This dissertation has focused on studying the effect of four glycine derivatives on the solid state properties of mannitol, glycine, and sucrose when freeze dried into blended mixtures. The primary goal was to assess their value for use in the stabilisation of vaccines in the solid state, by examining key physical and chemical characteristics, which have been documented to be beneficial to the stabilisation of biopharmaceutical formulations. The novel excipients; dimethyl glycine, and trimethyl glycine, were shown to retard the crystallisation and increase the overall glass transition temperature, of mannitol, when freeze dried as evidenced by DSC and Powder X-ray diffraction. Mannitol’s glass transition temperature increased from 100C to 12.650C and 13.610C when mixed with methyl-glycine and dimethyl glycine respectively. The glycine derivatives did not show the same effect on sucrose which remained amorphous regardless of the concentration of the other excipient. The different behaviour with the sucrose system was thought to be due to relatively high glass transition temperature of sucrose. Conversely glycine remained highly crystalline due it’s relatively low glass transition temperature. The novel excipient formulations were also assessed for their effect on the aggregation of the adjuvant aluminium hydroxide when freeze dried by Dynamic Light Scattering (DLS).The formulations containing the glycine derivatives all caused a decrease in the aggregation size of the adjuvant from ~26 μm, to 185 nm in the presence of methyl glycine. The effects of lysozyme and viral antigen on the adjuvants were also examined showing that the addition of the virus did not affect the size of the aggregates formed, however lysozyme showed significant decreases in the aggregates formed. Examination of the freezing method were also made showing that faster freezing rates produced smaller aggregates of the adjuvant. When investigating the rate at which the excipients lost water during secondary drying there was evidence of the formation of hydrates of glycine, trimethyl glycine, and mannitol has shown that the glycine derivatives have attributes which would be beneficial in stabilising vaccines in the solid state when freeze dried.

Made available in DSpace on 2016-08-03T12:29:27Z (GMT). No. of bitstreams: 1 Vanderli Duarte de Carvalho 1_194.pdf: 2604830 bytes, checksum: 6aae3c2066d9140325e0e1a05861f79c (MD5) Previous issue date: 2011-06-28 / A questão relacional na área da saúde envolve o imaginário sociocultural. Nos casos de mulheres com câncer de mama, denota um caráter emergencial em virtude do elevado número de ocorrências ou pela falta de percepção feminina da doença, o que dificulta a prevenção e o tratamento em tempo hábil. Este estudo pretende analisar como e de que maneira ocorrem e repercutem as práticas discursivas entre os profissionais da saúde e as pacientes com câncer de mama. Para isso, delineamos como pressupostos teóricos as barreiras da comunicação, seja interpessoal, intrapessoal e não verbal. A metodologia foi com base na Teoria das Representações Sociais de Serge Moscovici e no Discurso do Sujeito Coletivo (DSC) de Ana Maria Cavalcanti Lefévre e Fernando Lefévre. Nas análises dos relatos das mulheres com câncer de mama, identificamos conflitos de ordem sociocultural, como crenças, valores pessoais, estereótipos, enfim, distorções provenientes do senso comum e do imaginário coletivo, disseminadas nas representações da doença levadas a público pela mídia em geral. Nas considerações finais, constatamos que tais representações (estigmas sociais) interferem na relação com os profissionais de saúde, influenciando, assim, a adesão ao tratamento da doença. Os aspectos comunicacionais são aqui apontados de maneira tácita.

A wireless sensor network (WSN) is a collection of sensor nodes distributed over a geographical region to obtain the environmental data. It can have different types of applications ranging from low data rate event driven and monitoring applications to high data rate real time industry and military applications. Energy efficiency and reliability are the two major design issues which should be handled efficiently at all the layers of communication protocol stack, due to resource constraint sensor nodes and erroneous nature of wireless channel respectively. Media access control (MAC) is the protocol which deals with the problem of packet collision due to simultaneous transmissions by more than one neighboring sensor nodes. Time Division Multiple Access based (TDMA-based) and contention-based are the two major types of MAC protocols used in WSNs. In general, the TDMA-based channel access mechanisms perform better than the contention-based channel access mechanisms, in terms of channel utilization, reliability and power consumption, specially for high data rate applications in wireless sensor networks (WSNs). TDMA-based channel access employs a predefined schedule so that the nodes can transmit at their allotted time slots. Based on the frequency of scheduling requirement, the existing distributed TDMA-scheduling techniques can be classified as either static or dynamic. The primary purpose of static TDMA-scheduling algorithms is to improve the channel utilization by generating a schedule of smaller length. But, they usually take longer time to generate such a schedule, and hence, are not suitable for WSNs, in which the network topology changes dynamically. On the other hand, dynamic TDMA-scheduling algorithms generate a schedule quickly, but they are not efficient in terms of generated schedule length. We suggest a new approach to TDMA-scheduling for WSNs, that can bridge the gap between these two extreme types of TDMA-scheduling techniques, by providing the flexibility to trade-off between the schedule length and the time required to generate the schedule, as per the requirements of the underlying applications and channel conditions. The suggested TDMA-scheduling works in two phases. In the first phase, we generate a valid TDMA schedule quickly, which need not have to be very efficient in terms of schedule length. In the second phase, we iteratively reduce the schedule length in a manner, such that the process of schedule length reduction can be terminated after the execution of an arbitrary number of iterations, and still be left with a valid schedule. This step provides the flexibility to trade-off the schedule length with the time required to generate the schedule. In the first phase of above TDMA-scheduling approach, we propose two randomized, distributed and parallel TDMA-scheduling algorithms viz., Distributed TDMA Slot Scheduling (DTSS) and Randomized and Distributed TDMA (RD-TDMA) scheduling algorithm. Both the algorithms are based on graph coloring approach, which generate a TDMA schedule quickly with a fixed schedule length ( Colouring), where is the maximum degree of any node in the graph to be colored. The two algorithms differ in the channel access mechanism used by them to transmit control messages, and in the generated schedule for different modes of communication, i.e., unicast, multicast and broadcast. The novelty of the proposed algorithms lies in the methods, by which an uncolored node detects that the slot picked by it is different from the slots picked by all the neighboring nodes, and the selection of probabilities with which the available slots can be picked up. Furthermore, to achieve faster convergence we introduce the idea of dynamic slot-probability update as per which the nodes update their slot-probability by considering the current slot-probability of their neighboring nodes. Under the second phase of the proposed TDMA-scheduling approach, we provide two randomized and distributed schedule compaction algorithms, viz., Distributed Schedule Compaction (DSC) and Distributed Schedule Length Reduction (DSLR) algorithm, as the mechanism to trade-off the scheduling time with the generated schedule length. These algorithms start with a valid TDMA schedule and progressively compress it in each round of execution. Additionally, Furthermore, the execution of these algorithms can be stopped after an arbitrary number of rounds as per the requirements of underlying applications. Even though TDMA-based MAC protocols avoid packet loss due to collision, due to erroneous nature of wireless medium, they alone are not sufficient to ensure the reliable transmission in WSNs. Automatic Repeat reQuest (ARQ) is the technique commonly used to provide error control for unicast data transmission. Unfortunately, ARQ mechanisms cannot be used for reliable multicast/broadcast transmission in WSNs. To solve this issue, we propose a virtual token-based channel access and feedback protocol (VTCAF) for link level reliable multicasting in single-hop wireless networks. The VTCAF protocol introduces a virtual (implicit) token passing mechanism based on carrier sensing to avoid the collision between feedback messages. The delay performance is improved in VTCAF protocol by reducing the number of feedback messages. Besides, the VTCAF protocol is parametric in nature and can easily trade-off reliability with the delay as per the requirements of the underlying applications. Finally, by integrating all the works, viz., TDMA-scheduling algorithms (DTSS/RD-TDMA), schedule compaction algorithms and link layer feedback mechanism for reliable multicast/ broadcast, we propose a TDMA-based energy aware and reliable MAC protocol, named TEA-MAC for multi-hop WSNs. Similar to VTCAF, TEA-MAC protocol uses the combination of ACK-based and NACK-based approaches to ensure reliable communication. But, instead of using virtual token-based channel access, it uses contention-based channel access for NACK transmission. All the algorithms and protocols proposed in this thesis are distributed, parallel and fault tolerant against packet losses to support scalability, faster execution and robustness respectively. The simulations have been performed using Castalia network simulator to evaluate the performance of proposed algorithms/protocols and also to compare their performance with the existing algorithms/protocols. We have also performed theoretical analysis of these algorithms/protocols to evaluate their performance. Additionally, we have shown the correctness of proposed algorithms/protocols by providing the necessary proofs, whenever it was required. The simulation results together with theoretical analysis show that, in addition to the advantage of trading the runtime with schedule length, the proposed TDMA scheduling approach achieves better runtime and schedule length performance than existing algorithms. Additionally, the TEA-MAC protocol is able to considerably improve the reliability and delay performance of multicast communication in WSNs.

The aim of the thesis is the design and realization of the oscilloscope module with wireless data transfer. One part of the thesis is a short overview of the different types of AD converters. The main part is focused on the hardware configuration that allows modification of the wireless module of the oscilloscope, and the possibility of using in the industrial zone. The design takes into account reducing of consumption and EMC compatibility.

Aim of this diploma thesis is to choose new pattern wax for Fimes a.s. foundry. New wax should substitute old not fully satisfactory pattern wax which caused problems in technological process resulting in increased number of rejects. New pattern wax should eliminate current problems and help foundry with producing large, thin-walled, high-quality castings. Numbers of pattern waxes supplied by world’s leading wax manufacturers were subjected to laboratory tests and pilot study. This diploma thesis is part of project Alfa TA01010766: „Research and development of production technology large, thin and high quality castings of aluminium alloys “

1 Abstract Diamond is a unique material for its physical and chemical stability. However, many advance applications rely on surface functionalisation. Here, two types of diamond were modified on the surface - thin layer of chemical vapor deposition (CVD) and nanodiamond particles (NDs) high pressure and high temperature (HPHT). The aim of CVD surface modification was to prepare photosensitised, conductive, diamond electrodes for dye sensitized solar cells (DSSC). For this purpose, a thin diamond layer doped with boron was deposited on the silicon wafer. Boron doping provided p-type (semi)conductivity to diamonds. The surface of the diamond was hydrogenated with H-plasma, and a short carbon linker with a protected amino group was UV-photografted to the surface. In another study, a photoconverting dye (P1) was covalently attached to the amine-linker. Furthermore, a dye designed based on donor-π-acceptor (D-π-A) concepts was attached to the surface. Finally, a systematic study was done for differently conductive diamond layer and the underlying silicon wafer These experiments gradually lead to the highest ever reported photocurrents of 6.6 µA cm2 for a flat photosensitised boron-doped-diamond (BDD) electrode. Monomolecular layer surface functionalizations on CVD diamond are difficult to detect or even quantify...

Die Arbeit beschreibt neuartige Isocyanat- und Initiierungsreaktionen von speziellen Basen mit dem Imin-Strukturinkrement. Gegenstand des ersten Teils ist die Synthese und Charakterisierung neuer Imidazolin-Isocyanat-Adduksysteme, welche genutzt werden um organische Netzwerke auf der Basis von 1-Ethylimidazolin und diversen Diisocyanaten aufzubauen. Ferner wurden die unterschiedlichen Adduktsysteme hinsichtlich ihrer Anwendbarkeit als blockierte Isocyanate untersucht. Hierzu wurden thermische Analysen wie DSC- und TG-MS-Messungen durchgeführt. Durch experimentelle Ergebnisse und quantenchemische Rechnungen konnte ein neuartiger Reaktionsmechanismus einer Adduktbildung gefunden werden. Die Imidazolin-Isocyanat-Adduktnetzwerke wurden als Macroinitiatoren für die radikalische Polymerisation von Methylmethacrylat (MMA) verwendet, wodurch Adduktnetzwerk-PMMA-Kompositmaterialien erhalten wurden. Gegenstand des zweiten Teils dieser Arbeit ist die Entwicklung eines neuartigen Initiatorsystems für die radikalische Polymerisation von MMA und Styrol, auf der Grundlage der Iminbase-(Meth-)Acrylat-induzierten Polymerisation (IBA-Polymerisation). Hierzu wurden unterschiedlich substituierte Isoxazolone synthetisiert und als Starter für die Polymerisation eingesetzt. Der radikalische Charakter der Polymerisation wurde mittels Copolymerisationsexperimenten belegt.:Abkürzungsverzeichnis 1. Einleitung und Zielsetzung 1.1. Einleitung 1.2. Zielsetzung und Motivation 2. Theoretische Grundlagen 2.1. Isocyanat-Imidazolin-Adduktsysteme als blockierte Isocyanate 2.1.1. Blockierte Isocyanate 2.1.2. Iminbasen-Isocyanat-Addukte 2.2. Radikalische Polymerisation 2.2.2. Autoinitiierung von Styrol und Methylmethacrylat 2.2.3. Definition der IBA- und IBI-Polymerisation 3. Ergebnisse und Diskussion 3.1. Isocyanat-Imidazolin-Adduktsysteme als blockierte Isocyanate 3.1.1. 3 : 1-Isocyanat-Imidazolin-Addukte basierend auf 1-Ethylimidazolin 3.1.2. Organische Netzwerke basierend auf 3 : 1-Isocyanat-Imidazolin-Addukten 3.1.3. 2 : 1-Isocyanat-Imidazolin-Addukte basierend auf 1-Ethyl-2-iso-propyl-imidazolin 3.1.4. 2 : 1-Isocyanat-Imidazolin-Addukte basierend auf 1-Ethyl-2-methyl-imidazolin 3.2. IBA-Polymerisation mittels Isoxazolonen 3.2.1. Tautormerie und thermische Analysen von Isoxazolonderivaten 3.2.2. Polymerisation von Acrylatmonomeren mit Isoxazolonen 3.2.3. Kinetik der IBA-Polymerisation mit Isoxazolonen 3.2.4. IBA-Polymerisation von Styrol mit 3-Phenyl-5-isoxazolon 3.2.5. Mechanistische Studien der IBA-Polymerisation initiiert durch Isoxazolone 4. Zusammenfassung und Ausblick 5. Experimenteller Teil 5.1. Geräte und Chemikalien 5.2. Synthese der Iminbasen 5.3. Synthese der Iminbase–Isocyanat–Addukte 5.4. Synthese der 3 : 1 Adduktnetzwerke 5.5. Synthese von Isoxazolonderivaten 5.6. Polymerisationen von MMA und Styrol mit Isoxazolonen 6. Literatur 7. Anhang Danksagung Lebenslauf Liste an Veröffentlichungen Selbstständigkeitserklärung

This dissertation has focused on studying the effect of four glycine derivatives on the solid state properties of mannitol, glycine, and sucrose when freeze dried into blended mixtures. The primary goal was to assess their value for use in the stabilisation of vaccines in the solid state, by examining key physical and chemical characteristics, which have been documented to be beneficial to the stabilisation of biopharmaceutical formulations. The novel excipients; dimethyl glycine, and trimethyl glycine, were shown to retard the crystallisation and increase the overall glass transition temperature, of mannitol, when freeze dried as evidenced by DSC and Powder X-ray diffraction. Mannitol’s glass transition temperature increased from 100C to 12.650C and 13.610C when mixed with methyl-glycine and dimethyl glycine respectively. The glycine derivatives did not show the same effect on sucrose which remained amorphous regardless of the concentration of the other excipient. The different behaviour with the sucrose system was thought to be due to relatively high glass transition temperature of sucrose. Conversely glycine remained highly crystalline due it’s relatively low glass transition temperature. The novel excipient formulations were also assessed for their effect on the aggregation of the adjuvant aluminium hydroxide when freeze dried by Dynamic Light Scattering (DLS).The formulations containing the glycine derivatives all caused a decrease in the aggregation size of the adjuvant from ~26 μm, to 185 nm in the presence of methyl glycine. The effects of lysozyme and viral antigen on the adjuvants were also examined showing that the addition of the virus did not affect the size of the aggregates formed, however lysozyme showed significant decreases in the aggregates formed. Examination of the freezing method were also made showing that faster freezing rates produced smaller aggregates of the adjuvant. When investigating the rate at which the excipients lost water during secondary drying there was evidence of the formation of hydrates of glycine, trimethyl glycine, and mannitol has shown that the glycine derivatives have attributes which would be beneficial in stabilising vaccines in the solid state when freeze dried. / Stabilitech Ltd. and the Engineering and Physical Sciences Research Council (EPSRC).

No description available.

Non-stoichiometric strontium iron oxide is described by an abbreviated formula SrFeOx (2.5 ≤ x ≤ 3.0) exhibits a variety of interesting physical and chemical properties over a broad range of temperatures and in different gaseous environments. The oxide contains a mixture of iron in the trivalent and the rare tetravalent state. The material at elevated temperature is a mixed oxygen conductor and it, or its derivatives,can have practical applications in oxygen conducting devices such as pressure driven oxygen generators, partial oxidation reactors in electrodes for solid oxide fuel cells (SOFC). ¶ This thesis examines the behaviour of the material at ambient and elevated temperatures using a broad spectrum of solid state experimental techniques such as: x-ray and neutron powder diffraction,thermogravimetric and calorimetric methods,scanning electron microscopy and Mossbauer spectroscopy. Changes in the oxide were induced using conventional thermal treatment in various atmospheres as well as mechanical energy (ball milling). The first experimental chapter examines the formation of the ferrite from a mixture of reactants.It describes the chemical reactions and phase transitions that lead to the formation of the oxide. Ball milling of the reactants prior to annealing was found to eliminate transient phases from the reaction route and to increase the kinetics of the reaction at lower temperatures. Examination of the thermodynamics of iron oxide (hematite) used for the reactions led to a new route of synthesis of the ferrite frommagnetite and strontium carbonate.This chapter also explores the possibility of synthesis of the material at room temperature using ball milling. ¶ The ferrite strongly interacts with the gas phase so its behaviour was studied under different pressures of oxygen and in carbon dioxide.The changes in ferrite composition have an equilibrium character and depend on temperature and oxygen concentration in the atmosphere. Variations of the oxygen content x were described as a function of temperature and oxygen partial pressure, the results were used to plot an equilibrium composition diagram. The heat of oxidation was also measured as a function of temperature and oxygen partial pressure. ¶ Interaction of the ferrite with carbon dioxide below a critical temperature causes decomposition of the material to strontium carbonate and SrFe12O19 . The critical temperature depends on the partial pressure of CO2 and above the critical temperature the carbonate and SrFe12O19 are converted back into the ferrite.The resulting SrFe12O19 is very resistant towards carbonation and the thermal carbonation reaction does not lead to a complete decomposition of SrFeOx to hematite and strontium carbonate. ¶ The thermally induced oxidation and carbonation reactions cease at room temperature due to sluggish kinetics however,they can be carried out at ambient temperature using ball milling.The reaction routes for these processes are different from the thermal routes.The mechanical oxidation induces two or more concurrent reactions which lead to samples containing two or more phases. The mechanical carbonation on the other hand produces an unknown metastable iron carbonate and leads a complete decomposition of the ferrite to strontiumcarbonate and hematite. ¶ Thermally and mechanically oxidized samples were studied using Mossbauer spectroscopy. The author proposes a new interpretation of the Sr4Fe4O11 (x=2.75) and Sr8Fe8O23 (x=2.875)spectra.The interpretation is based on the chemistry of the compounds and provides a simpler explanation of the observed absorption lines.The Mossbauer results froma range of compositions revealed the roomtemperature phase behaviour of the ferrite also examined using x-ray diffraction. ¶ The high-temperature crystal structure of the ferrite was examined using neutron powder diffraction.The measurements were done at temperatures up to 1273K in argon and air atmospheres.The former atmosphere protects Sr2Fe2O5 (x=2.5) against oxidation and the measurements in air allowed variation of the composition of the oxide in the range 2.56 ≤ x ≤ 2.81. Sr2Fe2O5 is an antiferromagnet and undergoes phase transitions to the paramagnetic state at 692K and from the orthorhombic to the cubic structure around 1140K.The oxidized formof the ferrite also undergoes a transition to the high-temperature cubic form.The author proposes a new structural model for the cubic phase based on a unit cell with the Fm3c symmetry. The new model allows a description of the high-temperature cubic form of the ferrite as a solid solution of the composition end members.The results were used to draw a phase diagramfor the SrFeOx system. ¶ The last chapter summarizes the findings and suggests directions for further research.