<p> The advantageous properties of siloxanes find use in a wide range of applications. Unfortunately, the dynamic nature of silicones which is responsible for these properties is often a limitation in the controlled synthesis and modification of siloxane materials. Gaining greater control over these processes would allow for the synthesis of siloxane materials with more explicit structures, giving them a narrower range of properties and expanding application. Furthermore, the ability to synthesize more siloxane architectures with greater control would allow for an increased understanding of the relationship between structural features and physical properties.</p> <p> The synthesis of hydrosilane-rich siloxane elastomers and subsequent controlled modification, particularly with poly(ethylene oxide), is described. The effect of chain length and functionality (mono- or di-) was found to influence the morphology of grafted polymer. It was also possible to take advantage of the intrinsic properties of siloxanes to sequester hydrophilic moieties to the interior of the elastomer. Utilizing the same hydrosilane rich elastomers, a method for the independent modification of the interior and exterior of hydrosilane rich elastomers is presented. The careful selection of grafting moieties and solvents is used to provide or deny transport to the interior of the elastomer. This method is used to synthesize PEO modified elastomers with various subsequent internal modifications.</p> <p> A method for controlled synthesis of silicone-carbohydrate composites is also described. Utilizing bifunctional silane linkers, protected carbohydrates were functionalized with bulky diisopropyl hydrosilane groups before linkage to short and long silicones. Alternatively, the linker could first be joined to a silicone, followed by silylation of unprotected saccharides using the resultant hindered chlorosilane functional silicone. This method gave preferential silylation at primary hydroxyl groups.</p> <p> Finally, a method is presented for the synthesis of explicit branched siloxane architectures. The B(C6F5)3 catalyzed dehydrocarbonative coupling of hydrosilanes with alkoxysilanes was used to construct branched siloxane architectures in a stepwise fashion. High levels of control were available through manipulation of steric parameters: careful selection of starting materials and conditions allowed for the synthesis of explicit alkoxysilane functional branched siloxanes. These could be grafted to hydrosilane functional silicone polymers, or used to assemble explicit branched siloxanes. Further explorations demonstrated that the assembly process was not inhibited by the presence of organohalide- or alkene functional groups, allowing for the synthesis of functional siloxane moieties with explicit structures.</p> / Thesis / Doctor of Philosophy (PhD)

No description available.

The adhesion of poly(dimethyl siloxane) (PDMS) to silica substrates was measured by 90 degree peel testing of PDMS strips cast on silica substrates. The objective of this work was to investigate the effects of silica surface chemistry on the adhesion between PDMS and silica substrate. Silica substrates with different surface chemistry were prepared by both chemical modification and physical adsorption. Silane coupling agents were used to provide octyl chains and primary amino groups on the silica surfaces. Also silica surfaces were coated with cetyltrimethylammonium bromide (CTAB), polyvinylamine (PVAm) or poly(N-isopropylacrylamide) (PNIPAM) by physical adsorption. The adhesion samples were prepared by casting Sylgard® 184 silicone elastomers on silica surfaces followed by thermal curing. Water contact angle measurements, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared microscopy (FTIR) were performed to measure the surface properties of the peel test samples. It is believed that hydrogen bonding between siloxane bonds in PDMS and silanol groups on silica substrate contributes to the strong adhesion of PDMS and silica surface. The adhesion forces significantly reduced by the adsorption of PVAm and PNIPAM onto silica surfaces. In addition, the introduction of primary amino groups on silica surface would poison the catalyst during the curing of PDMS, which causes the formation of low crosslinking PDMS in the outer surface and is expected to decline the adhesion force. Lastly, the slightly reduce of adsorbed PVAm (340 kDa) on the silica substrate after peel test is considered to be useful for long-term lubrication. / Thesis / Master of Applied Science (MASc)

De part leurs nombreuses activités biologiques et leur propriétés physicochmiques et structurales, les peptides présentent un intérêt considérable pour la conception de molécules actives mais aussi pour l'élaboration de biomatériaux. Pour lutter contre l'alopécie (perte de cheveux) et la canitie (blanchiment des cheveux), nous avons axé nos travaux sur la recherche de peptides bioactifs. Pour cela, nous avons identifié des peptides têtes de série provenant soit de la littérature soit d'un criblage réalisé par l'institut européen de biologie (IEB). Ces peptides têtes de séries ont été modifiés afin d'améliorer leur activité et leur biodisponibilité tout en tenant compte du mode d'administration par voie topique. Lors de ce travail, nous avons également développé deux nouvelles méthodologies permettant la polymérisation de séquences peptidiques. En effet, les polymères à base de peptide présentent un intérêt majeur pour des applications en biotechnologie (tissus artificiels, implants), ou comme systèmes de transport ou de délivrance de principes actifs. Nous avons notamment mis au point la polymérisation de peptides hybrides présentant des fonctions dimethylsilanol ainsi que la polymérisation par ouverture du cycle de N-carboxyanhydrides portant une séquence peptidique. Ces deux stratégies ont permis d'obtenir des polymères linéaires ou en peigne. / Because of their numerous biological activities and their structural and physico-chemical properties, peptides are of considerable interest for the design of active molecules but also for the development of biomaterials. To fight against alopecia (hair loss) and canities (whitning hair), we focused our attention on the research of bioactive peptides. In this context, we have identified leads peptides either from the literature or from a screening conducted by the European Institute of Biology (IEB). These Leads were modified to improve their activity and bioavailability knowing that they will be applied topically. In this work, we have also developed two new methodologies for the polymerization of peptide sequences. Indeed, peptide-based polymers are of major interest for applications in biotechnology (i.e. artificial tissue,implants), or as systems of transport and delivery of drug. The first methodology relies on the polymerization of the hybrid peptides displaying dimethyl hydroxysilane functions. The other one involves the ring opening polymerization of N-carboxyanhydrides bearing a peptide sequence. Both strategies were used to obtain linear or comb peptide-polymers.

Ziel dieser Arbeit war es, die Permeationseigenschaften von Polysiloxan-Membranen im Hinblick auf ihre definierte Mikrostruktur näher zu analysieren. Es konnte gezeigt werden, dass die Mikrostruktur der Membranen einen statistisch signifikanten Einfluss auf die Permeationsgeschwindigkeit der untersuchten Substanzen hat. Zum besseren Verständnis der Permeation wurden auch die Diffusionsvorgänge innerhalb der Membran untersucht. Durch den Einsatz der Konfokalen Raman-Spektroskopie ist es gelungen, den Aufbau eines Konzentrationsgradienten innerhalb der Membran zu zeigen. Weiterhin konnte der Einfluss der Mikrostruktur der Membranen auf die Geschwindigkeit des Aufbaus dieses Gradienten nachgewiesen werden. / It was the aim of this project to find out how the permeability of a given molecule through a polysiloxane membrane with defined microstructure is determined by its physico-chemical properties. It turned out that the network chain length takes a statistically significant influence on the permeability of the tested compounds. Confocal Raman-spectroscopy was taken as a pioneering method to investigate the kinetics of diffusion within a membrane before the steady state has been reached. It was able to show the formation of the concentration gradient of ß-carotene in polysiloxane membranes. Additionally the influence of the microstructure before reaching steady state conditions could be observed.

Zugl.: Stuttgart, Univ., Diss., 2009

Triarylamine type materials with vastly altered physical properties are synthesized by hybridizing organic semiconducting structures with silicone and siloxane groups. By altering the silicon content of these materials, we can tune their physical composition from free flowing liquids, to amorphous glasses, to cross-linked films. Much of this modification is enabled by the unique use of a metal-free Si-H activation chemistry; the Piers-Rubinsztajn reaction. This chemistry is demonstrated to be a general and rapid way to build up hybrid semiconducting structures. Key to the utility of these materials in electronic devices, it is shown that hybridization with silicon groups has a negligible effect on the useful electrochemical properties of the base materials. Building on this, it is shown that charge carrier mobility through a prototypical liquid organic semiconductor is similar to the base materials and transport is described by existing dispersive transport theories. Finally, two side projects in the area of organic electronics are discussed. New phthalonitrile based fluorophores are characterized and their utility as deep-blue emitting dopants in organic light emitting diodes is demonstrated. These same π-extended phthalonitriles can also be used as precursors to new red-shifted BsubPcs which display exceptional electrochemical stability and tuning.

Triarylamine type materials with vastly altered physical properties are synthesized by hybridizing organic semiconducting structures with silicone and siloxane groups. By altering the silicon content of these materials, we can tune their physical composition from free flowing liquids, to amorphous glasses, to cross-linked films. Much of this modification is enabled by the unique use of a metal-free Si-H activation chemistry; the Piers-Rubinsztajn reaction. This chemistry is demonstrated to be a general and rapid way to build up hybrid semiconducting structures. Key to the utility of these materials in electronic devices, it is shown that hybridization with silicon groups has a negligible effect on the useful electrochemical properties of the base materials. Building on this, it is shown that charge carrier mobility through a prototypical liquid organic semiconductor is similar to the base materials and transport is described by existing dispersive transport theories. Finally, two side projects in the area of organic electronics are discussed. New phthalonitrile based fluorophores are characterized and their utility as deep-blue emitting dopants in organic light emitting diodes is demonstrated. These same π-extended phthalonitriles can also be used as precursors to new red-shifted BsubPcs which display exceptional electrochemical stability and tuning.

Zugl.: Darmstadt, Techn. Univ., Diss., 2008

Universiẗat, Diss., 2003--Bielefeld.