Nesse trabalho foram desenvolvidos novos materiais à base de sílica, amorfos e nanoestruturados, pelo método sol-gel de síntese e a adição de precursores com grupos funcionais específicos. Inicialmente foi investigado o comportamento fotofísico de benzazolas dispersas em xerogéis híbridos com diferentes hidrofobicidades, preparados com a adição de diferentes porcentagens molares do precursor dimetildimetoxisilano (DDMS). Nos espectros normalizados de emissão de fluorescência do corante 2-(5’-amino-2’-hidroxifenil) benzimidazol (5-AHBI) disperso nos xerogéis híbridos foram observadas duas bandas, uma delas atribuída a emissão normal (N*) e a outra atribuída a emissão pelo mecanismo de transferência protônica intramolecular no estado excitado - ESIPT (E*), com deslocamento de Stokes próximo a 150 nm. Nos híbridos contendo o corante 2-(5’-amino-2’-hidroxifenil) benzotiazol (5-AHBT), observou-se uma banda bastante alargada em que a emissão de fluorescência mostrou-se dependente da polaridade da matriz, com a emissão máxima variando de 496 para 533 nm com o aumento da porcentagem de DDMS nas sínteses. Sílicas mesoporosas ordenadas do tipo MCM-41 e SBA-15 foram sintetizadas e os resultados de difração de raios X (XRD) e das isotermas de adsorção-dessorção de N2 desses materiais mostraram organização hexagonal de poros, elevadas áreas superficiais específicas, volume de poros de 0,90 cm3 g-1 e distribuição uniforme de mesoporos. Adicionalmente, o uso de autoclave na síntese da sílica MCM-41 parece ter contribuído para uma melhor organização estrutural. Nanopartículas de paládio (NPPd) estabilizadas em solução aquosa pelo silsesquioxano iônico DABCOSIL foram então suportadas nas sílicas mesoporosas ordenadas. As imagens de microscopia eletrônica de transmissão (TEM) mostraram NPPd com tamanho médio de 4 nm nos canais da matriz de sílica SBA-15, que se mostrou mais eficiente como suporte das NPPd em relação à sílica MCM-41. A sílica SBA-15 contendo as NPPd foi utilizada como catalisador heterogêneo em reações de acoplamento Suzuki, com taxas de conversão na ordem de 90 % para o 4-bromotolueno após quatro ciclos de reação. A influência da quantidade e do tipo de precursor contendo grupos orgânicos em ponte na formação de Organossílicas Mesoporosas Ordenadas (PMOs) também foi investigada. Foram preparadas PMOs usando-se o precursor 1,4-bis(trietoxisililpropilureido) benzeno (BDU) em diferentes porcentagens molares e brometo de hexadeciltrimetilamônio (CTAB) como agente direcionador de estrutura, em meio básico. O aumento da quantidade do grupo orgânico do precursor nos híbridos foi confirmada por análise elementar (CHN), análise termogravimétrica (TGA), ressonância magnética nuclear no estado sólido (29Si-NMR) e espectroscopia de absorção no infravermelho (FTIR). As propriedades estruturais e texturais dos híbridos foram analisadas por difração de raios X (XRD) e isotermas de adsorção-dessorção de N2 respectivamente, observando-se que o aumento na porcentagem de BDU provocou diminuição na organização estrutural e colapso dos mesoporos. Também foram preparadas PMOs com o silsesquioxano iônico DABCOSIL, usando-se diferentes direcionadores de estrutura e variando-se o pH do meio. O híbrido sintetizado de forma semelhante à sílica MCM-41 contendo o silsesquioxano iônico DABCOSIL, designado por MDABCO, mostrou maior organização estrutural que o híbrido preparado com o precursor BDU, nas mesmas condições de síntese. Imagens de TEM indicaram a presença de organização hexagonal de mesoporos para o híbrido designado por SDABCO, obtido com o silsesquioxano iônico DABCOSIL em condições experimentais semelhantes à sílica SBA-15. O híbrido SDABCO apresentou elevada área específica (610,5 m2 g-1), distribuição unimodal de mesoporos com máximo em aproximadamente 6,2 nm e volume de poros de 0,87 cm3 g-1. Os resultados indicaram que a incorporação do DABCOSIL na formação de PMOs ocorreu preservando a estrutura hexagonal, o volume e tamanho de poros. Em outro trabalho, foram obtidas diferentes matrizes à base de sílica contendo o organossilano fluorescente 2,5-bis(3-(3-trietoxisilil)propil) ureido)tereftalato de dietila (BT) ligado quimicamente. Os híbridos obtidos pelo método da co-condensação (BTC) e pelo método de enxerto (BTG) mostraram organização hexagonal de poros, que foi confirmada pelas imagens de TEM e pelos resultados de XRD. Estes híbridos apresentaram distribuição uniforme de mesoporos em torno de 6 nm e áreas superficiais específicas na faixa de 600 m2 g-1, maiores do que os valores encontrados para o xerogel híbrido BTX. A análise morfológica do híbrido BTG foi realizada por microscopia eletrônica de varredura (SEM), sendo observadas partículas com uniformidade de tamanho e morfologia. O estudo fotofísico dos híbridos com o corante BT foi realizado por espectroscopia de refletância difusa na região do UV-Vis e por medidas de emissão de fluorescência no estado sólido. Os novos materiais híbridos fluorescentes apresentaram propriedades fotofísicas similares ao corante em etanol, indicando que nos híbridos o corante encontra-se disperso no nível molecular e sua estrutura eletrônica não foi perturbada de forma significativa após sua inserção nas matrizes sólidas. / In this work new silica based materials, amorphous and with nanostructural organization, were developed by the sol-gel method and the addition of precursors with specific functional groups. Initially it was investigated the photophysical behavior of benzazoles dispersed in hybrid xerogels with different hydrophobicities, which were prepared by the addition of different molar percentages of dimethoxydimethylsilane (DDMS) precursor. Two bands were observed in the normalized fluorescent emission spectra of 2-(5-amino-2-hydroxyphenyl)benzimidazole dye (5-AHBI) dispersed in the hybrid xerogels. One is ascribed to normal emission (N*) and another to the Excited State Intramolecular Proton Transfer - ESIPT emission (E*), with Stokes shift near to 150 nm. For the xerogels containing the 2-(5-amino-2-hydroxyphenyl)benzothiazole dye (5-AHBT) it was observed a large band where the fluorescence emission was dependent on the matrix polarity, with the maximum emission varying from 496 to 533 nm in the xerogels with 0 to 50 % of DDMS. Ordered mesoporous silica MCM-41 e SBA-15 were synthesized and the results of X-ray diffraction (XRD) and of N2 adsorption-desorption isotherms of these materials showed hexagonal organization, high specific surface areas, pore volume of 0,90 cm3 g-1 and uniform distribution of mesopores. Additionally the use of the autoclave in the synthesis of silica MCM-41 seems to have contributed to the improvement of the structural organization. Palladium nanoparticles (NPPd) stabilized in aqueous solution by the ionic silsesquioxane DACOSIL was supported in the mesoporous silica. The transmission electron microscopy (TEM) images showed NPPd with average size of 4 nm in the SBA-15 silica channels, which showed to be more efficient as support for NPPd than the MCM-41 silica. The silica SBA15 containing the NPPd was applied as heterogeneous catalyst in Suzuki coupling reactions, with conversion rates near 90% after four cycles of reaction with the 4-bromotoluene. The influence of the quantity and of the type of precursor containing bridged organic groups, in the formation of Periodic Mesoporous Organosilicas (PMOs) was investigated. The precursor 1,4-bridged diureylenebenzene silsesquioxanes (BDU) was used in different molar percentages in the synthesis of PMOs using cetyl trimethyl ammonium chloride (CTAB) as structural directing agent in basic medium. The increasing in the amount of precursor organic group in the hybrids was confirmed by elemental analysis (CHN), thermogravimetric analysis (TGA), solid state nuclear magnetic resonance (29Si-NMR) and infrared absorption spectroscopy (FTIR). The structural and textural properties of hybrids were obtained by XRD and N2 adsorption-desorption isotherms respectively, being observed that the increasing in the BDU percentage caused the decreasing in the structural organization and the collapse of mesopores. Other PMOs, called MDABCO and SDABCO, were prepared with the ionic silsesquioxane DACOSIL, using different structural directing agents and changing the pH of medium. The hybrid prepared in the similar way to MCM41 silica containing the ionic silsesquioxane dabcosil, called MDABCO, showed higher structural organization than the hybrid prepared with the BDU precursor, in the same synthesis conditions. For the hybrid SDABCO, which was obtained in similar experimental conditions to SBA-15 silica, the TEM images indicated the presence of hexagonal organization. The hybrid SDABCO also showed high specific surface area (610,5 m2 g-1), unimodal mesopore distribution with maximum near 6.2 nm and pore volume of ,87 cm3g-1. The results indicated that the incorporation of DABCOSIL in the PMOs formation occurred preserving the hexagonal structure, the pore volume and size. In another work different silica based matrices containing the fluorescent organosilane diethyl 2,5-bis[N,N-(3-triethoxysilyl)propylurea]terephtalate (BT) chemically bonded were obtained. The hybrids BTC and BTG, obtained by co-condensation method and grafting respectively, showed hexagonal organization that was confirmed by TEM images and by the XRD results. These hybrids showed uniform mesopore distribution near 6 nm and specific surface areas of 600 m2 g-1, which were higher than values found for the hybrid xerogel BTX. The morphological analysis of the BTG hybrid was made using the scanning electron microscopy (SEM), being observed particles with uniform size and morphology. The photophysical study of hybrids with the BT dye was made by diffuse reflectance spectroscopy in the UV-Vis region and by solid state fluorescence emission measurements. The new hybrid fluorescent materials presented photophysical properties similar to the dyes in ethanol, indicating that in the hybrids the dye is dispersed in molecular level and its electronic structure was not disturbed in significant form after the insertion in solid matrices.

Orientador : Yoshitaka Gushikem / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-19T03:04:37Z (GMT). No. of bitstreams: 1 Denofre_Silvia_D.pdf: 3297196 bytes, checksum: 81f7916927ca9f902625d985f8b3c196 (MD5) Previous issue date: 1994 / Doutorado

Orientador : Claudio Airoldi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-19T03:01:46Z (GMT). No. of bitstreams: 1 Alcantara_EdesioFernandesdaCosta_D.pdf: 25341923 bytes, checksum: 9e7e0a25428410cf1893cf24d6e33289 (MD5) Previous issue date: 1993 / Doutorado

Orientadores: Carlos Kenichi Suzuki, Antonio Celso de Fonseca Arruda / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-07-19T08:04:11Z (GMT). No. of bitstreams: 1 Torikai_Delson_D.pdf: 4527800 bytes, checksum: 2af6a2e69255f465ca64a2b58f41f899 (MD5) Previous issue date: 1994 / Resumo: A sílica vítrea é um do" únicos materiais que cobinam excelentes propriedades térmicas, ópticas, dielétricas, mecânicas, assim como alta durabilidade química com o alto grau dc pureza. Tradicionalmente, o quartzo brasileiro na forma de lascas tem sido um insumo básico de grande importância na fabricação da sílica vítrea. A seleção de jazidas com quartzo da melhor qualidade em termos dc impurezas, e processos industriais dc purificação tornam-no um material com concentração total da ordem de 10 ppm de impurezas metálicas. Entretanto, nestes últimos anos, um novo insumo (pó de sílica) tem sido desenvolvido por processo sol-gel chegando a um grau de pureza extrema (< 0.1 ppm DD total de impurezas metálicas); e o mais importante, a sua produção independe da matéria-prima quartzo natural. Na presente pesquisa, utilizamos esses novos insumos de elevada pureza, obtidos por processo sol-gel, na preparação da sílica vítrea por fusão em chama (técnica de Verneuil), que resultou num produto inédito em termos das propriedades pureza e resistência mecânica. Contamos, para isso, com a participação de duas empresas, a Nitto Chemical e a Mitsubishi Rasei, para o fornecimento desses novos insumos, ainda em fase de desenvolvimento, através do canal de cooperação técnica entre a UNICAMP e o NIRiN. Realizamos um estudo sobre a influência das principais características das pós de sílica e do processo de fusão nas propriedades da sílica fundida como a transmitância no infra-vermelho e ultra-violeta, e em particular na viscosidade do material. 0 processo Verneuil de fusão utilizado neste trabalho, mostrou ser um processo limpo, não apresentando contaminações metálicas acima da ordem de 0.1 ppm, A agregação de radicais OH mostrou ser reduzida dependendo do tipo de chama (redutora), como por exemplo pela utilização da chama do gás liquefeito de petróleo (GLP), com contaminação da ordem de 100 ppm em comparação com a contaminação de 200 - 250 ppm verificado para a chama de hidrogênio. A viscosidade da sílica vítrea mostrou ser mais vulnerável à presença de alcalinos nas sílicas livres de Alumínio, tendo sua viscosidade reduzida em uma ordem de grandeza para concentrações de sódio de apenas alguns ppm. A sílica vítrea obtida pela fusão em chama à partir do pó de sílica sol-gel, apresenta conteúdos de impurezas metálicas equivalentes à da sílica vítrea comercial obtida pelo processo sintético de deposição química no estado vapor (CVD) por chama de Hz. Apresenta a vantagem de possuir concentrações de OH 5 vezes inferior, e valores dc viscosidade uma ordem de grandeza superior, além do menor custo do processo de fusão por chama em relação ao processo CVD. / Abstract: Not informed. / Doutorado / Doutor em Engenharia Mecânica

Orientador : Yoshitaka Gushikem / Tese (doutorado) Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-19T12:01:00Z (GMT). No. of bitstreams: 1 Andreotti_ElzaIsabelSuely_D.pdf: 3081210 bytes, checksum: 0ac09ad7c5237d73667a594ccb5df8cd (MD5) Previous issue date: 1994 / Doutorado

Orientador: Yoshitaka Gushikem / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-20T07:18:33Z (GMT). No. of bitstreams: 1 Prado_LiliandeLourdesLorencetti_D.pdf: 1756235 bytes, checksum: 292bf553ce3fc3260f4f3bce3b57a853 (MD5) Previous issue date: 1995 / Doutorado

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Mineral biocements are brittle materials, which usually results in catastrophic failure during mechanical loading. Here, previous works demonstrated the feasibility of reducing brittleness by a dual-setting approach, in which a silica sol was simultaneously gelled during the setting of a brushite forming cement. The current thesis aimed at further improving this concept by both using a novel silicate based cement matrix for an enhanced bonding between cement and silica matrix as well as multifunctional silica precursors to increase the network density of the gel. Due to its well-known biocompatibility and osteogenic regeneration capacity, baghdadite was chosen as mineral component of such composites. This required in a first approach the conversion of baghdadite ceramics into self-setting cement formulations. This was investigated initially by using baghdadite as reactive filler in a brushite forming cement (Chapter 4). Here, the ß-TCP component in a equimolar mixture of ß-TCP and acidic monocalcium phosphate anhydrous was subsequently replaced by baghdadite at various concentrations (0, 5, 10, 20, 30, 50, and 100 wt%) to study the influence on physicochemical cement properties such as mechanical performance, radiopacity, phase composition and microstructure. X-ray diffraction profiles demonstrated the dissolution of baghdadite during the cement reaction without affecting the crystal structure of the precipitated brushite phase. In addition, EDX analysis showed that calcium is homogeneously distributed in the cement matrix, while zirconium and silicon form cluster-like aggregates ranging in size from a few micrometers to more than 50 µm. X-ray images and µ-CT analyses indicate improved X-ray visibility with increased incorporation of baghdadite in brushite cement, with an aluminum equivalent thickness nearly doubling at a baghdadite content of 50 wt%. At the same time, the compressive strength of brushite cement increased from 12.9 ± 3.1 MPa to 21.1 ± 4.1 MPa at a baghdadite content of 10 wt%. Cell culture medium conditioned with powdered brushite cement approached physiological pH values when increasing amounts of baghdadite were added to the cement (pH = 6.47 for pure brushite, pH = 7.02 for brushite with 20 wt% baghdadite substitution). Baghdadite substitution also affected the ion content in the culture medium and thus the proliferation activity of primary human osteoblasts in vitro. The results demonstrated for the first time the suitability of baghdadite as a reactive cement additive for improving the radiopacity, mechanical performance, and cytocompatibility of brushite cements. A second approach (Chapter 5) aimed to produce single component baghdadite cements by an increase of baghdadite solubility to initiate a self-setting cement reaction. For this, the material was mechanically activated by longer grinding times of up to 24h leading to both a decrease in particle and crystallite size as well as a partial amorphization of baghdadite. Baghdadite cements were formed by adding water at a powder to liquid ratio of 2.0 g/ml. Maximum compressive strengths were determined to be ~2 MPa after 3 days of setting for a 24-hour ground material. Inductively coupled plasma mass spectrometry (ICP-MS) measurements showed an incongruent dissolution profile of the set cements, with preferential dissolution of calcium and only minor release of zirconium ions. Cement formation occurs under alkaline conditions, with the unground raw powder resulting in a pH of 11.9 during setting, while prolonged grinding increases the pH to about 12.3. Finally, mechanically activated baghdadite cements were combined with inorganic silica networks (Chapter 6) to create dual-setting cements with a further improvement of mechanical performance. While a modification of the cement pastes with a TEOS derived sol was already thought to improve strength, it was hypothesized that using multi-arm silica precursors can further enhance their mechanical performance due to a higher network density. In addition, this should also reduce pore size of both gels and cement and hence will be able to adjust the release kinetics of incorporated drugs. For this, multi-armed silica precursors were synthesized by the reaction of various multivalent alcohols (ethylene glycol, glycerine, pentaerythrit) with an isocyanate modified silica precursor. After hydrolysis under acidic conditions, the sols were mixed with baghdadite cement powders in order to allow a simultaneous gel formation and cement setting. Since the silica monomers have a high degree of linkage sites, this resulted in a branched network that interpenetrated with the growing cement crystals. In addition to minor changes in the crystalline phase composition as determined by X-ray diffraction, the novel composites exhibited improved mechanical properties with up to 20 times higher compressive strength and further benefit from an about 50% lower overall porosity than the reference pure baghdadite cement. In addition, the initial burst release of the model drug vancomycin was completely inhibited by the added silica matrix. This observation was verified by testing for the antimicrobial activity with Staphylococcus aureus by measuring the inhibition zones of selected samples after 24 h and 48 h, whereas the antimicrobial effectiveness of a constant vancomycin release could be demonstrated. The current thesis clearly demonstrated the high potential of baghdadite as a cement formulation for medical application. The initially poor mechanical properties of such cements can be overcome by special processing techniques or by combination with silica networks. The achieved mechanical performance is > 10 MPa and hence suitable for bone replacement under non-load bearing conditions. The high intrinsic radiopacity as well as the alkaline pH during setting may open the way ahead to further dental applications, e.g. as root canal sealers or filler in dental composites. Here, the high pH is thought to lead to antimicrobial properties of such materials similar to commonly applied calcium hydroxide or calcium silicates, however combined with an intrinsic radiopacity for X-ray imaging. This would simplify such formulations to single component materials which are less susceptible to demixing processes during transport, storage or processing. / Mineralische Biozemente sind spröde Materialien, die bei mechanischer Belastung in der Regel ein katastrophales Versagen zeigen. In früheren Arbeiten konnte die Sprödigkeit durch einen dual-härtenden Materialansatz verringert werden, bei dem ein dem Zement zugesetztes Kieselsol während des Aushärtens eines Bruschit-bildenden Zements simultan geliert und so die Matrix verstärkt. Die vorliegende Arbeit zielte darauf ab, dieses Konzept weiter zu verbessern, indem sowohl eine neuartige Zementmatrix auf Silikatbasis für eine verbesserte Bindung zwischen Zement und Kieselsäurematrix als auch multifunktionale Kieselsäure Precursoren zur Erhöhung der Netzwerkdichte des Gels verwendet wurden. Aufgrund der nachgewiesenen Biokompatibilität und osteogenen Regenerationsfähigkeit wurde Baghdadit als mineralischer Bestandteil solcher Komposite gewählt. Dies erforderte in einem ersten Ansatz die Umwandlung von Baghdadit-Keramik in selbsthärtende Zementformulierungen. Dies wurde zunächst durch die Verwendung von Baghdadit als reaktiver Füllstoff in einem Bruschit-bildenden Zement untersucht (Kapitel 4). Dabei wurde die β-TCP-Komponente in einem äquimolaren Gemisch aus β-TCP und saurem Monocalciumphosphat sukzessive durch Baghdadit in verschiedenen Konzentrationen (0, 5, 10, 20, 30, 50 und 100 Gew.-%) ersetzt, um den Einfluss auf die physikalisch-chemischen Zementeigenschaften, wie mechanische Festigkeit, Röntgenopazität, Phasenzusammensetzung und Mikrostruktur zu untersuchen. Röntgenbeugungsprofile zeigten die Auflösung von Baghdadit während der Zementreaktion, ohne die Kristallstruktur der ausgefällten Bruschitphase zu beeinträchtigen. Darüber hinaus zeigte die EDX-Analyse, dass Calcium homogen in der Zementmatrix verteilt ist, während Zirkon und Silizium clusterartige Aggregate mit einer Größe von einigen Mikrometern bis zu mehr als 50 µm bilden. Röntgenbilder und µ-CT-Analysen zeigen eine verbesserte Röntgensichtbarkeit bei erhöhtem Baghdadit-Anteil im Bruschit-Zement, wobei sich die Aluminium-Äquivalentdicke bei einem Baghdadit-Gehalt von 50 Gew.-% nahezu verdoppelt. Gleichzeitig stieg die Druckfestigkeit von Bruschitzement von 12,9 ± 3,1 MPa auf 21,1 ± 4,1 MPa bei einem Baghdaditgehalt von 10 Gew.-%. Zellkulturmedium, das mit pulverförmigem Bruschitzement konditioniert wurde, näherte sich physiologischen pH-Werten an, wenn dem Zement steigende Mengen an Baghdadit zugesetzt wurden (pH = 6,47 für reinen Bruschitzement, pH = 7,02 für Bruschitzement mit 20 Gew.-% Baghdadit-Substitution). Die Baghdadit-Substitution wirkte sich auch auf den Ionengehalt im Kulturmedium und damit auf die Proliferationsaktivität von primären menschlichen Osteoblasten in vitro aus. Die Ergebnisse zeigten zum ersten Mal die Eignung von Baghdadit als reaktives Zementadditiv zur Verbesserung der Röntgenopazität, der mechanischen Eigenschaften und der Zytokompatibilität von Bruschitzementen. Ein zweiter Ansatz (Kapitel 5) zielte auf die Herstellung einkomponentiger Baghdadit-Zemente durch eine Erhöhung der Baghdadit-Löslichkeit ab, um eine Zementreaktion zu initiieren. Dazu wurde das Material durch längere Mahlung von bis zu 24 Stunden mechanisch aktiviert, was sowohl zu einer Abnahme der Partikel- und Kristallitgröße, als auch zu einer teilweisen Amorphisierung von Baghdadit führte. Baghdadit-Zemente wurden durch Zugabe von Wasser bei einem Verhältnis von Pulver zu Flüssigkeit von 2,0 g/ml erhalten. Die maximalen Druckfestigkeiten wurden mit ~2 MPa nach 3 Tagen Aushärtung für ein 24 Stunden gemahlenes Material ermittelt. Massenspektrometrische Messungen mit induktiv gekoppeltem Plasma (ICP-MS) ergaben ein inkongruentes Auflösungsprofil der abgebundenen Zemente mit einer bevorzugten Auflösung von Calcium und einer nur geringen Freisetzung von Zirkonium-Ionen. Die Zementbildung erfolgt unter alkalischen Bedingungen, wobei das ungemahlene Rohpulver während des Abbindens einen pH-Wert von 11.9 aufweist, während ein längeres Mahlen den pH-Wert auf etwa 12.3 erhöht. Abschließend wurden mechanisch aktivierte Baghdadit-Zemente mit anorganischen Silica-Netzwerken kombiniert (Kapitel 6), um dual härtende Zemente mit einer weiteren Verbesserung der mechanischen Eigenschaften zu erhalten. Während eine Modifikation der Zementpasten mit einem TEOS-abgeleiteten Sol bereits die Festigkeit verbessern sollte, wurde angenommen, dass die Verwendung von mehrarmigen Kieselsäure-Precursoren die mechanische Festigkeit aufgrund einer höheren Netzwerkdichte weiter verbessern kann. Darüber hinaus sollte sich auch die Porengröße von Gelen und Zement verringern, so dass die Freisetzungskinetik von inkorporierten Wirkstoffen angepasst werden kann. Zu diesem Zweck wurden mehrarmige Kieselsäure-Precursoren durch die Reaktion verschiedener mehrwertiger Alkohole (Ethylenglykol, Glycerin, Pentaerythrit) mit einem isocyanatmodifizierten Kieselsäure-Precursor synthetisiert. Nach der Hydrolyse unter sauren Bedingungen wurden die Sole mit Baghdadit-Zementpulvern gemischt, um eine gleichzeitige Gelbildung und Zementabbindung zu ermöglichen. Da die Kieselsäuremonomere einen hohen Grad an Verknüpfungsstellen aufweisen, führte dies zu einem verzweigten Netzwerk, das die ausfallenden Zementkristalle durchdrang. Neben geringfügigen Veränderungen in der Zusammensetzung der durch Röntgenbeugung bestimmten kristallinen Phasen, wiesen die neuartigen Komposite verbesserte mechanische Eigenschaften mit einer bis zu 20-fach höheren Druckfestigkeit auf und profitierten außerdem von einer um etwa 50 % geringeren Gesamtporosität als der reine Baghdadit-Referenzzement. Darüber hinaus wurde die anfängliche starke Freisetzung („burst release“) des Modellwirkstoffs Vancomycin durch die zugesetzte Silica-Matrix vollständig gehemmt. Diese Beobachtung wurde durch Prüfung der antimikrobiellen Aktivität mit Staphylococcus aureus durch Messung des Hemmhofs im Agar-Diffusionstest ausgewählter Proben nach 24 h und 48 h verifiziert, wobei die antimikrobielle Wirksamkeit einer konstanten Vancomycin-Freisetzung nachgewiesen werden konnte. Die vorliegende Arbeit zeigte deutlich das hohe Potenzial von Baghdadit Zementformulierungen für medizinische Anwendungen. Die anfänglich schlechten mechanischen Eigenschaften solcher Zemente können durch spezielle Verarbeitungstechniken oder durch die Kombination mit Silicanetzwerken überwunden werden. Die erzielten mechanischen Eigenschaften liegen bei > 10 MPa und die Materialien eignen sich daher für den Knochenersatz unter nicht-lasttragenden Bedingungen. Die hohe intrinsische Röntgenopazität sowie der alkalische pH-Wert während der Aushärtung könnten den Weg für weitere dentale Anwendungen öffnen, z. B. als Wurzelkanal-Zemente oder Füllstoff in Dentalkompositen. Hier ist davon auszugehen, dass der hohe pH-Wert zu antimikrobiellen Eigenschaften solcher Materialien führt, ähnlich wie bei den üblicherweise verwendeten Calciumhydroxiden oder Calciumsilikaten, jedoch in Kombination mit einer intrinsischen Röntgenopazität. Dies würde solche Formulierungen zu einkomponentigen Systemen vereinfachen, die weniger anfällig für Entmischungsprozesse während Transport, Lagerung oder Verarbeitung sind.

Paraffin is used as a main household energy source for cooking, lighting and heating by low-income communities in South Africa. It is highly inflammable and spillages from paraffin can be considered as one of the major causes of fires that lead to the destruction of dwellings in the informal settlement. The situation is made worse due to the close proximity of the dwellings to each other which cause the fires to spread very quickly from one dwelling to the next leaving suffering and most often death in its wake (Schwebel et al., 2009:700). It has been shown by Muller et al. (2003:2018) that most of the informal rural communities use paraffin in non-ventilated and windowless environments and this causes major respiratory problems. The government has made a huge effort towards replacing paraffin as main cooking fuel in rural and informal settlements with ethanol gel. Ethanol gel is a healthier, safer alternative to paraffin because ethanol gel does not burn unless it is contained within a cooking device that concentrates the flame. It also fails to emit lung irritants or other dangerous chemical vapours when burned indoors (Bizzo et al., 2004:67). Commercial ethanol gels are manufactured with imported gelling agents that make their costs unaffordable to the rural poor communities. It is the objective of this study to determine whether gelling agents extracted from the local endemic species of cactacea viz. Opuntia fiscus-indica and Cereus Jamacaru can be used to synthesise ethanol gel comparable or better than the commercial gels. The two species chosen have been declared pests (Nel et al., 2004:61) and are continuously uprooted from arable land and burned by local farmers (Van Wilgen et al., 2001:162) This study showed that Opuntia ficas-indica stems gave a better cellulose yield (15.0 ± 6.7 wt. %) than Cereus Jamacaru (11.5 ± 7.8wt %). Chemical composition analyses and FT-IR analyses showed that the hemicelluloses and lignin were completely removed from the extracted cellulose and the extraction was more effective for Opuntia ficasindica than for Cereus Jamacaru. Ethanol gel produced by using the extracted cellulose, as was investigated during this study, was compared to commercial gels with respect to viscosity, burn time, calorific values and residue and a good comparison was obtained. / Thesis (M.Sc. Engineering Sciences (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

Paraffin is used as a main household energy source for cooking, lighting and heating by low-income communities in South Africa. It is highly inflammable and spillages from paraffin can be considered as one of the major causes of fires that lead to the destruction of dwellings in the informal settlement. The situation is made worse due to the close proximity of the dwellings to each other which cause the fires to spread very quickly from one dwelling to the next leaving suffering and most often death in its wake (Schwebel et al., 2009:700). It has been shown by Muller et al. (2003:2018) that most of the informal rural communities use paraffin in non-ventilated and windowless environments and this causes major respiratory problems. The government has made a huge effort towards replacing paraffin as main cooking fuel in rural and informal settlements with ethanol gel. Ethanol gel is a healthier, safer alternative to paraffin because ethanol gel does not burn unless it is contained within a cooking device that concentrates the flame. It also fails to emit lung irritants or other dangerous chemical vapours when burned indoors (Bizzo et al., 2004:67). Commercial ethanol gels are manufactured with imported gelling agents that make their costs unaffordable to the rural poor communities. It is the objective of this study to determine whether gelling agents extracted from the local endemic species of cactacea viz. Opuntia fiscus-indica and Cereus Jamacaru can be used to synthesise ethanol gel comparable or better than the commercial gels. The two species chosen have been declared pests (Nel et al., 2004:61) and are continuously uprooted from arable land and burned by local farmers (Van Wilgen et al., 2001:162) This study showed that Opuntia ficas-indica stems gave a better cellulose yield (15.0 ± 6.7 wt. %) than Cereus Jamacaru (11.5 ± 7.8wt %). Chemical composition analyses and FT-IR analyses showed that the hemicelluloses and lignin were completely removed from the extracted cellulose and the extraction was more effective for Opuntia ficasindica than for Cereus Jamacaru. Ethanol gel produced by using the extracted cellulose, as was investigated during this study, was compared to commercial gels with respect to viscosity, burn time, calorific values and residue and a good comparison was obtained. / Thesis (M.Sc. Engineering Sciences (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.