity in the environment. The resilience and stability of prion proteins could lead to soils becoming a potential reservoir of TSE infectivity as a result of contamination from activities such as infected carcass burial or the dispersion of effluents from slaughter houses, or by contamination of pastures by infected animals, (e.g. scrapie in sheep). Knowledge of the fate of prion proteins in soils, and associated physico-chemical conditions which favour migration, can be used to help prevent re-infection of animals through grazing, to protect watercourses and develop good management practices. In two consecutive experiments of 9 and 6 months, the migration of recombinant ovine PrP (recPrP) in soil columns was followed under contrasting levels of microbial activity (normal versus reduced), under varying regimes of soil water content and redox potential, and in two different soil types (loamy sand and clay loam). At each analysis time (1, 3, 6 or 9 months), in both soil types, full-length recPrP was detected in the original contaminated layer, indicating the resilience and stability of recPrP under varied soil conditions, even in the presence of active soil microbial populations. Evidence of protein migration was found in every soil column at the earliest analysis time (1 or 3 months), but was restricted to a maximum distance of 1 cm, indicative of limited initial mobility in soils followed by strong adsorption over the following days to weeks. The survival of recPrP in the soil over a period of at least 9 months was demonstrated. In this study, recPrP was used as an indicator for potential TSE infectivity, although infectivity tests should be carried out before conclusions can be drawn regarding the infection risk posed by prions in soil. However, it has been demonstrated that soil is likely to act as a significant barrier to the dispersion of contaminated material at storage or burial sites. (c) 2007 Elsevier Ltd. All rights reserved.

Context-aware visual exploration of molecular databases

Facilitating the visual exploration of scientific data has received increasing attention in the past decade or so. Especially in life science related application areas the amount of available data has grown at a breath taking pace. In this paper we describe an approach that allows for visual inspection of large collections of molecular compounds. In contrast to classical visualizations of such spaces we incorporate a specific focus of analysis, for example the outcome of a biological experiment such as high throughout screening results. The presented method uses this experimental data to select molecular fragments of the underlying molecules that have interesting properties and uses the resulting space to generate a two dimensional map based on a singular value decomposition algorithm and a self organizing map. Experiments on real datasets show that the resulting visual landscape groups molecules of similar chemical properties in densely connected regions.

Fast training of self organizing maps for the visual exploration of molecular compounds

Visual exploration of scientific data in life science area is a growing research field due to the large amount of available data. The Kohonen’s Self Organizing Map (SOM) is a widely used tool for visualization of multidimensional data. In this paper we present a fast learning algorithm for SOMs that uses a simulated annealing method to adapt the learning parameters. The algorithm has been adopted in a data analysis framework for the generation of similarity maps. Such maps provide an effective tool for the visual exploration of large and multi-dimensional input spaces. The approach has been applied to data generated during the High Throughput Screening of molecular compounds; the generated maps allow a visual exploration of molecules with similar topological properties. The experimental analysis on real world data from the National Cancer Institute shows the speed up of the proposed SOM training process in comparison to a traditional approach. The resulting visual landscape groups molecules with similar chemical properties in densely connected regions.