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A. Eisenfragment-substituierte Heterosiloxane von Aluminium, Gallium und Indium Die Umsetzung der Ferrio-silanole 5a-c mit Trimethylaluminium, Triisobutylaluminium, Trimethylgallium bzw. Trimethylindium liefert unter Alkaneliminierung die Ferrio-siloxyalane, -gallane bzw. -indane 7a-d, 8a,b und 9a,b in Form von dimeren Aggregaten, welche im Fall von 7b,8b,9a sowie 9b auch röntgenstrukturanalytisch charakterisiert sind. Durch Reaktion der chiralen Ferrio-silanole Cp(OC)2Fe-Si(Me)(R)OH bzw. Cp(OC)(Ph3P)Fe-Si(Me)(R)OH mit AlMe3, GaMe3 bzw. InMe3 erhält man die diastereomeren Ferrio-siloxyalane, -gallane bzw. -indane 8c,9c,11a,b und 12a-c in Form von Dimeren, bei denen man die Aggregation auch NMR-spektroskopisch nachweisen kann. Die Reaktion der Ferrio-silandiole Cp(OC)2Fe-SiR(OH)2 (13a-c) mit einem bzw. zwei Äquivalenten Trimethylgallium (6c) bzw. Trimethylindium (6e) liefert unter Methaneliminierung die dimeren Eisen-substituierten Gallium- bzw. Indiumsiloxanole 14a-e in einem Diastereomerenverhältnis von 50 : 50. 14a-e, die über eine freie Silanolfunktion verfügen, zersetzen sich in Lösung infolge Übertragung des Wasserstoffs vom Sauerstoff auf das Eisenatom. Als Zersetzungsprodukte werden die Eisenhydrid-Verbindung Cp(OC)2Fe-H und Polyheterosiloxane des Typs [RSi(OEMe2)O]n erhalten. Bei der Umsetzung von Cp(OC)2Fe-Si(OH)3 (17) mit Trimethylgallium (6c) bzw. Trimethylindium (6e) erhält man unter Methanabspaltung das Eisen-substituierte Gallium- bzw. Indiumsiloxandiol (18a,b). Setzt man das Ferrio-silantriol 17 mit zwei Äquivalenten Trimethylgallium (6c) in siedendem n-Hexan in Anwesenheit von vier Äquivalenten Tetrahydrofuran um, so resultiert das auch röntgenstrukturanalytisch gesicherte Käfigheterosiloxan 19. Die Umsetzung des Ferriomethyl-silanols Cp(OC)2Fe-CH2-SiMe2OH (20) mit den Trialkylverbindungen der Gruppe 13 (6b-e) liefert unter Alkaneliminierung glatt die Ferriomethyl-substituierten Heterosiloxane 21a-d. Die Aggregation zu Dimeren ist für 21b-d sowohl durch Röntgenstrukturanalyse als auch durch Molgewichtsbestimmung gesichert. B. Phosphan-substituierte Ferrio-silanole und -silantriole: Synthese und Kondensation mit Dimethylchlorsilan Die zweifach Phosphan-substituierten Ferrio-silanole 4a,b können über die Hydrolyse der Ferrio-chlorsilane 2a,b in Anwesenheit von Al2O3 und Triethylamin dargestellt werden. Als alternativer Zugang findet sich der Co2(CO)8-katalysierte H/OH-Austausch an den Ferrio-silanen 3a,b in Gegenwart von Wasser. Der als Zwischenstufe postulierte, zweikernige Komplex Cp(Me3P)2Fe- Si(Me)(p-Tol)Co(CO)4 (5) kann durch Reaktion des Ferrio-silans 3b mit Co2(CO)8 erhalten werden. Das Triphenylphosphan-substituierte Ferrio-trichlorsilan Cp(OC)(Ph3P)Fe-SiCl3 (9) kann im Zweiphasensystem THF/H2O zum Phosphan-substituierten Ferrio-silantriol 10 hydrolysiert werden. Die entsprechende Hydrolyse des kinetisch deaktiverten Cp(Me3P)2Fe-SiCl3 (8b) muß durch Al2O3-Zusatz aktiviert werden. Die Umsetzung der Ferrio-silantriole 10, 11 mit drei Äquivalenten Dimethylchlorsilan und Triethylamin als Hilfsbase führt glatt zu den entsprechenden Ferrio-tetrasiloxanen 12a,b. C. Polychlorierte Metallo-siloxane: Synthese und Austausch- reaktionen mit Methanol und Wasser Die Synthese der polychlorierten Metallo-siloxane 3-5 gelingt durch Umsetzung der Metallate Na[Fe(CO)2Cp] (1a) bzw. Li[W(CO)2(PMe3)Cp] (1b) mit Hexachloro-disiloxan (2a) bzw. Octachlorotetrasiloxan (2b). Das Ferrio-disiloxan 3 kann durch Reaktion mit einem weiteren Äquivalent des Natriumferrats 1a in die Bis(ferrio)-Spezies 6 überführt werden. Die NEt3-assistierte Methanolyse des Ferrio-disiloxans 3 mit drei Äquivalenten MeOH führt unter regiospezifischem Cl/OMe-Austausch am g-Si-Atom zum Trimethoxy-substituierten Ferrio-disiloxan 7, das durch Lösen in Methanol oder Zugabe eines Überschusses an MeOH in eine etherische Lösung von 7 in das vollständig Methoxy-substituierte Derivat 8 umgewandelt werden kann. Bei der Umsetzung des Bis(ferrio)-siloxans 6 mit Methanol bzw. H2O als Nucleophil erhält man sowohl das Tetramethoxy- (10a) als auch das eigenkondensationsstabile Tetrahydroxy-disiloxan 10b, welches mit vier Äquivalenten Dimethylchlorsilan zum entsprechenden Hexasiloxan 11 umgesetzt werden kann. D. Primäre Ferrio-silylamine: Synthese und strukturelle Charakterisierung Die Einwirkung von Natriumamid auf die Phosphan-substituierten Ferrio-chlorsilane 2a-c führt zu den entsprechenden primären Ferrio-silylaminen 3a-c, welche die ersten Übergangsmetall-substituierten primären Silylamine darstellen. Die Molekülstruktur von 3b zeigt im Vergleich zu Organosilylaminen eine signifikante Verlängerung für die Si-N-Bindungslänge mit 1.751(4) Å an. / A. Ironfragment-substituted Heterosiloxanes of Aluminium, Gallium and Indium The reaction of the ferrio-silanols 5a-c with trimethylaluminium, triisobutylaluminium, trimethylgallium and trimethylindium, respectively, yields the corresponding ferrio-siloxyalanes, -gallanes and -indanes 7a-d, 8a,b and 9a,b via elimination of alkane as dimeric aggregates. This molecular arrangement is in addition proved by X-ray analysis for 7b,8b,9a and 9b. The diastereomeric ferrio-siloxyalanes, -gallanes and -indanes 8c,9c,11a,b and 12a-c are obtained by reaction of the chiral ferrio-silanols Cp(OC)2Fe-Si(Me)(R)OH and Cp(OC)(Ph3P)Fe-Si(Me)(R)OH with AlMe3, GaMe3 and InMe3, respectively. The aggregation to dimers can be proved directly by NMR-spectroscopy. The alkane eliminiation reaction of the ferrio-silanediols Cp(OC)2Fe-SiR(OH)2 (13a-c) with one or two equivalents of trimethylgallium (6c) or trimethylindium (6e) generates the dimeric ferrio-substituted gallium- and indiumsiloxanols 14a-e (d.r. 50 : 50). The decomposition of 14a-e in solution proceeds via hydrogen transfer from the oxygen to the iron atom with the formation of the polymeric heterosiloxanes [RSi(OEMe2)O]n and iron hydride Cp(OC)2Fe-H. The iron-substituted galliumsiloxanediol 18a, and indiumsiloxanediol 18b are obtained from the ferrio-silanetriol Cp(OC)2Fe-Si(OH)3 (17) via the alkane elimination process with trimethylgallium (6c) or trimethylindium (6e), respectively. The reaction of the ferrio-silanetriol 17 with two equivalents of trimethylgallium (6c) in boiling n-hexane in the presence of four equivalents of THF yields the cage-like heterosiloxane 19. The molecular structure of 19 is also proved by X-ray analysis. The ferriomethyl-substituted heterosiloxanes 21a-d can be easily generated by reaction of the ferriomethyl-silanol Cp(OC)2Fe-CH2-SiMe2OH (20) with the group 13 triorganyls 6b-e. The aggregation to dimers is proved for 21b-d by X-ray analyses and molecular weight determination. B. Phosphine-Substituted Ferrio-Silanols and -Silanetriols: Synthesis and Condensation with Dimethylchlorosilane The double phosphine-substituted ferrio-silanols 4a,b can be generated by hydrolysis of the corresponding ferrio-chlorosilanes 2a,b in the presence of Al2O3 and triethylamine. An alternative approach is offered by the Co2(CO)8-catalyzed H/OH-exchange reaction of the ferrio-silanes 3a,b with water. The confirmation of the intermediate dinuclear species Cp(Me3P)2Fe-Si(Me)(p-Tol)Co(CO)4 (5) is proved by independent synthesis starting from the ferrio-silane 3b and Co2(CO)8. The hydrolysis of the phosphine-substituted ferrio-trichlorosilanes Cp(OC)(Ph3P)Fe-SiCl3 (9) and Cp(Me3P)2Fe-SiCl3 (8b) is achieved either in the two-phase system THF/H2O, or assisted by Al2O3, yielding the ferrio-silanetriols 10 and 11. The ferrio-silanetriols 10,11 are transformed into the corresponding ferrio-tetrasiloxanes 12a,b by the Et3N-assisted condensation with three equivalents of dimethylchlorosilane. C. Polychlorinated Metallo-Siloxanes: Synthesis and Exchange Reaction with Methanol and Water The synthesis of polychlorinated metallo-siloxanes 3-5 can be achieved by reaction of the metalates Na[Fe(CO)2Cp] (1a) and Li[W(CO)2(PMe3)Cp] (1b) with hexachloro-disiloxane (2a) and octachlorotetrasiloxane (2b), respectively. The ferrio-disiloxane 3 can be transformed into the bis(ferrio) species 6 by substitution of a chlorine by another equivalent of sodium ferrate 1a. The NEt3-assisted methanolysis of the ferrio-disiloxane 3 with three equivalents of MeOH yields the trimethoxy-substituted ferrio-disiloxane 7 provided by regiospecific Cl/OMe-exchange at the g-Si-atom. The completely methoxy-substituted derivative 8 is obtained by dissolving 7 in methanol or addition of an excess of MeOH to an ethereal solution of 7. Using methanol or water in a nucleophilic substitution reaction with the bis(ferrio)-siloxane 6 leads to the tetramethoxy- (10a) or the tetrahydroxy-disiloxane 10b, which is stable towards self-condensation and can be converted to the hexasiloxane 11 by addition of four equivalents of dimethylchlorosilane. Reaction of the ferrio-dimethylsilanol Cp(OC)2Fe-SiMe2OH (12) with hexachloro-disiloxane (2a) generates the monometalated trisiloxane 13, which reacts with another equivalent of 12 to the bismetalated tetrasiloxane 14. 13 and 14 can be converted into the fully methoxy-substituted derivatives 15 and 16 by methanolysis in the presence of NEt3. D. Primary Ferrio-Silylamines: Synthesis and Structural Characterization The phosphine-substituted ferrio-chlorosilanes 2a-c react with sodium amide to yield the primary ferrio-silylamines 3a-c, which represent the first transition metal substituted primary silylamines. The molecular structure of 3b reveals a significant elongation of the Si-N-bond length [1.751(4) Å], compared to organosilylamines. The NEt3-assisted reaction of 3a with dimethylchlorosilane yields the ferrio-silazane 4.

In den vergangenen Jahren wurden vermehrt sogenannte Alginatersatzmaterialien für Indikationsbereiche entwickelt, für die bislang hauptsächlich Alginate verwendet wurden. In dieser in-vitro Studie wurden acht Alginatersatzmaterialien auf Basis von additionsvernetzenden Silikonen und vier Alginate auf ausgewählte mechanische Werkstoffeigenschaften hin untersucht, um beide Materialarten zu vergleichen und daraus Anwendungsempfehlungen ableiten zu können. Die getesteten Alginate waren Alginoplast Regular Set, Blueprint XCreme, Jeltrate Regular Set und Xantalgin select Fast Set. Die getesteten A-Silikone waren AlgiNot FS Cartridge und Volume, AlginX Ultra Cartridge, Position Penta, Silginat, Status Blue, Xantasil Cartridge und Dynamix fast set. Dabei wurden folgenden Materialeigenschaften untersucht: Verformung unter Druck, Rückstellung nach Verformung, Detailwiedergabegenauigkeit, Dimensionsstabilität, Reißfestigkeit, -dehnung, -energie, Toughness, E-Modul und Homogenität. Die Messverfahren, die verwendet wurden, sind in den Normen DIN EN ISO 4823, DIN EN 21563 und DIN 53504 beschrieben. Zur Messung der Dimensionsstabilität wurde ein neues Verfahren angewendet. Der Vergleich der Homogenität richtete sich nach rein optischen Kriterien der abgebundenen Abformmaterialien. Die Ergebnisse zeigen, dass die getesteten Alginatsubstitute gegenüber den Alginaten vorteilhafte Eigenschaften besitzen. Alginate sind gegenüber äußeren Kräften nicht annähernd so widerstandsfähig wie Silikone und lassen sich bei gleicher Krafteinwirkung stärker komprimieren (Verformung unter Druck). Alginate sind leichter, aber weniger weit dehnbar (Reißdehnung). Die Alginate reißen bei deutlich geringerer Zugbelastung (Reißfestigkeit), vor allem in Bereichen, in denen das Abformmaterial nur dünn ausgelaufen ist (Toughness). Die elastische Rückstellungsrate der Alginate und von AlgiNot nach Druckbelastung liegt zwar noch im Normbereich, ist jedoch deutlich geringer als bei den anderen Silikonen, welche eine nahezu vollständige Rückstellung aufweisen. Sowohl Silikone als auch Alginate sind prinzipiell in der Lage, auch feinste Strukturen von 20µm Breite gut abzuformen (Detailwiedergabegenauigkeit). Der Versuch zur Messung der Dimensionsänderung zeigt, dass Alginatabformungen selbst unter optimalen Lagerungsbedingungen bereits nach weniger als 24 Stunden so stark geschrumpft sind, dass es ratsam ist die Abformung zu wiederholen. Die Silikone können mit Ausnahme von Silginat mindesten 14 Tage gelagert werden. Für Silginatabformungen wird eine Lagerungsdauer von maximal sieben Tagen empfohlen. Die Beobachtungen zur Homogenität der angemischten Materialien lassen schließen, dass Silikone bei Verwendung von Automischmaschinen besser und gleichmäßiger vermischt werden. Aufgrund der besseren Materialeigenschaften eignen sich Alginatsubstitute vor allem für Abformungen, die über längere Zeit gelagert werden müssen, bevor ein Gipsmodell hergestellt werden kann und haben den Vorteil, dass aus einer Abformung mehrere Modelle hergestellt werden können. Für die meisten Indikationen genügen die Eigenschaften der Alginate zur Herstellung hinreichend genauer Modelle. Alginate haben außerdem den Vorteil, dass Abformungen mit deutlich geringerer Kraft aus dem Mund entnommen werden können. / Over the last decade, an increasing number of alginate substitutes have been developed for use in areas where alginates had dominated so far. This in-vitro study examined eight alginate substitutes on the basis of addition-silicones and four alginates for selected mechanical properties in order to draw a comparison between both types of material and give recommendations for application. Alginates examined were Alginoplast Regular Set, Blueprint XCreme, Jeltrate Regular Set, and Xantalgin select Fast Set. A-silicones examined were AlgiNot FS Cartridge und Volume, AlginX Ultra Cartridge, Position Penta, Silginat, Status Blue, Xantasil Cartridge, and Dynamix fast set. The following properties were assessed: Strain in compression, elastic recovery, detail reproduction, linear dimensional change, tear strength, elongation at break, toughness, modulus of elasticity, and homogeneity. Measuring methods used are described in DIN standards EN ISO 4823, EN 21563, and 53504. In order to examine dimensional stability, a new method was applied. Comparisons of homogeneity were based on visual criteria regarding set impression materials. Results indicate that between the two tested material groups, alginate substitutes appear superior to alginates. Alginates are less resilient to external forces than silicones and confronted with equal pressure, they compress more quickly (strain in compression). Alginates expand more easily but to a lesser degree (elongation at break). Tear strength in alginates is considerably lower, especially in areas, where there is merely a thin layer of impression material (toughness). Elastic recovery of alginates and AlginNot after compression is within normal range, but substantially lower than with other silicones, with the latter recovering almost completely. Both silicones and alginates can in principle mould finest textures of 20µm width (detail reproduction). The test for linear dimensional change shows that even under optimum storage conditions, within less than 24 hours, alginate impressions have shrunk so strongly that moulding should be repeated. With the exception of Silginat, silicones can be stored for a minimum of 14 days. Silginat impressions are recommended to be stored for up to seven days. Observations concerning homogeneity of mixed materials suggest that automatic mixing leads to better and more evenly mixed silicones. Due to superior properties, alginate substitutes are particularly suitable for impressions which are to be stored for a longer period of time before a plaster model can be produced. A further advantage is the possibility to produce more than one model from an impression. Alginate properties suffice for the production of adequate models regarding most indications. Moreover they can be removed with considerably less force.

The goal of this thesis is to design both liquid crystal hosts and photochromic dopants terminated with short siloxane oligomers in order to produce homogeneous liquid crystal mixtures containing a photochromic component for liquid crystal photoswitches. Some of the liquid crystals terminated with short siloxane oligomers were also found to form 'de Vries'-type SmA phases, which minimize the formation of chevrons and zigzag defects that severely degrade the quality of electro-optic devices. In the first part of the thesis, siloxane-terminated phenylpyrimidine liquid crystals were synthesized and characterized. They form SmC phases and, in some cases, SmA phases. Addition of a terminal halogen substituent on the alkoxy side-chain broadens the SmA temperature range. It was shown that combining a structural element that promotes the formation of a SmC phase with one that promotes the formation of a SmA phase in a mesogen with a 2-phenylpyrimidine core results in a maximum layer contraction of 1.6% for 2-(4-(11-(1,1,1,3,3,5,5-heptamethyltrisiloxanyl)undecyloxy)phenyl)-5-(1-chlorooctyloxy)pyrimidine (33a), which may be considered a ‘de Vries’ material. As an extension of the result obtained in the first project, siloxane-terminated biphenyl benzoate and phenyl benzoate liquid crystals were synthesized and their phase behavior studied. They form SmC phases and, in some cases, SmA and SmI phases. Addition of a terminal chloro substituent on alkoxy side-chain results in a broader SmA temperature range and, in some cases, also affects the nature of the mesophase formed. The compound 4-[6-(1,1,1,3,3,5,5-heptamethyltrisiloxanyl)hexanoyloxy]phenyl 4-(8-chlorooctyloxy)benzoate (40b) is characterized by a maximum layer shrinkage of only 1.7%, which may be considered to possess some ‘de Vries’ character. Finally, siloxane-terminated fulgide derivatives were designed as photochromic dopants for liquid crystal photoswitches. Compound 41 was designed and synthesized and proved to be an oil at room temperature. Solid fulgide precusors 42, 43a and 44b were then assessed as photochromic dopants in terms of fast switching and high quantum yield requirements of a photoswitch, and their photophysical properties were studied in solution. The isomer composition at the photostationary state suggests that the competition from E-Z isomerization is likely too high for compounds 42, 43a and 44b to be suitable as photochromic dopants for photoswitches. / Thesis (Ph.D, Chemistry) -- Queen's University, 2009-05-28 12:46:13.992

Techn. Univ., Diss.--Braunschweig, 2008.

Universiẗat, Diss., 2005--Würzburg.

University, Diss., 2002--Tübingen. / Text. engl.

abstract: Amphipathic molecules consist of hydrophilic and hydrophobic regions, which make them surface-active molecules. The uniqueness of these compounds results in inducing low surface tension and self-assembly of the molecules inside a solvent which have been exploited in personal care, the oil industry and agriculture industry. Amphipathic molecules are also used in the healthcare industry as drug delivery systems and other bio-nanotechnology applications. In this thesis, a novel series of grafted siloxanes have been explored for their probable application in the healthcare industry. The siloxanes are grafted with poly(ethylene glycol) (PEG) and quaternary ammonium salt (QUAT). The effects of varying 1) molar ratios of QUAT to PEG and 2) PEG chain length on contact angle, surface tension, critical micelle concentration (CMC), and micelle assembly properties were studied. In contact angle experiments, the hydrophilicity of grafted siloxanes increased by grafting PEG and QUAT. The amphiphilicity increases and CMC decreases as the PEG chain length shortens. Adding QUAT also reduces CMC. These trends were observed in surface tension and Isothermal Titration Calorimetry experiments. A change in self-assembly behaviour was also observed in Dynamic Light Scattering experiments upon increasing the PEG chain length and its ratio relative to the quaternary ammonium in the siloxane polymer. These polymers have also been studied for their probable application as a sensitive 1H NMR spectroscopy indicator of tissue oxygenation (pO2) based on spectroscopic spin-lattice relaxometry. The proton imaging of siloxanes to map tissue oxygenation levels (PISTOL) technique is used to map T1 of siloxane polymer, which is correlated to dynamic changes in tissue pO2 at various locations by a linear relationship between pO2 and 1/T1. The T1-weighted echo spin signals were observed in an initial study of siloxanes using the PISTOL technique. The change in the ratio of QUAT to PEG and the varying chain length of PEG have a significant effect on the physical property characteristics of siloxane graft copolymers. The conclusions and observations of the present work serve as a benchmark study for further development of adaptive polymers and for the creation of integrated “nanoscale” probes for PISTOL oximetry and drug delivery. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2018

Orientadores: Inez Valeria Pagotto Yoshida, Wilson de Figueiredo Jardim / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-13T12:54:30Z (GMT). No. of bitstreams: 1 PachecoeSilva_Viviane_D.pdf: 3480980 bytes, checksum: 4c99b3d79e0972f6849d577fd58e285e (MD5) Previous issue date: 2009 / Resumo: Este trabalho relata a imobilização do TiO2 em matrizes de siloxano, como alternativa ao emprego do TiO2-pó em suspensão, para a fotodegradação de espécies orgânicas em solução aquosa, sob radiação UV-Vis ou radiação solar, tendo o ácido salicílico (AS) como modelo de poluente. Incorporou-se o TiO2-pó em uma matriz elastomérica de silicona com grau de reticulação relativamente baixo, obtida a partir de goma de poli(dimetilsiloxano) de alta massa molar, obtendo-se compósitos elastoméricos na forma de monólitos. O TiO2-pó também foi incorporado em uma matriz de silicona altamente reticulada, na presença de um agente porogênico, obtendo-se um compósito monolítico rígido e poroso, com características de ¿ceramer¿. Sintetizou-se ainda o TiO2 in situ na forma anatásio, por síntese hidrotérmica, empregando-se como matriz os compósitos contendo TiO2-pó, e placas porosas de vidro. Comparando-se a eficiência dos compósitos elastoméricos com diferentes composições, frente à fotodegradação do AS, sugeriu-se que apenas os sítios de TiO2 mais próximos da superfície iluminada tiveram acesso à radiação UVVis. Apesar das amostras com matriz elastomérica terem apresentado os maiores valores de sorção de AS, o material que apresentou a maior eficiência fotocatalítica sob radiação UV-Vis, superando inclusive o desempenho do TiO2-pó, foi o compósito poroso contendo também o TiO2 gerado in situ, provavelmente devido a sua maior área superficial. Os experimentos conduzidos com esse compósito sob radiação solar evidenciaram uma diminuição na porcentagem de fotodegradação do AS, provavelmente pela menor intensidade da radiação solar, em relação à lâmpada UVVis, associada ao efeito da atenuação da radiação no monólito. Observou-se um pequeno aumento na atividade fotocatalítica do TiO2 com o aumento no tamanho dos cristalitos de anatásio sintetizados in situ, após o tratamento térmico das placas porosas de vidro a 600°C. Os resultados apresentados neste estudo sugerem grande potencialidade na imobilização do TiO2 em matrizes de silicona, tanto pela incorporação do TiO2-pó, quanto pela síntese in situ da fase anatásio / Abstract: This study reports the immobilization of TiO2 in siloxane matrices, as an alternative to the use of TiO2-powder in suspension, for the photodegradation of organic species in aqueous solution, under UV-Vis radiation or solar radiation, having the salicylic acid (SA) as model pollutant. TiO2-powder was incorporated in an elastomeric silicone matrix with a relatively low crosslinking degree, obtained from a poly(dimethylsiloxane) gum with high molecular weight, giving rise to monolithic elastomeric composites. TiO2-powder was also incorporated in a silicone matrix with a high crosslinking degree, in the presence of a pore forming agent, resulting in a hard and porous monolithic composite, with ¿ceramer¿ characteristics. TiO2 in the anatase form was obtained in situ, by hydrothermal synthesis, on the previously prepared composites containing TiO2-powder, and also on glass porous plates. Comparing the efficiency of the elastomeric composites with different compositions, in relation to the SA photodegradation, the results suggested that only the TiO2 sites near the illuminated surface were accessed by the UV-Vis radiation. Although the samples with the elastomeric matrix presented the highest SA adsorption values, the porous composite containing the in situ obtained-TiO2 presented the highest photocatalytic efficiency, with better performance than the TiO2-powder, probably due to the high surface area of this material. When this porous composite was tested under solar radiation, the lower intensity of this radiation, in relation to the UV-Vis lamp, associated to the radiation attenuation effect in the monolith, promoted a decrease in the percentage of SA photodegradation. An increase in the size of the in situ obtained-anatase crystallites, promoted by the thermal treatment of the glass porous plates at 600°C, resulted in an increase in the photocatalytic activity of the TiO2. The results presented in this study suggest a great potential in the immobilization of TiO2 in silicone matrices, either by the incorporation of TiO2-powder, as by the in situ synthesis of the anatase form / Doutorado / Quimica Inorganica / Doutor em Ciências