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Mun, Ellina A. "Functionalised organosilica nanoparticles : synthesis, mucoadhesion and diffusion". Thesis, University of Reading, 2014. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.659018.
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Organosilica nanoparticles, due to their versatile properties, attract considerable attention for pharmaceutical applications. The first chapter of this thesis gives an introduction to organosilica materials and traditional methods of their synthesis, provides a literature review on functionalisaUon of silica nanoparticles, in particular PEGylation, and describes recently investigated routes of their application in pharmaceutical science. This is followed by a brief description of methods and techniques used in the current study for synthesis and characterisation of organosilica nanoparticles. Chapter 3 represents a novel size-controlled method of synthesis of thiolated and PEGylated organosilica nanoparticles from 3-mercaptopropyltrimethoxysilane (MPTS) using various organic solvents as media. The mechanism of the nanoparticle formation is proposed, the dependence of nanoparticles size on solvent's dielectric constant is determined, and other factors affecting the nanoparticle size are investigated. Thiol-groups on the surface of organosilica nanoparticles are available for a direct conjugation. Therefore, their surfaces were funcUonalised with two types of fluorescent dyes and PEG maleimide of two molecular weights (750and 5000 Oa). Additionally, polymer- and surfactant-templated mechanisms of MPTS nanoparticle formaUon are reported. The synthesis chapter is followed by studying the properties of thiolated and PEGylated organosilica nanoparticles. Mucoadhesive properties of silica nanoparticles were investigated using a newlyintroduced in vitro method assessing their retention ability on the urinary bladder by the means of fluorescence microscopy. The main factors affecting mucoadhesive properties of MPTS nanoparticles were revealed and thiolated nanoparticles were demonstrated to be promising mucoadhesive materials for intravesical drug delivery. PEGylated nanoparticles were found to be less mucoadhesive which led to the hypothesis of providing better permeation by PEGylation. This was considered in the subsequent chapter (chapter 5), studying the barrier functions of the cornea using thiolated and PEGylated nanoparticles. The "whole eye" in vitro method combined with the fluorescence microscopy demonstrated a good permeation of the latter through de-epithelialised ocular tissue into the stroma. This revealed the interaction of nanoparticles with the corneal surface to be a more impcrtant factor than the particle size, determining their permeation ability. As most organs of the human body are covered with biological hydrogels, the ability of silica nanoparticles to permeate through biological tissues has risen an interest in studying their capability to diffuse through such gels. Therefore, the diffusion of thiolated and PEGylated nanoparticles in different polymer solutions, which were selected as prototypes of biological hydrogels, was studied using NanoSight tracking analysis with fluorescent detection. The main factors affecting the diffusion of organosilica nanoparticles were revealed, and it was demonstrated that the presence of strong attractive interactions between the nanoparticles and macromolecules present in solutions can hamper the diffusion. This was followed by studying biocompatible properties of organosilica nanoparticles using an alternative to traditional methods, a slug mucosal irritation test, revealing their non-irritant nature. Finally, the general results of the current study are summarised and discussed in the last chapter of the thesis, proposing plans for the future work and expansion of the investigations on organosilica nanoparticles presented so far.
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Jahns, Mandy [Verfasser]. "Nanoporöse Organosilica-Materialien für biomedizinische Anwendungen / Mandy Jahns". Hannover : Gottfried Wilhelm Leibniz Universität Hannover, 2019. http://d-nb.info/1190283433/34.
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Terpstra, Andrea Susanne. "Chiral nematic mesoporous organosilica materials templated with cellulose nanocrystals". Thesis, University of British Columbia, 2017. http://hdl.handle.net/2429/64160.
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Voß, Rebecca. "Mesoporous organosilica materials with amine functions : surface characteristics and chirality". Phd thesis, Universität Potsdam, 2005. http://opus.kobv.de/ubp/volltexte/2005/528/.
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In this work mesoporous organisilica materials are synthesized through the silica sol-gel process. For this a new class of precursors which are also surfactant are synthesized and self-assembled. This leads to a high surface area functionality which is analysized with copper (II) and water adsorption.Im Rahmen dieser Arbeit werden mesoporöse Amin-funktionalisierte Organo-Silikate durch den Silika Sol-Gel Prozess hergestellt. Dabei werden neue Alkoxysilyl-Precursoren synthetisiert und condensiert die die gewünschte Funktion auf die Oberfläche dirigieren. Herstellt werden primäre, secundäre und chirale Amine. Die Oberflächenfunktionalität wird mit Kupfer (II) und Wasser Adsorption analysiert.
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Gehring, Julia Johanna [Verfasser]. "Mesoporous organosilica nanoparticles as antibacterial coating materials / Julia Johanna Gehring". Konstanz : Bibliothek der Universität Konstanz, 2016. http://d-nb.info/1118316541/34.
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Voss, Rebecca. "Mesoporous organosilica materials with amine functions surface characteristics and chirality /". [S.l. : s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=975976362.
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De, Witt Joanna Christine. "Switching the reflection in chiral nematic mesoporous silica and organosilica films". Thesis, University of British Columbia, 2012. http://hdl.handle.net/2429/43781.
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Simon, Tamás [Verfasser] y Michael [Akademischer Betreuer] Fröba. "Periodisch Mesoporöse Organosilica - Mit speziellen Morphologien - / Tamás Simon ; Betreuer: Michael Fröba". Hamburg : Staats- und Universitätsbibliothek Hamburg, 2019. http://d-nb.info/1186891874/34.
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Ide, Andreas Hans Peter. "Self-Structuring of functionalized micro- and mesoporous organosilicas using boron-silane-precursors". Phd thesis, Universität Potsdam, 2008. http://opus.kobv.de/ubp/volltexte/2008/2371/.
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The structuring of porous silica materials at the nanometer scale and their surface functionalization are important issues of current materials research. Many innovations in chromatography, catalysis and electronic devices benefit from this knowledge.
The work at hand is dedicated to the targeted design of functional organosilica materials. In this context a new precursor concept based on boron-silanes is presented. These precursors combine the properties of a structure directing group and a silica source by covalent borane linkage. Formation of the precursor is easily realized by a sequential two-step hydroboration, firstly on bis(triethoxysilyl)ethene, and secondly on an unsaturated structure directing moiety such as alkenes or polymers. The so prepared precursors self-organize when hydrolysis of their inorganic moiety takes place via an aggregation of their organic side chains into hydrophobic domains. In this way, the additional use of a surfactant as a template is not necessary. Chemical cleavage of these moieties (e.g. by ammonolysis or oxidative saponification) yields an organosilica where all functionalities are exclusively located at the pore wall and therefore accessible. The accessibility of the functionalities is a vital point for applications and is not necessarily granted for common silica functionalization approaches. Further advantages of the boron-silane concept are the possibility to introduce a variety of surface functionalities by heterolytic cleavage of the boron linker and the control of the pore morphology. For that purpose the covalent linkage of different alkyl groups and polymers was studied. Another aspect is the access to chiral boron silane precursors yielding functionalized mesoporous organosilica with chiral functionalities exclusively located at the pore walls after condensation and removal of the structure directing moiety. These materials possess great potential for applications documented by preliminary investigations on chiral resolution of a racemic mixture by HPLC and asymmetric catalysis.
In the course of this work valuable insights into the targeted structuring and surface functionalization of organosilicas were gained. A promising outlook for further investigations is the extension of this concept by altering the structure directing moieties of the precursor. That way the morphology of the final organosilica might be controlled by for example mesogens. Furthermore, the use of the boron linker enables the introduction of multiple functionalities into organosilicas, making the obtained material unique in its performance.Die Nanostrukturierung von funktionalisierten porösen Materialien auf Silikatbasis steht im Brennpunkt der aktuellen Forschung. Anwendungen wie Chromatographie, Katalyse oder die Herstellung elektronischer Bauteile profitieren von den Erkenntnissen, die auf diesem Gebiet gewonnen werden. Die vorliegende Arbeit soll einen Beitrag zur gezielten Herstellung dieser Funktions-materialien leisten. Hierfür wurde ein neues Precursor-Konzept auf der Basis von Borsilanen vorgestellt. Diese Precursoren werden über eine sequentielle zweistufige Hydroborierung an Bis(triethoxysilyl)ethene und ein Alken oder ein ungesättigtes Polymer erhalten. Über den zweiten Schritt wird hierbei die so genannte strukturgebende Gruppe eingeführt und damit das Template kovalent gebunden. Dadurch entfällt im Vergleich zum bekannten Nanocasting-Mechanismus zum einen die Verwendung des herkömmlichen Templates für die Bildung der Porenstruktur und zusätzlich führt die Mikrophasenseparation während der Kondensation zu einer Anordnung der strukturgebenden Gruppen des Precursors an der Silikatphasengrenze. Nach der chemischen Abspaltung dieser Gruppen, die gleichzeitig zur Einführung funktioneller Gruppen führt, werden somit hochporöse Organosilikate erhalten, in denen sich die funktionellen Gruppen ausschließlich an der Porenoberfläche befinden. Ein Vorteil der Verwendung der Hydroborieung wird in der Vielfalt der funktionellen Gruppen deutlich, die eingeführt werden können. Die Zugänglichkeit der funktionellen Gruppen ist entscheidend für potentielle Anwendungen und bei herkömmlichen Organosilikaten nicht zwangsläufig gegeben. Ein herausragender Aspekt dieses Konzepts besteht in der Möglichkeit, sehr einfach chirale Precursoren und damit Organosilikate mit hoch funktionalisierten, chiralen Oberflächen herzustellen. Es konnte gezeigt werden, dass sich diese Materialien sowohl für die chromatographische Trennung von Racematen mittels HPLC als auch für die asymmetrische Katalyse eignen. Durch die in dieser Arbeit erhaltenen Ergebnisse konnten wertvolle Erkenntnisse zur Ober-flächenfunktionalisierung und Strukturierung von mesoporösen Silikaten gewonnen werden. Die Möglichkeit, das vorgestellte Konzept auf andere strukturgebende Gruppen wie zum Beispiel Mesogene zu übertragen und damit die Porenmorphologie gezielt zu steuern, eröffnet viele weitere interessante Materialeigenschaften.
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Parameswaran, Priya. "Photoresponsive glasses: Control of physical and chemical effects in hybrid organosilica sol-gels with light /". Available to subscribers only, 2006. http://proquest.umi.com/pqdweb?did=1136089781&sid=12&Fmt=2&clientId=1509&RQT=309&VName=PQD.
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Maddala, Sai P. "Synthesis of phosphonate functionalized silica nanoparticles for protein immobilization, intracellular protein delivery and catalytic applications". Thesis, Queen Mary, University of London, 2014. http://qmro.qmul.ac.uk/xmlui/handle/123456789/8961.
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Organosilica nanoparticles have attracted a lot of research interest in a variety of areas such as drug delivery and catalysis because of their properties which include high surface area as well as tunable particle and pore size. In particular, nanoparticles with large pore sizes are of great interest because of their potential to host large guest molecules such as proteins and as catalysts. The focus of the work in the thesis was to develop phosphonate functionalized organosilica nanoparticles for biomedical and catalytic applications. Raspberry textured phosphonatesilica nanoparticles denoted, RNPPME(2.5) (where the number in the brackets represents the moles of organophosphonate per gram), with large pore size (11–17 nm), uniform particle size (70 – 90 nm) and high surface area were produced through the use of template directed base catalysed synthesis, using tetraethylorthosilicate (TEOS) and dimethylphosphonatoethyltrimethoxysilane (DMPTMS) as the silica sources. The role of the reaction conditions such as temperature, surfactant concentration, pH, organosilane concentration and type were investigated and a mechanism for the raspberry nanoparticle formation was proposed. The particles were characterized using electron microscopy (SEM and TEM), Dynamic light scattering (DLS), silicon and phosphorus solid state NMR, and solution phase proton NMR of base digested particles, FT–IR, nitrogen adsorption porosimetry and thermal analysis (TGA). The ability of the particles to host protein molecules of the model protein, bovine serum albumin (BSA) was investigated and the particle–protein composite was characterized using circular dichroism (CD). Raspberry textured nanoparticles were found to host large quantities (26 wt%) of protein. Studies on other (small pore (3 nm) phosphonate functionalized nanoparticles NP_PME(0.2) and NP_PME(1.0)) and (3 nm pore) unfunctionalized mesoporous silica nanoparticles (MSN) revealed that phosphonate loading and the pore size influenced the protein uptake In addition to high protein uptake, the RNP_PME(2.5) particles also absorbed protein molecules rapidly (~ 20 minutes to maximum load). CD studies determined that the particle bound protein structure was not affected at physiological pH (7.40). The vast majority of the previously reported studies involving protein immobilization involved the use of bulk silica materials, which cannot be dispersed and hence those materials were unsuitable for in vivo protein delivery applications. The BSA@RNP_PME(2.5) particles showed good protein load and dispersion properties and hence are excellent protein delivery agents. Dispersions of nanoparticle composite BSA#@RNP*_PME(2.5) (where BSA# represents fluorescein isothiocyanate labelled BSA and RNP*_PME(2.5) represents rhodamine B isothiocyanate labelled RNP_PME(2.5)) was used to successfully deliver membrane impermeable protein BSA into HeLa cells. Intracellular protein delivery has attracted great interest due to its potential therapeutic applications and research tool value (e.g. for studying various cellular pathways). The toxicity of the guest free particles RNP*_PME(2.5) and the protein loaded particles BSA#@RNP*_PME(2.5) was studied using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay. The particles and the protein-particle composite were found to be non-toxic. The mechanism of the particle uptake by the cells was also studied. The unloaded (protein free) particles were found to be taken up by caveolar endocytosis pathway and the protein loaded particles were taken up by folic acid mediated pathway. The results indicated that the particles can successfully deliver membrane impermeable protein across the cell membrane. This result suggested that the particles can potentially be used for intracellular protein delivery applications. Raspberry textured nanoparticles RNP_PME(2.5) were also used to host the enzyme lipase. It was demonstrated that immobilization increased the maximum velocity and Michaelis constant of the enzyme and also that the particles offered protection against the denaturing agent, urea. Finally, in a chemical catalysis application, the RNP_PME(2.5) particles were used to synthesize the platform chemical HMF, through Brönsted acid catalysed dehydration of fructose. High yields of HMF (87 %) were achieved when 10 wt% fructose was used. The particles demonstrated good recyclability and also the ability to convert up to 50 wt% fructose into HMF (80 % yield). The particles therefore acted as protective agents for enzymes and can therefore be used as enzyme immobilizing agents. Additionally, they also acted as excellent Brönsted acid catalysts.
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Grabicka, Bogna E. "Microwave-Assisted Synthesis of Ordered Mesoporous Organosilicas with Surface and Bridging Groups". Kent State University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=kent1290459085.
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Moitra, Nirmalya. "Silices hybrides fonctionnelles : matériaux dérivés d'alcaloïdes pour organocatalyse ; réactions "click" pour le sol˗gel". Thesis, Montpellier, Ecole nationale supérieure de chimie, 2011. http://www.theses.fr/2011ENCM0003.
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Cette thèse s'intéresse à la préparation de silices hybrides organique/inorganiques à base de fragments alcaloïdes cinchona, et à une nouvelle méthode de synthèse de précurseurs silylés hydrolysables via une réaction ‘click' de CuAAC. La première partie de ce travail est dédiée à une présentation bibliographique du domaine de la catalyse supportée sur matériaux hybrides, et est principalement focalisée sur l'organocatalyse supportée, un champ de recherche en plein développement. Dans la seconde partie, différentes méthodes d'immobilisation d'alcaloïdes dans une matrice de silice sont décrites, dans le but de les utiliser comme organocatalyseurs pour une réaction de décarboxylation asymétrique. La troisième partie est dédiée à une nouvelle méthode de préparation de précurseurs silylés via une réaction de CuAAC. Cette méthodologie montre un potentiel important pour la formation de nouveaux composés fonctionnels. Finalement, la synthèse de nanoparticules de silice mésoporeuse contenant des groupes azoture ou alcyne et leur post-fonctionalisation sont présentéesThis thesis deals with the preparation of organic-inorganic hybrid silica based on cinchona alkaloids fragments and with a new method of synthesis for hydrolysable silylated precursors via CuAAC “click” reactions. The first part of this work is dedicated to a bibliographic presentation of the area of supported catalysis on hybrid materials and is mainly focused on supported organocatalysis, an emerging area of research. In the second part, different methods for immobilization of alkaloids within a silica matrix are described aiming at using them as organocatalysts for an asymmetric decarboxylation reaction. The third part is devoted to a new method of preparation of silylated precursors by CuAAC “click” reactions. This methodology shows a high potential in the formation of new functional compounds. Finally the synthesis of mesoporous silica nanoparticles bearing azide or alkyne groups and their post-functionalization by CuAAC reactions are presented
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Steeples, Elliot [Verfasser] y Markus [Akademischer Betreuer] Antonietti. "Amino acid-derived imidazolium salts: platform molecules for N-Heterocyclic carbene metal complexes and organosilica materials / Elliot Steeples ; Betreuer: Markus Antonietti". Potsdam : Universität Potsdam, 2016. http://d-nb.info/1219077534/34.
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Noureddine, Achraf. "Approches Click en Chimie Sol-Gel". Thesis, Montpellier, Ecole nationale supérieure de chimie, 2014. http://www.theses.fr/2014ENCM0005/document.
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Nous visons dans ce travail de thèse à développer une méthodologie de fonctionnalisation par chimie click des silices hybrides synthétisées par voie sol-gel. La réaction click de cycloaddition azoture-alcyne catalysée au cuivre (CuAAC) offre une tolérance exceptionnelle pour les fonctions organiques en plus de conversions très élevées. Dans cette optique, nous avons mis en œuvre en premier lieu des matériaux clickables à base d'organosilice pure (organosilice à mésoporosité périodique (PMO) et silsesquioxanes pontés (BS)) qui ont permis une conversion quasi-quantitative de greffage par CuAAC. Nous avons ensuite utilisé cette particularité pour contrôler les propriétés de surface des BS en modifiant leur caractère hydrophile/lipophile. Dans le second axe de travail, nous nous sommes intéressés à l'apport de la chimie click pour la préparation de nanoparticules mésoporeuses de silice multifonctionnelles, dites mécanisées, pour des systèmes à délivrance contrôlée de principes actifsThe present work aims to develop a trustful methodology of functionalization for hybrid silica materials made by the sol-gel process using the copper-catalyzed alkyne-azide cycloaddition (CuAAC)Click reaction. This transformation can be highly useful in materials science thanks to its high conversions and the excellent functional group tolerance. In this prospect, we have synthesized fully clickable bridged silisesquioxanes and periodic mesoporous organosilica that show high extents of click grafting. CuAAC was then used for tailoring the surface of bridged silsesquioxane and fine-tuning the hydrophilic/lipophilic balance. Finally, the click reaction was used as an efficient way to obtain multiply functionalized mesoporous silica nanoparticles in order to make nanomachines for controlled delivery of cargo molecules
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Svoboda, Tomáš. "Příprava a vlastnosti organokřemičitých pojiv pro nanočásticové vrstvy oxidu titaničitého". Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2017. http://www.nusl.cz/ntk/nusl-316147.
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This diploma thesis deals with the synthesis of an organosilica polymer which could be used as a binder for titanium dioxide photocatalytic layers. The main reason for incorporating the binder into the photocatalytic layers is not only the improving of the mechanical properties, but above all, the binder could help with production of low-temperature photocatalytic layers, that could be applied to heat-sensitive materials such as plastic materials. This could create layers on flexible materials that could be easily made into any shape. The work focuses on the synthesis of organosilica polymer from the organosilica precursor and subsequent characterization of the binder. Surface tension, viscosity, density, XRD, thermal analysis of silica binder solutions was performed. Titanium dioxide compositions with this binder were prepared, then they were printed and the layers were treated with UV and plasma. Treated layers were examined by FT-IR and a voltamperometric characterization was performed.
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Voisin, Doria. "Structuration d’organosilices : assemblage covalent et auto-organisation de T8- silsesquioxanes octa-fonctionnalisés". Thesis, Montpellier, Ecole nationale supérieure de chimie, 2016. http://www.theses.fr/2016ENCM0017/document.
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Le présent travail vise la synthèse d’organosilices nano-structurées à partir de briques élémentaires de silsesquioxanes polyédriques fonctionnalisées (T8-POSS) de structure cube (RSiO1,5)8. L’assemblage de briques fonctionnelles T8-POSS a été étudié selon deux voies : par des interactions fortes en formant des liaisons covalentes et par des interactions faibles en formant des liaisons hydrogène.La première partie décrit la formation de réseaux hybrides covalents à partir de structure T8 POSS portant huit fonctions aldéhydes. La synthèse et la structure cristalline de ces « cubes » fonctionnalisés sont décrites et la réactivité des fonctions aldéhydes est examinée. La formation de liaisons C=N par réaction d’amines conduit à des réseaux tridimensionnels grâce à la formation de ponts organiques bis-imines joignant les unités silsesquioxanes. Bien que la formation d’imine soit réversible, les solides obtenus ne présentent pas d’ordre à longue distance. La formation de liaisons C=C, dans des conditions de synthèse non réversibles, par réaction de bis-ylures de phosphonium avec les aldéhydes a également été étudiée. Ces réactions de type Wittig engendrent la formation de réseaux hybrides amorphes contenant des sous-structures phenylène-vinylènes dotées de propriétés de fluorescence. La deuxième partie décrit la synthèse de nouvelles molécules de T8-POSS, possédant des fonctions organiques amines ou acides carboxyliques capables d’interactions intermoléculaires grâce à des liaisons hydrogène. Ces interactions permettent l’assemblage des dérivés du T8-POSS fonctionnalisés par huit fonctions acides carboxyliques en un réseau 3D ordonné. Les briques élémentaires T8- POSS s’auto-assemblent par dimérisation des fonctions acides pour engendrer des silices hybrides cristallines. Les structures ont été déterminées par diffraction de rayons X. Les fonctions acides carboxyliques sont intéressantes non seulement par leur capacité à former des liaisons hydrogènes mais également par leur aptitude à former des carboxylates métalliques. Ces derniers ouvrent des perspectives pour la formation de réseaux d’oragnosilices incorporant des métauxThe present work aimed at synthesising nano-structured organosilicas using polyhedral silsesquioxane building blocks (T8-POSS) having a cube structure. The assembly of T8-POSS building blocks to form a 3D network was studied in two ways: first by formation of strong covalent bonds and secondly by formation of weak hydrogen bonds.The first part described the formation of covalent hybrid networks from T8-POSS structures with eight aldehyde functional groups. The synthesis and crystal structure of these functionalised silsesquioxane cubes is described and the reactivity of the aldehyde groups is studied. The formation of C=N bonds upon reaction with amines lead to tree-dimensional networks upon formation of bis-imine bridges linking the silsesquioxane units. Despite the imine formation was reversible, the resulting solids were amorphous materials and exhibited no long distance order. The formation of C=C bonds, under non-reversible reaction conditions, was achieved by reaction of phosphonium bis-ylides. The Wittig type reactions generated amorphous hybrid networks containing bridging phenylene-vinylene substructures with fluorescence properties.The second part described the synthesis of new functionalised T8-POSS cubes with eight amine or carboxylic acid functions capable of intermolecular interactions by hydrogen bonding. It allowed the assembly of the octa-carboxylique acid cubes to form an ordered 3D hybrid network. The T8-POSS building blocks self-assembled upon dimerization of the acid groups and generated crystalline hybrid silicas. The crystal structures were determined by X-ray diffraction. The use carboxylic acid groups is interesting because of its ability to form hydrogen bonds and also because of its ability to form metal carboxylate derivatives. It could lead to hybrid metal organic silica frameworks
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El-Kaddar, Yousef Younis. "Organosilicon reaction mechanisms". Thesis, University of Sussex, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375169.
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This thesis is concerned with the preparation and reactions of some highly sterically hindered organosilicon compounds, mainly of the type TeiSiMe2X where Tsi denotes the (Me3Si)3C group. The first detailed study of the reactions of TsiS1Me20CN has shown that reactions with NaN3 in MeOH or KSCN or KOCN in MeCN give exclusively the corresponding TsiSiMe2X compounds (X = N3, NCS, or NCO), whereas those with other salts, viz. LiCl, CsF, KSCN, and KOCN, give the TsiSiMe2X species along· with other products, including in many cases TsiSiMe2NCO and TsiSiMe20H (from traces of water), and (in MeOH) TsiSiMe20Me. The reaction with MeOH alone was never found to give less than 10% ot TslSiMe20H, along with the expected TsiSiMe20Me, however carefully the MeOH was dried. The extreme sensitivity of the cyanate towards water was illustrated by the fact that the rate ot solvolysis in 'dry' MeOH was increased by~. 90% by addition of 0.05 vol-% of H2o, and the hydroxide was the sole product, whereas the rate for the triflate TsiSiMe2- OS02CF3 was increased by only 13% and the product was a 60:40 mixture of TsiSiMe20Me and TsiSiMe20H. The rate constant for the triflate increased linearly with the water concentration but that of the cyanate did not. The presence of NaOMe in MeOH led to rapid isomerization of the cyanate to the isocyanate, TsiSiMe2NCO, with the rate of isomerization being proportional to the base concentration: a possible explanation of this effect of base is suggested. Isomerization catalysed by ICI in CC14 was found to be of ca. second order with respect to both the cyanate and the IcI: A detailed kinetic study has been carried out of the the reactions of TsiSiMe2X compounds, with X c I, Br, Cl, or ON02' with various alkali metal salts, MY, viz. NaN3' CsF, KSCN, and KOCN in MeOH and with KSCN in MeCN. For X • I, Br, or Cl, the reactions have been shown to be much more complex than was previously thought, the compounds TsiSiMe20Me, TsiSiMe20H, and (Me3Si}2CHSiMe2oMe commonly being formed along with TsiSiMe2Y. The order of effectiveness of the salts in the formation of TsiSiMe2Y is CsF > NaN3 > KSCN > KOCN, except that for X - I the order for CsF and NaN3 is reversed. Approximate values of the activation parameters have been obtained: the activation entropies have very high negative values, consistent with formation of a very crowded transition state. The nitrate is markedly more reactive even than the iodide, and gives cleaner conversions into TsSiMe2Y compounds: the activation energies are much lower and the activation entropies much more negative than those tor the halides. Reactions of the compounds (Me3Si)2C(SiMe2H)(SiMe2Cl) with alkali metal salts have been shown to be much faster than those of TsiSiMe2Cl, casting doubt on an earlier suggestion that the ease of solvolysis of the former chloride might be due to anchimeric assistance by y-H.
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Li, Yan. "Periodic mesoporous organosilicas with functional chromophores". Diss., Ludwig-Maximilians-Universität München, 2012. http://nbn-resolving.de/urn:nbn:de:bvb:19-173286.
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Croissant, Jonas. "NANOMÉDECINE THÉRANOSTIQUE ACTIVÉE À DEUX-PHOTONS POUR LE TRAITEMENT DU CANCER". Thesis, Montpellier, Ecole nationale supérieure de chimie, 2014. http://www.theses.fr/2014ENCM0004/document.
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La nanomédecine activée à deux-photon est devenue l'un des principaux candidats à l'accomplissement de la sélectivité spatiotemporelle nécessaire pour la nanomédecine. En effet, la raison d'être de l'application médicale de nanotechnologie dans le domaine du traitement du cancer est de diminuer et supprimer les effets secondaires causés par les techniques actuelles telles que la chimiothérapie et la radiothérapie, à cause de leur manque de sélectivité. Parmi diverses nanoparticules (NPs), les nanoparticules de silice mésoporeuse (MSN) ont attiré une attention croissante dans la dernière décennie pour leur faible cytotoxicité, leur internalisation cellulaire et excrétion, et leur capacité de combiner de nombreuses fonctions à la fois pour le diagnostique et la thérapie de cancers via un seul nanovéhicule : l'ainsi appelée nanomédecine théranostique.Dans cette thèse, des MSN pour l'activation à un et deux-photon d'imagerie par fluorescence, de délivrance de principe actifs et d'acides nucléiques, et de photothérapie dynamique (PTD), seront présentées. Premièrement, le relargage contrôlé de molécules encapsulées dans des MSN fonctionnalisées avec des nanovalves est considéré par effet plasmonique. La photodégradation contrôlée de la silice soumise à l'effet photothermique de NPs d'or est ensuite étudiée. Deuxièmement, l'activation biphotonique est considérée pour la délivrance contrôlée de molécules anticancéreuses in-vitro par avec des nano-rotor et des nano-valves, ainsi que la fonctionnalisation de surface des NPs par des dérivés d'ammonium- azobenzene pour la délivrance d'acides nucléiques. Troisièmement, des MSN multifonctionnelles incorporant des photosensibilisateurs à deux-photon sont systématiquement étudiées en termes de leurs propriétés optiques et photophysiques; la sélection du meilleur matériau est suivie d'applications biomédicales in-vitro.De plus, deux types de nanomatériaux émergeant sont également élaborés pour la nanomédecine activée à deux-photon, des NPs de polysilsesquioxane pontés (BS) et d'organosilice mésoporeuse périodiques (PMO). Ces matériaux furent élaborés sans précurseur de silice (tétraéthoxysilane par exemple), et seulement à partir de bis- ou multi-organoalkoxysilane, afin d'obtenir le plus haut pourcentage de matière organique pour l'application ciblée. En conséquence, des NPs de BS et de PMO hybrides à base de disulfures se révélèrent être des outils biodégradables, et les NPs à base de photosensibilisateurs furent appliquées pour la PTD à deux-photon. Des NPs de BS et de cœur-coquille d'or-BS sont synthétisées pour d'efficaces imagerie et PTD à deux-photon, tandis que des NPs de PMO servirent de nano-plateformes théranostiques. En outre, diverse NPs de PMO multipodes à surface spécifique très élevées sont présentées pour la construction de structuration complexe à l'échelle nanométrique.Enfin, des nano-conteneurs d'MSN composées de cœur d'oxyde de fer (Fe3O4@MSN) sont décrites pour de multiples applications. D'une part, l'élaboration de NPs MSN (et PMO) magnétiques sensibles à deux-photon est étudiée en tant que perspective pour la délivrance de gène combinant l'imagerie par résonance magnétique. D'autre part, les conteneurs de Fe3O4@MSN sont misent en œuvre et appliqués pour la dépollution de métaux lourds via la fonctionnalisation d'un ligand de type acide diéthylène triamine penta acétique. L'augmentation de l'efficacité de la dépollution est étudiée par la fonctionnalisation de la surface extérieure et/ou des pores des Fe3O4@MSNTwo-photon actuated nanomedicine has become one of the main proponents for the achievement of the spatiotemporal selectivity needed for nanomedicine. Indeed, the raison d'être of the medical application of nanotechnology in the field of cancer treatment is to lower and suppress the side effects caused by current techniques such as chemotherapy and radiotherapy, due to their lack of selectivity. Among various nanoparticles (NPs), mesoporous silica nanoparticles (MSN) have attracted increasing attention over the past decade for their low cytotoxicity, cellular internalization and excretion, and the ability to carry multiple features for both the diagnosis and therapy of cancers in a single nanovehicle: the so-called theranostic nanomedicine.In this dissertation, I will describe MSN for one and/or two-photon-actuated fluorescence imaging, drug-delivery, gene delivery and photodynamic therapy (PDT). First, plasmonically-triggered cargo delivery via MSN nanovalves and designed mesoporous silica photodegradation is presented. Then, in-vitro two-photon-triggered drug delivery with azobenzene-functionalized MSN such as nanoimpellers and fluorescent nanovalves, along with preliminary studies of gene delivery via ammonium-functionalized nanoimpellers are discussed. Multifunctional MSN incorporating a two-photon photosensitizer are systematically studied in terms of the resulting optical and photophysical properties of the NPs, and then used for in-vitro biomedical applications.Furthermore, two kinds of emerging nanomaterials are also designed for two-photon actuated nanomedicine, bridged silsesquioxane (BS) and periodic mesoporous organosilica (PMO) NPs. These nanomaterials are elaborated without silica precursor (e.g. tetraethoxysilane) and solely with bis- or tetra-organoalkoxysilanes, thus providing materials with the highest organic content for the targeted applications. Consequently, disulfide-based hybrid BS and PMO NPs were elaborated as biodegradable nanomedical tools, and photosensitizer-based BS and PMO NPs were used for efficient in-vitro PDT. BS and gold-BS core-shells NPs are constructed for ultrabright two-photon imaging and efficient PDT, while two-photon functionalized PMO NPs serve as theranostic nanocarriers. Besides, versatile multipodal ethylene-benzene PMO NPs with very high surface areas are presented as a promising strategy for the design of structural complexities at the nanoscale.Finally, iron oxide core MSN shell (Fe3O4@MSN) nanocontainers are described for versatile applications. The design of two-photon-sensitive magnetic MSN and PMO core-shell nanovehicles is presented as a perspective for gene delivery and magnetic resonance imaging. Furthermore, Fe3O4@MSN containers are constructed for heavy metal removal of twelve of the most toxic metal ions through the diethylene triamine pentaacetic acid (DTPA) ligand. The enhancement of the pollutant removal efficiency is studied by selective surface and/or porous DTPA functionalizations
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Wang, Wenhui. "Preparation and characterization of periodic mesoporous organosilicas". Thesis, University of Ottawa (Canada), 2004. http://hdl.handle.net/10393/26798.
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Periodic mesoporous organosilicates (PMOs) are hybrid materials whose framework is comprised of alternating organic and inorganic species. These materials are prepared via supramolecular templating assembly using bridged silsesquioxanes (RO)3Si-R'-Si(OR) 3 as precursors, and surfactants as templates. This thesis is devoted to the preparation and characterization of phenyl- and ethenylene-bridged PMOs. The phenylene-containing precursor (bis(triethoxysilyl)benzene was synthesized by Barbier-Grignard reaction, whereas the ethylene derivative bis(triethoxysilyl)ethylene was prepared by self-metathesis reaction. They were characterized by 1H and 13C NMR, and mass spectrometry.
The corresponding mesoporous materials were prepared using these precursors in the presence of different types of surfactants including oligomeric alkyl polyethylene oxide, triblock polyalkylene oxide copolymer and alkyltrimethylammonium surfactants. To obtain highly ordered mesoporous organosilicates, different synthesis conditions were employed and optimized. All materials were characterized using XRD, TEM, SEM, nitrogen adsorption, 29Si and 13C solid state NMR. In addition, some post-synthesis reactions using these materials were investigated.
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Trussell, Stephen John. "Transition metal-mediated organosilicon chemistry". Thesis, Imperial College London, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.298136.
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Kwak, Young-Woo. "Isomerization Reactions in Organosilicon Chemistry". Thesis, North Texas State University, 1985. https://digital.library.unt.edu/ark:/67531/metadc332336/.
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Dimethylsilene, generated from the thermal gas phase reaction of 1,1-dimethyl-1-silacyclobutane, reacts with alkynes to produce silacyclobutenes or acyclic silanes. The temperature dependence of the product ratios have been determined and the relative reactivities of three different alkynes toward the 1,1-dimethylsilene has been determined. 1-Hydrido-1-methylsilene has been generated by gas phase thermal decomposition from three different precursors. Trapping studies with butadiene and trimethylsilane lead to products expected from dimethylsilylene. The most plausible explanation for these observations is that hydridomethylsilenes undergo a facile isomerization to divalent dimethylsilylene. Cycloaddition of 1,1-dimethylsilene to allene at 600°C in a flow vacuum pyrolysis system affords the first synthesis of 2-methylene-1,1-dimethylsilacyclobutane and smaller amounts of six other products. For static pyrolysis at 421°C, the 2-methylene-1,1-dimethyIsilacyclobutane isomerizes to 1,1-dimethylsilacyclopentenes. The kinetics of gas phase thermal decomposition of cyclopropyltrimethylsilane has been studied over the temperature range, 689.6-751.1 K at pressures near 14 torr. The Arrhenius parameters for formation of allyltrimethylsilane are k_1(sec^-1)=10^14.3 ± 0.1 exp(-56.5 ± 0.2 kcal mol^-1/RT) and those for the formation of E- and Z-1-propenyltrimethyIsilane are k_2(sec^-1)=10^14.9 ± 0.3 exp(-61.9 ± 0.8 kcal mol^-1/RT). The difference between activation energies has been interpreted in terms of anchimeric assistance or the β effect of the silicon atom. The syntheses of 3-trimethylsilyl-1-pyrazoline and 1-trimethyl-2-pyrazoline are described. The thermal decomposition of either pyrazoline affords four different products along with elimination of a nitrogen molecule. It was suggested that the relative rates of methylene-hydrogen migration to radical centers α and γ to silicon are approximately equal. The thermal isomerization of 3-trimethylsilyl-1-pyrazoline to 1-trimethylsilyl-2-pyrazoline has been investigated kinetically at 65°C by proton NMR spectroscopy and the reverse reaction has been detected by gas phase pyrolysis.
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Lourenço, Mirtha Alejandra de Oliveira. "Tuning functionalized periodic mesoporous organosilicas for CO2/CH". Doctoral thesis, Universidade de Aveiro, 2016. http://hdl.handle.net/10773/21817.
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Doutoramento em Ciência e Engenharia de MateriaisEsta tese de doutoramento teve como principal objetivo a conceção de novas organossílicas mesoporosas periódicas (PMOs) para aplicação na separação de misturas gasosas de dióxido de carbono e metano. Materiais PMOs, com grupos fenileno e bifenileno bissililados, foram modificados por introdução de grupos funcionais amina, utilizando uma das seguintes metodologias: i) reação de co-condensação; ii) pós-modificação da ponte orgânica; iii) "grafting". O tamanho dos poros das PMOs funcionalizadas e não funcionalizadas foi definido pelo tamanho da cadeia alquilada da molécula molde (surfactante) utilizada na síntese do material poroso. Estudou-se o efeito do diâmetro dos poros na separação de CO2/CH4. Investigou-se também estratégias alternativas para modificar as propriedades físico-químicas dos materiais através de reações de superfície utilizando irradiação de micro-ondas; deposição de camada atómica (ALD) de óxido de alumínio; e carbonização dos materiais em atmosfera inerte. A investigação experimental foi efectuada em paralelo com estudos computacionais. Realizou-se um estudo de simulação molecular recorrendo ao método de DFT, e usando um arranjo regular de grupos fenileno-sílica, para determinar as características ideais dos materiais para promover a separação de metano do dióxido de carbono em misturas destes gases. Foi utilizado um modelo simples, obtido pela repetição de uma célula unitária com 3 anéis fenileno, para simular a parede dos materiais PMOs e desta forma selecionar e avaliar as interações entre os gases e os grupos funcionais presentes na superfície dos materiais. A tendência do rácio entre energias de interação entre a estrutura da parede do fenileno - PMO e as moléculas de CO2 e de CH4 foi concordante com os rácios das constantes de Henry obtidos pela técnica de adsorção. Demonstrou-se uma boa sinergia entre tarefas experimentais e computacionais, o que permite a otimização de recursos, evitando a síntese desnecessária de materiais que se antecipem serem pouco eficazes para o processo de separação de misturas gasosas CO2 e CH4. Assim, a abordagem seguida nesta tese para alcançar adsorventes eficazes foi baseada numa conjugação interdisciplinar envolvendo troca de informação entre as tarefas de síntese, modelação computacional e adsorção.
The main objective of this PhD Thesis was the design of periodic mesoporous organosilicas (PMOs) for applications in carbon dioxide and methane separation. Novel PMOs were prepared by the modification of phenylene and biphenylene PMO materials with different amine functionalities through one of the three following synthetic strategies: i) co-condensation reaction; ii) organic bridge post-modification; or/and iii) grafting. The pore size of both functionalized and non-functionalized phenylene PMOs was regulated by the size of the alkyl-chain in the surfactant template. Materials with different pore sizes were used to understand the influence of the pore diameter on the CO2/CH4 separation. Additionally, it was aimed to explore alternative strategies to modify the physical-chemical properties of the materials such as microwave-assisted functionalization; atomic layer deposition (ALD) of aluminum oxide at the PMO surfaces; and carbonization of the PMO materials. The experimental research was performed in parallel with computational studies. A molecular simulation study, using the DFT method and a regular arrangement of phenylene-silica groups, of the ideal characteristics of the adsorbent materials, for CO2/CH4 separation was performed. It was used a simple model of the wall of the PMO materials obtained by the repetition of a unit cell with 3 phenylene rings, to select and evaluate interactions between gases and functional groups in the surface of the materials. The tendency between the ratio of the interaction energies between the wall structure of the phenylene-PMO and the CO2 and CH4 molecules was in good agreement with the ratio of the Henry constants achieved by the adsorption technique. Therefore, a good synergy between experimental and computational tasks was implemented to optimize the resources, avoiding the synthesis of ineffective materials. Thus, the strategy of this PhD Thesis to achieve effective adsorbents was based on an interdisciplinary approach and on the ability to link and interchange information between synthetic, computer modeling and adsorption experiments
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Thach, Ut Dong. "Echanges d’anions sur ionosilices : de l'élaboration des matériaux aux études physicochimiques et leurs applications en séparation et catalyse". Thesis, Montpellier, 2016. http://www.theses.fr/2016MONTT239/document.
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L'objectif de cette thèse est le développement de nouveaux échangeurs d'anions à base d’ionosilices. Différents matériaux contenant des entités ammoniums ont été synthétisés par la procédure d'hydrolyse-polycondensation à partir de précurseurs silylés d'ammonium. Ces solides, présentant différentes textures, différentes architectures ou des morphologies ont été obtenus en faisant varier des paramètres de réaction, comme par exemple la nature du tensioactif utilisé. Outre les caractérisations structurales et texturales (adsorption-désorption d’azote, DRX, MET / MEB), nous nous sommes concentrés sur les analyses plus détaillée des propriétés physico-chimiques de ces ionosilices. En particulier, elles présentent une contribution hydrophile élevée par rapport aux silices mésoporeuses classiques ou les organosilices du type PMO (Periodic Mesoporous Organosilica). En outre, ces propriétés interfaciales d’hydrophilie peuvent être modulées soit par l'utilisation de différents précurseurs d'ammonium, soit par l'incorporation par échange d'anions hydrophobes. Enfin, nous avons utilisé ces nouveaux matériaux pour la rétention d’espèces anioniques en milieu aqueux. Nos études montrent que ces ionosilices sont des échangeurs d'anions très efficaces présentant une capacité d'adsorption de Cr (VI) élevée (jusqu’à 2.5 mmol g-1). Ces matériaux possèdent également une capacité d’adsorption d’iodure élevée combinée à une bonne stabilité radiolytique pour des applications de rétention de radionucléides. Des résultats similaires ont été obtenus pour des polluants organiques anioniques tels que les principes actifs (le diclofénac, le sulindac et le p-aminosalicylate) ou des colorants (méthyl orange). Outre le grand potentiel d’application de ces matériaux dans les procédés de séparation, cette étude donne un aperçu intéressant de la morphologie des matériaux grâce à l'accessibilité presque complète des sites cationiques. Toutes ces caractéristiques font de ces matériaux des systèmes de choix pour les applications dans le traitement de l’eau polluée, le stockage à long terme des déchets radioactifs et en tant que support de catalyseurThe objective of this thesis is the development of new anion exchangers based on ionosilica materials. Various materials containing ammonium groups were synthesized by template directed hydrolysis-polycondensation reactions starting from silylated ammonium precursors. Solids displaying different textures, architectures and morphologies were obtained via the modifications of reaction parameters, such as the nature of the used surfactant. Besides the standard structural and textural characterizations (N2 adsorption, XRD, TEM / SEM), we focused on a more detailed physico-chemical analysis of these original and innovative materials. Ionosilicas show an unusually high hydrophilicity compared to classical mesoporous silica or organosilicas of the PMO-type (Periodic Mesoporous Organosilica). Furthermore, the hydrophilicity of ionosilicas can be finely tuned either by the use of various ammonium precursors or the incorporation via exchange of hydrophobic anions. Finally, we used these new anion exchangers for the removal of various anionic species in aqueous media. Our studies show that ionosilicas are highly efficient anion exchanger displaying high capacity for the adsorption of Cr (VI) (up to 2.5 mmol g-1). These materials exhibit also high capacity of iodide combined with high radiolytic stability for radionuclides uptake. Similar results were obtained for organic anionic pollutants, e.g. drugs (diclofénac, sulindac and p-aminosalicylate) and dyes (methyl orange). Besides the high potential of these materials in separation processes, this study gives interesting insights in the materials morphology through the nearly complete accessibility of the cationic sites. All these features make ionosilicas materials of choice for solid-liquid separation processes in water treatment, depollution of industrial wastewater, the nuclear fuel cycle or catalytic support
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Hughes, K. J. "Chemistry of gaseous organosilicon reactive intermediates". Thesis, University of Leicester, 1987. http://hdl.handle.net/2381/33745.
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Chapter one provides a brief history and current state of knowledge of the chemistry of organosilicon reactive intermediates relevant to this thesis. Chapter two outlines the experimental techniques used in the majority of work carried out in this thesis. Chapter three describes an experimental investigation of the pyrolysis of 4-dimethylsilylbut-l-ene and 5-dimethylsilylpent-l-ene, with and without excess methylchloride as a silyl radical trap. The results of computer modelling of the pyrolysis of 4-dimethylsilylbut-1-ene with excess methylchloride are described, in which information concerning the isomerisation of an alpha-silyl radical to a silyl radical via a hydrogen shift is obtained. Chapter four describes the results of an experimental investigation of the reactions of dimethylsilene and dimethylsilylene with anions. Chapters five and six contain the results of computer modelling of three related pyrolysis mechanisms composed of complex series of unimolecular rearrangements of silylenes, silenes, disilenes and disilacyclopropanes. Chapter seven describes an experimental determination of Arrhenius parameters for the trapping of dimethylsilene by butadiene, together with the results of pyrolysis of butadiene adducts of methylsilene, dimethylsilene and dimethylsilylene. Chapter eight is an experimental investigation of the pyrolysis of cis and trans dimethy1(1-propenyl)vinylsilane with excess 2,3-dimethylbutadiene as a silylene trap. Interpretation of the results as a cis-trans isomerisation and decomposition of the cis isomer via a silacyclopropane intermediate are reinforced by the results of computer modelling of both systems. Chapter nine describes an experimental investigation of the pyrolysis of 1, 2-dimethyldisilane with and without butadiene as a silylene trap. Computer modelling of the pyrolysis with the absence of butadiene is used to clarify the pyrolysis mechanism. Chapter ten is an experimental investigation of the pyrolysis of silacyclobutane and methylsilacyclobutane with excess butadiene to trap silylene intermediates and thus suppress secondary decomposition. Arrhenius parameters for the primary decomposition pathways are determined.
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Jiang, Jianxiong. "Coordination and reactivity in organosilicon compounds". Thesis, Open University, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.291298.
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Gage, David Maxwell. "Fracture of nanoporous organosilicate thin films /". May be available electronically:, 2008. http://proquest.umi.com/login?COPT=REJTPTU1MTUmSU5UPTAmVkVSPTI=&clientId=12498.
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Yeh, Li-Tain. "Novel synthetic routes to organosilicon species". Case Western Reserve University School of Graduate Studies / OhioLINK, 1991. http://rave.ohiolink.edu/etdc/view?acc_num=case1055525594.
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Sohal, Wazir Singh. "The synthesis of chemistry of organosilicon cations". Thesis, Imperial College London, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.405220.
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Mehreteab, Tesfamariam. "Preparation of mesoporous Ti - Organosilicate epoxidation catalysts". DigitalCommons@Robert W. Woodruff Library, Atlanta University Center, 2009. http://digitalcommons.auctr.edu/dissertations/85.
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Following the methodology used in sol—gel chemistry to functionalize amorphous silica, organic functionalized mesoporous silica were prepared by the co-condensation of tetraethoxysilane and organoalkoxysilanes in the presence of surfactant templates. A series of titanium catalysts containing Ti-MCM-41 with different bridging and pendant organic functional groups (such as methyl triethoxysilane (MTEOS), phenyl triethoxysilane (PTEOS), diphenyl triethoxysilane (DPTEOS), bis (triethoxysilyl) ethane (BTSE), 1,4 bis(triethoxysiyl) benzene (BTSB), bis( triethoxysilyl) biphenyl (BTSDP) and two catalysts with different organic-inorganic ratios (90% TEOS with 10% phenyl, 70% TEOS with 30% phenyl) were synthesized. The catalysts were characterized by elemental analysis, XRD, FTIR, UVDRS, by solid state 13C and 29Si MAS NMR, and BET surface area analysis. The catalytic activities of the synthesized materials were evaluated for epoxidation of cyclohexene with TBIIP. The materials yielded improved conversion compared to the conversion results obtained from the traditional titanium containing mesoporous silica (Ti-MCM-41). The hydrophobic character of the synthesized catalysts was tested in the epoxidation of cyclohexene by using wet TBIIP. Ti-MCM41 with bridged organosilane showed almost the same conversion in the presence of water, while for Ti-MCM-41 with organosilane pendant groups. conversion decreased almost 36%. This implies that the silylation of the surface ofTi-MCM4I protected the active sites. The effect of substrate: oxidant molar ratio in these reactions were studied and high conversion, high selectivity were achieved at 1:1 molar ratio.
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Whittaker, Stephen Mark. "Some chemistry of sterically hindered organosilicon compounds". Thesis, University of Salford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239973.
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Van-Straaten, Manon. "Dépôt de films minces de poly(méthacrylates) par iCVD : des mécanismes de croissance à la Polymérisation Radicalaire Contrôlée". Thesis, Lyon, 2019. http://www.theses.fr/2019LYSE1154.
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Les récentes avancées dans les micros et nanotechnologies ont nécessité le développement de nouvelles techniques de synthèse de films minces de nouveaux matériaux. Parmi eux, les polymères possèdent des propriétés intéressantes, notamment pour des domaines comme la microélectronique ou le biomédical. Pour pallier ce besoin, les techniques de dépôt de vapeur chimique (Chemical Vapor Deposition, CVD) se sont multipliées. Ces travaux portent sur la synthèse de couches minces de poly(méthacrylates) par un une nouvelle méthode de dépôt chimique en phase vapeur par une polymérisation amorcée in-situ ou initiated Chemical Vapor Deposition (iCVD). Cette technique possède de nombreux avantages parmi lesquels se trouvent ses conditions opératoires douces (absence de solvant, emploi de faibles températures), sa versatilité et sa conformité. Afin de mieux comprendre le procédé de synthèse des films minces de polymères par iCVD, une partie de ces travaux de thèse concerne l’étude de la cinétique de croissance des poly(méthacrylates). Une cinétique en deux régimes a été identifiée pour les deux polymères. Les analyses microscopiques et macroscopiques de couches minces issues des deux régimes ont permis la proposition d’un modèle de croissance. Le premier régime, au début de la croissance, est caractérisé par une faible vitesse de dépôt et des polymères de faibles masses molaires. Lorsque le second régime est atteint, la vitesse de dépôt est plus importante et devient constante. Les chaînes synthétisées possèdent des masses molaires plus élevées. Ce changement a pu être expliqué en mettant en avant la capacité du film en formation à se gorger de monomères, ce qui augmente la concentration locale de monomères. La cinétique de croissance des poly(méthacrylates) a aussi été étudiée sur des sous-couches de polymères et d’organosiliciés poreux. L’iCVD s’est révélée être une méthode capable de remplir de manière quasiment instantanée les pores nanométriques d’une couche mince. De plus, pour obtenir un meilleur contrôle des polymères synthétisés par iCVD au niveau de leur architecture macromoléculaire ou de leur masse molaire, la mise en place d’une technique de polymérisation radicalaire contrôlée est discutée. La dernière parte de cette thèse concerne l’application du procédé de polymérisation RAFT (polymérisation radicalaire par transfert de chaînes réversible par addition/fragmentation) en iCVD à l’aide de coupons de silicium fonctionnalisés au préalable avec des agents RAFTRecent progress in micro and nanotechnologies require the development of new synthesis process for various material thin films. Polymers, thanks to their properties, are very interesting for fields like microelectronic or biomedical. To respond to this need, many Chemical Vapor Deposition (CVD) technologies are studied. This work focuses on a new method called initied Chemical Vapor Deposition (iCVD). This deposition method gives many advantages as its soft operational conditions (solvent free, low temperature), versatility and conformity. In order to improve the understanding of synthesis mechanism in iCVD, the first part of this work is about the poly(methacrylates) thin films growth kinetic. The study reveals two-regime growth kinetics. A model for the growth mechanism based on the microscopic and macroscopic analysis of thin layers from the two regimes is proposed. The first regime, at the early stage of the growth, is characterized by a slow deposition rate and polymers with low molecular mass. When the second regime appears, the deposition rate is higher and constant and polymers have higher molecular mass. These evolutions could to be explain by the growth film ability to stock monomers and thus increase the local monomer concentration. Poly(methacryaltes) growth kinetics are also investigated on polymeric and porous organosilicate layers. It appears than iCVD is a deposition method that can fill nanometrics pores with polymer really quickly. Moreover, to have a better control on polymer synthesized by iCVD (molecular weight, macromolecular architecture), the possibility to used a Reversible-Deactivation Radical Polymerization (RDRP) method with iCVD process is discussed. The last part of this work concerns the use of Reversible Addition Fragmentation chain Transfer (RAFT) polymerization with the iCVD process thanks to silicon samples pre-functionalized with RAFT agent
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Styan, Katie Graduate School of Biomedical Engineering Faculty of Engineering UNSW. "Polyurethane organosilicate nanocomposites for novel use as biomaterials". Awarded by:University of New South Wales. Graduate School of Biomedical Engineering, 2006. http://handle.unsw.edu.au/1959.4/25218.
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Polymer organosilicate nanocomposites have attracted significant attention over the last decade due to improved mechanical, thermal, and barrier properties. Several nanocomposite researchers have recognised potential for biomedical applications, however none have conducted biological investigations. In this project, the predicted ability of the organosilicate to enhance biostability, modulate the release of included drugs, and confer biofunctionality and control over the host response, were assessed as the three primary hypotheses. The studies were conducted with the objective being employment as urinary device biomaterials. Of prime importance was that no detrimental change in cytocompatibility was resultant. Biomedical thermoplastic elastomeric polyurethane organosilicate nanocomposites were prepared from poly(ether)urethane of 1000g/mol poly(tetramethylene oxide) polyol, 4,4??? diphenylmethane diisocyanate, and 1,4 butanediol chain extender chemistry, and various organosilicates with loadings from 1w% to 15w%, using a solution casting technique. Initially, partially exfoliated nanocomposites were produced using a commercially available organosilicate, Cloisite?? 30B. These nanocomposites displayed several advantageous properties, namely i) significant anti-bacterial activity, reducing S. epidermidis adherence after 24h to ~20% for a 15w% organosilicate loading, ii) enhanced biostability, with a 15w% organosilicate loading displaying only slight degradation after a 6 week subcutaneous in vivo ovine implantation, and iii) static modulation of model drug release as a factor of drug properties and organosilicate loading. The former was attributed to the Cloisite?? 30B quaternary ammonium compound, while the latter two were likely primarily barrier effect related and due to changes to poly(ether)urethane permeability. Electrostatic and chemical interactivity between drug and organosilicate was also implicated in the observed drug release modulation. Unfortunately, a lack of in vitro cytocompatibility and poor in vivo inflammatory response will limit in vivo use. Utilising bioinert 1-aminoundecanoic acid as an alternative organic modification, cytocompatible intercalated nanocomposites were produced thus likely allowing in vivo nanocomposite use and exploitation of the barrier effect related properties. However, these nanocomposites were not antibacterial. Variation of the organic modification and/or use of co-modification were viable means of modulating host response and biofunctionality, however nanoscale dispersion of co-modified silicate was poor. Use of nanocomposite technology was concluded beneficial to existing biomaterials, and specifically to biomaterial application as urinary catheters / stents.
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Martinez, Nelson Yohan Reidy Richard F. "Wettability of silicon, silicon dioxide, and organosilicate glass". [Denton, Tex.] : University of North Texas, 2009. http://digital.library.unt.edu/ark:/67531/metadc12161.
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Miura, Katsukiyo. "Studies on New Radical Reactions of Organosilicon Compounds". Kyoto University, 1993. http://hdl.handle.net/2433/168868.
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本文データは平成22年度国立国会図書館の学位論文(博士)のデジタル化実施により作成された画像ファイルを基にpdf変換したものであるKyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第5393号
工博第1284号
新制||工||902(附属図書館)
UT51-93-F150
京都大学大学院工学研究科工業化学専攻
(主査)教授 内本 喜一朗, 教授 高谷 秀正, 教授 伊藤 嘉彦
学位規則第4条第1項該当
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Martinez, Nelson. "Wettability of Silicon, Silicon Dioxide, and Organosilicate Glass". Thesis, University of North Texas, 2009. https://digital.library.unt.edu/ark:/67531/metadc12161/.
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Wetting of a substance has been widely investigated since it has many applications to many different fields. Wetting principles can be applied to better select cleans for front end of line (FEOL) and back end of line (BEOL) cleaning processes. These principles can also be used to help determine processes that best repel water from a semiconductor device. It is known that the value of the dielectric constant in an insulator increases when water is absorbed. These contact angle experiments will determine which processes can eliminate water absorption. Wetting is measured by the contact angle between a solid and a liquid. It is known that roughness plays a crucial role on the wetting of a substance. Different surface groups also affect the wetting of a surface. In this work, it was investigated how wetting was affected by different solid surfaces with different chemistries and different roughness. Four different materials were used: silicon; thermally grown silicon dioxide on silicon; chemically vapor deposited (CVD) silicon dioxide on silicon made from tetraethyl orthosilicate (TEOS); and organosilicate glass (OSG) on silicon. The contact angle of each of the samples was measured using a goniometer. The roughness of the samples was measured by atomic force microscopy (AFM). The chemistry of each of the samples were characterized by using X-ray photoelectron spectroscopy (XPS) and grazing angle total attenuated total reflection Fourier transform infrared spectroscopy (FTIR/GATR). Also, the contact angle was measured at the micro scale by using an environmental scanning electron microscope (ESEM).
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Fukushima, Motoo. "Synthesis and Electrical Conductive Properties of Organosilicon Polymers". Kyoto University, 1999. http://hdl.handle.net/2433/182375.
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Ayoko, G. A. "Mechanistic studies on some sterically hindered organosilicon compounds". Thesis, University of Sussex, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.370428.
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Najim, S. T. "Mechanistic studies on some sterically hindered organosilicon compounds". Thesis, University of Sussex, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.373132.
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Li, Yan [Verfasser] y Thomas [Akademischer Betreuer] Bein. "Periodic mesoporous organosilicas with functional chromophores / Yan Li. Betreuer: Thomas Bein". München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2012. http://d-nb.info/1056876697/34.
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Moudgil, Suniti 1976. "Organosilicate nanoparticles as gene delivery vehicles for bone cells". Thesis, Massachusetts Institute of Technology, 2004. http://hdl.handle.net/1721.1/28307.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2004.Includes bibliographical references.
(cont.) proliferation. The metabolic response of these cells after particle ingestion was also characterized in order to ensure that the osteoblasts retained their phenotype. The expression of various proteins involved in bone formation, such as alkaline phosphatase, osteocalcin, osteopontin and fibronectin was quantified. The results indicated that osteoblasts retained their phenotype after organosilicate nanoparticle ingestion. The levels of various cytokines expressed during inflammatory response remained low due to the biocompatibility of amorphous silica. An optimized Ca-SiO₂ nanoparticulate system was developed with maximum particle uptake that enhanced cell viability. A model gene delivery system was created by complexing these nanoparticles with plasmid DNA that encoded for green fluorescent protein (GFP). The effects of nanoparticle size, composition and surface charge on complex size, DNA binding affinity and subsequent GFP expression in osteoblasts were investigated in detail. In addition to primary and immortalized osteoblasts, we have studied the effect of this gene delivery system on two other control cell lines: fibroblasts (connective tissue cells) and hepatocytes (non-connective tissue cells). The Ca-SiO₂-DNA complexes displayed significantly higher transfection efficiencies in osteoblasts and fibroblasts relative to hepatocytes compared to lipofectamine-DNA complexes. In addition, Ca-SiO₂-DNA complexes enhanced osteoblast cell proliferation while achieving successful transfection ...
While bone has a substantial capacity to heal itself, there are approximately 1 million fractures that occur in the U.S. annually that are difficult to heal. These include fractures that occur at sites of low vascularity, fractures that result in a large amount of tissue loss, and fractures that result from bone fragility syndromes such as osteoporosis. There has been a great deal of interest in the tissue engineering of bone in order to treat such fractures. One major aspect of the tissue engineering approach involves the addition of growth factors or proteins to synthetic grafts to accelerate bone regeneration. However, delivering these proteins at the appropriate times and therapeutic levels poses significant challenges. Alternatively, delivering the genes that encode for these proteins could offer a more effective treatment, since proper incorporation of the appropriate genes into cellular nuclei would allow the cells to manufacture authentic protein products. The motivation of this research was to design new materials for gene delivery to bone cells. Conventional non-viral vectors are plagued by toxicity and low transfection efficiencies. The purpose of this work was to design bioactive nanoparticles that could enter the osteoblast membrane without inducing toxicity. These materials were silicate-based, since doped silicates have been shown to possess osteogenic properties. A method to synthesize monodisperse, spherical organosilicate nanoparticles using a surfactant-stabilized sol-gel technique was developed. Surface dopants such as Ca, Mg and Na were found to influence cellular response to nanoparticles. In addition to particle composition, particle size was also found to have a significant effect on osteoblast uptake and cell
by Suniti Moudgil.
Ph.D.
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Cave, Nigel Graeme. "The adsorption and adhesion of long-chained organosilicon primers". Thesis, Imperial College London, 1990. http://hdl.handle.net/10044/1/47795.
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Vassilaras, Plousia E. "Alternative Synthetic Methodologies for the Synthesis of Organosilicon Compounds". Case Western Reserve University School of Graduate Studies / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=case1310150433.
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Grösch, Lyubov [Verfasser] y Michael [Akademischer Betreuer] Fröba. "Periodisch mesoporöse Organosilicas mit Förster-Resonanzenergietransfer-Eigenschaften / Lyubov Grösch. Betreuer: Michael Fröba". Hamburg : Staats- und Universitätsbibliothek Hamburg, 2013. http://d-nb.info/1045730386/34.
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Kolle, Joel Motaka. "Mesoporous Organosilicas for CO2 Capture and Utilization: Reaction Insight and Material Development". Thesis, Université d'Ottawa / University of Ottawa, 2020. http://hdl.handle.net/10393/40464.
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As mankind attempts to halt climate change and global warming, large-scale carbon dioxide (CO2) capture, utilization and storage (CCUS) technologies are viewed as an indispensable approach to curb CO2 emission. This thesis focused on better understanding CO2-amine interactions during adsorption, while developing in parallel covalently immobilized polyethylenimine (PEI) adsorbents for CO2 adsorption. In addition, catalyst reusability issues reported in the synthesis of cyclic carbonates (CCs) from CO2 and epoxides using metal-free supported immobilized quaternary ammonium salts are addressed, while developing new organosilicas for the synthesis of CCs.
The reaction between CO2 and amine was investigated at the gas-solid interface in an attempt to provide a unified CO2-amine interaction both in adsorption and absorption. A combination of density functional theory calculations and experimental data (FTIR and 13C NMR) showed that the formation of the zwitterion intermediate often reported in the literature is highly unlikely, instead a six-atom centered zwitterion mechanism involving the “assisting” effect of water, amine or other functional groups was found to be more feasible due to its lower activation energy. Moreover, evidence was provided to suggest that under humid conditions, bicarbonate and carbonate are formed from the reaction between water and CO2, and not the widely reported carbamate hydrolysis.
With a goal of minimizing the leaching of amines on PEI-impregnated adsorbents, PEI was covalently immobilized on mesoporous aluminosilica using 3-glycidoxypropyltrimethoxysilane or 3-triethoxysilylpropyl isocyanate as linkers. The resultant materials were found to be more resistant to leaching (in ethanol) and degradation (air at 100 oC) compared to their impregnated counterparts. Further enhancement in oxidation stability was achieved by covalently grafting epoxide-functionalized PEI onto mesoporous aluminosilica.
CO2 uptake over amine-containing adsorbents is widely reported to be enhanced in the presence of moisture. However, the same cannot be said for other adsorbents, such as, carbonaceous and zeolite-based materials, and most MOFs. In a soon to be submitted review manuscript, a comprehensive analysis on the role of water on CO2 uptake (equilibrium and kinetics), material structure and regeneration over a wide range of adsorbents is presented.
As for CO2-epoxides fixation to cyclic carbonates, a quaternary ammonium salt supported on SBA-15 was used to investigate the observed literature trend between product yield and substrate type with catalyst reuse. Under mild reaction conditions (1.0 MPa CO2, 100 oC and 4 h), 1,2-butylene carbonate was obtained in high yields (> 95%) over 5 cycles as the substrate is easy to activate and the product can be completely removed from the catalyst surface due to its low boiling point. Nonetheless, using styrene oxide led to decrease in yield over reuse cycles, mainly because styrene carbonate crystals were trapped on the catalysts surface (13C MAS NMR and TGA data), thereby blocking access to active sites. By extensively washing all spent catalysts in acetone and using chromatographic grade SiO2 as support material, styrene carbonate was obtained in very good yield (> 93%) over five cycles.
Finally, novel quaternary ammonium iodide-based organosilicas, grouped into disordered, ordered and periodic mesoporous organosilicas, were prepared and tested for the cycloaddition of CO2 to epoxide to yield cyclic carbonates. Under mild reaction conditions (0.5 MPa CO2, 50 oC and 10 – 15 h) catalysts with the ordered mesoporous organosilicas structure were found to be more active owing to their larger surface area and pore volume, enhancing the accessibility of active sites by epoxides.
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Gu, Shihai. "ADSORPTION AND STRUCTURAL PROPERTIES OF POLYMER-TEMPLATED ORDERED MESOPOROUS ORGANOSILICAS SYNTHESIZED BY USING REACTIVE ORGANOSILANES". Kent State University / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=kent1320082453.
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Masangane, Phindile Clemintine. "Some chemistry of sterically hindered tetrasilylmethane derivatives". Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.369193.
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Houlton, David Joseph. "Polyhedral oligometallasilsesquioxanes". Thesis, University of Liverpool, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.241467.
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Heaton, Stephen Nicholas. "Vinylsilane and silyl hydride complexes of platinum group metals". Thesis, University of York, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.295650.
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