Spelling suggestions: "subject:"silsesquioxane""
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Novel materials based on functionalised silsesquioxanes.Hardy, Julie. January 2000 (has links)
Thesis (Ph. D.)--Open University. BLDSC no. DXN043595.
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Hybrid Organic-Inorganic Bridged Silsesquioxane Nanoparticles for Cancer NanomedicineFatieiev, Yevhen 10 1900 (has links)
It is well established that cancer is one of the leading causes of death globally. Its complete eradication requires early detection and intensive drug treatment. In many cases it might also require surgery. Unfortunately, current medicine is still more focused on cancer treatment rather than elimination of its reason. The mechanism of tumor emergence and development is quite complicated, although, we are constantly advancing in this field. Nanomedicine is envisioned as the silver bullet against cancer. Thus, nanoscale systems with therapeutic and diagnostic modalities can simultaneously perform several functions: accurate detection of tumor site, precise targeting, and controlled drug release inside abnormal cells and tissues while being nontoxic to healthy ones. Moreover, surface modification of such nanoparticles allows them to be invisible to the immune system and have longer blood circulating time. The performed research in this dissertation is completely based on hybrid organicinorganic bridged silsesquioxane (also known as organosilica) nanomaterials, therefore comprising "soft" organic/bioorganic part which can imitate certain biorelevant structures and facilitates successful escape from the immune system for more efficient accumulation in cancer cells, while "hard" inorganic part serves as a rigid and stable basis for the creation of cargo nanocarriers and imaging agents. This dissertation discusses the 5 critical points of safe biodegradable nanoplatforms, delivery of large biomolecules, and cytotoxicity regarding the shape of nanoparticles. As a result novel fluorescent biodegradable oxamide-based organosilica nanoparticles were developed, light-triggered surface charge reversal for large biomolecule delivery was applied with hollow bridged silsesquioxane nanomaterials, and biocompatibility of periodic mesoporous organosilicas with different morphologies was studied. Furthermore, the current achievements and future perspectives of mesoporous silica organosilica, and silsesquioxane nanoparticles were considered in regards to their biomedical applications and summarized in two reviews.
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Functionalized polyhedral oligomeric silsesquioxane (POSS) for incorporation of chemically pendant chains = Utilização de silsesquioxanos oligoméricos poliédricos funcionalizados (POSS) no ancoramento de cadeias orgânicas à superfície / Utilização de silsesquioxanos oligoméricos poliédricos funcionalizados (POSS) no ancoramento de cadeias orgânicas à superfícieRiaz, Ali, 1981- 25 August 2018 (has links)
Orientador: José de Alencar Simoni / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T07:32:13Z (GMT). No. of bitstreams: 1
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Previous issue date: 2014 / Resumo: Este trabalho apresenta a síntese e caracterização de compostos silsesquioxanos gaiola cúbica (POSS) com cadeias orgânicas pendentes. O projeto foi iniciado com a idéia de sintetizar os silsesquioxanos cúbicos com cadeias organofuncionalizadas ancoradas, capazes de capturar os metais pesados, corantes e CO2. Mas foram enfrentadas algumas dificuldades como baixo rendimento (30-37%) e longo tempo de reação (5-35 dias). As reações foram investigadas para melhorar o rendimento, bem como para reduzir o tempo de reação. Algumas modificações em rotas de reação foram introduzidas, o que trouxe melhorias notáveis nos resultados, onde o rendimento aumentou cerca de 64 % e o tempo de reação foi reduzido para 24 horas em média. Na sequência, os produtos sintetizados foram caracterizados para elucidar suas estruturas, utilizando diferentes técnicas físicas tais como FTIR, CHN, XRD, MEV, TGA, 13CNMR e 29SiNMR no estado sólido, onde as gaiolas Si-O de todos os compostos foram evidenciadas por meio de 29SiRMN e dos seus espectros de FTIR, enquanto as cadeias ancorados às gaiolas de POSS foram confirmadas utilizando os resultados de 13CRMN, juntamente com seus respectivos espectros de FTIR. Os compostos sintetizados também foram testados quanto à sua estabilidade térmica utilizando a técnica de TGA. Após a otimização da síntese de silsesquioxanos cúbicos, os híbridos PAA-13-3, PAA-MTC e PAA-Ph foram avaliados por suas habilidades de captação de cátions bivalentes, tais como Cu2+, Cd2+ e Pb2+ de suas soluções aquosas, sendo que o Cu2+ apresentou maior afinidade de sorção em relação aos dois metais. Estes sistemas de sorção foram analisados através ICP-OES. Para explicar o comportamento de sorção destas amostras alguns modelos estatísticos como Langmuir, Freundlich, Temkin e Redlich-Peterson foram aplicadas, onde os dados de sorção de Cu2+ em PAA-13-3 foram melhor ajustados pelo modelo Langmuir, mostrando ser uma sorção monocamada, enquanto que no caso do PAA-MTC e PAA-Ph modelo de melhor ajuste foi o Freundlich, confirmando a sorção de múlti camadas. Um dos materiais sintetizados (PAA-13-3) foi avaliado quanto à sua capacidade de adsorver CO2 gasoso, mostrando-se promissor na remoção de CO2, mesmo a baixas pressões (máx. 100 mm Hg). A adsorção de CO2 no material também foi estudada por calorimetria de adsorção gás-sólido, em um calorímetro especialmente desenvolvido para tal, observando-se valores de entalpia de adsorção entre -36 e -7 kJ mol-1 / Abstract: This report presents the synthesis and characterization of POSS compounds having cubic silsesquioxane cage to which the organic pendant chains are anchored. The project was started with the idea to synthesize the cubic silsesquioxanes with organofunctionalized pendant chains, which are able to capture heavy metals, dyes and some acids like CO2. But in the beginning the hurdles like low % yields (30-37 %) and long reaction times (5-35 days) were to be faced. The reactions were worked out to enhance the % yields as well as to reduce the reaction time. Some modifications in reaction routes have been introduced, which brought up remarkable improvements in the results, where yield was increased upto 64 % and reaction time was reduced to 1 day. All the synthesized products were then characterized for their structure elucidations using different physical techniques like FTIR, CHN, TGA, 13CNMR & 29SiNMR in solid state, where Si¿O cages of all compounds were elaborated through 29Si-NMR in solid state as well as through their respective FTIR patterns, while the pendant chains anchored to the POSS cages were confirmed using 13C-NMR results along with their respective FTIR spectra. The synthesized compounds were then tested for their thermal stability using the TGA technique. After optimizing the synthesis of cubic silsesquioxanes, hybrids PAA-13-3, PAA-MTC and PAA-Ph were worked out for their abilities of capturing divalent cations like Cu2+, Cd2+ and Pb2+ from their aqueous solutions, where Cu2+ showed higher affinity of sorption than other two bivalent metals. These sorption systems were analyzed using the ICP-OES. To explain the sorption behaviour of these samples some statistical models like Langmuir, Freundlich, Sips, Temkin and Redlich-Peterson were applied to the sorption data, where the data for Cu2+ on to PAA-13-3 was best fitted by Langmuir adsorption isotherm model showing the sorption to be monolayer, while in case of PAA-MTC and PAA-Ph Freundlich model was found to be a best fit, confirming multilayer sorption. One of the synthesized materials (PAA-13-3) was also evaluated for its ability to adsorb gaseous CO2 and was proved to be promising in removing CO2, even at low pressures (max. 100 mmHg). The adsorption of CO2 in the material is also studied by solid-gas adsorption calorimetry through a calorimeter especially developed for this system, where enthalpy of adsorption values were found to be between -7 and -36 kJ mol-1 / Doutorado / Quimica Inorganica / Doutor em Ciências
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Highly Functionalized Bridged SilsesquioxanesZhou, Guannan, Simerly, Thomas, Golovko, Leonid, Tychinin, Igor, Trachevsky, Vladimir, Gomza, Yury, Vasiliev, Aleksey 01 June 2012 (has links)
The objective of this work was to synthesize functionalized mesoporous silsesquioxanes with high concentrations of amine groups. During typical sol-gel syntheses, these materials are obtained by co-condensation of organic precursors with suitable linkers, such as tetraethoxysilane, necessary to prevent the mesoporous structure from collapsing. Thus, concentrations of amine groups in organosilicas usually do not exceed 2.7-3.4 mmol g -1. The use of bridged bis-trimethoxysilanes, however, allowed formation of mesoporous materials with no linker. Polycondensation of bis-trimethoxysilanes containing amine groups was conducted in acidic, neutral and basic media, resulting in high yields of solid bridged silsesquioxanes. Gelation occurred quickly if no acid or base was added to the reaction mixture. The hybrid organic/ inorganic nature of obtained materials was confirmed by FT-IR and MAS CP NMR spectroscopy. Elemental analysis showed that amino group concentration in the products was 3.3-4.1 mmol g -1. Measurement of particle size distribution confirmed that choice of reaction media significantly affects particle sizes and agglomeration degrees, with the largest agglomerates (up to 50 μm) formed in basic media. A morphology study, using smallangle X-Ray scattering, displayed two-level fractal structures composed of aggregated 6.5-10.5 nm particles. Reactions in the presence of a surfactant resulted in formation of mesoporous structures. Furthermore, the obtained bridged silsesquioxanes were thermally stable down to 260 °C, but could reversibly absorb water and CO 2 at temperatures below 120 °C. Thus, condensation of the bridged precursor without a linker resulted in formation of a highly functionalized mesoporous material.
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Mesoporous Adsorbents for Perfluorinated CompoundsKuvayskaya, Anastasia, Lotsi, Bertha, Mohseni, Ray, Vasiliev, Aleksey 01 October 2020 (has links)
Effective adsorbents for polyfluorinated compounds (PFCs) were obtained and successfully tested in adsorption of perfluorooctanoic and perfluorooctanesulfonic acids. Bridged silsesquioxanes containing secondary and tertiary amino groups were synthesized by sol-gel condensation of bis[3-(trimethoxysilyl)propyl]amine and N-methyl-3,3′-bis(trimethoxysilyl)dipropylamine in acidic media in the presence of surfactants. Obtained materials were mesoporous with high BET surface area. They combine high structural stability with high concentration of surface amino groups serving as adsorption sites. Batch adsorption tests demonstrated their high adsorption capacity on PFCs: in some experiments it reached up to 88% of the adsorbent weight. Adsorption of PFCs changed the surfaces of the adsorbent nanoparticles from hydrophilic to hydrophobic thus providing their agglomeration and floatability. Column tests showed fast adsorption of PFCs even at high concentrations and high flow rates. Obtained results can be used in the development of an effective filtration device for clean-up of water contaminated by PFCs.
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Structure Property Relationships in Polymer Blends and Composites. Part I - Polymer/POSS Composites Part II - Poly(ethylene terepthalate) ionomer/Polyamide 6 Blends Part III - Elastomer/Boron Nitride CompositesIyer, Subramanian 06 July 2006 (has links)
No description available.
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Molecular Shape Amphiphile Based on Keggin Polyoxometalates and iso-Butyl Polyhedral Oligomeric Silsesquioxanes: Synthesis and CharacterizationShan, Wenpeng 17 September 2014 (has links)
No description available.
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Nanostructuration of epoxy networks by using polyhedral oligomeric silsesquioxanes POSS and its copolymersChen, Jiang Feng 08 June 2012 (has links) (PDF)
A series of hybrid component based on reactive polyhedral oligomeric silsesquioxane(POSS) precusors and its reactive copolymers of PGMA were synthesized and utilized to nanobuild in epoxy. Reactive POSS and copolymer dispersed in homogenous in matrix, overcomed POSS-POSS interaction, which resulted in macroscale phase separation. The nanocomposites obtained were analyzed by Scanning electron microscopy, Transmission electron microscopy, X-ray scattering and dynamic mechanical. An analogue of POSS (denoted as POSSMOCA) was synthesized via addition reaction, which had reactive amino group bonding into epoxy network and improved the thermostability, because of the structural silicon, nitrogen and halogen. Epoxy/polyhedral oligomeric silsesquioxanes (POSS) hybrid composites were prepared from prereaction between trifunctional silanol POSS-OH and diglycidyl ether of bisphenol A (DGEBA) via silanol and the oxirane group. Reactive POSS-PGMA was polymerized via Reversible addition-fragmentation transfer polymerization. It was easy to tail the compatibility of the epoxide block copolymer with a step-growth polymerized matrix, to form nanostructure via reaction with PGMA segements. In the case of inert POSS-PMMA copolymers modified epoxy, topology of copolymer defined the final morphology and interaction between epoxy and them, because of directional hydrogen bonding and dilution effect. Tg of different epoxide conversion, obeyed of Gordon-Taylor equation and Kwei equation, k which reflected the interaction of modifier and DGEBA/MEDA and epoxy/amine oligomers, was consistent of the rheology and dynamic results.
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Bridged Mesoporous Silsesquioxanes as Potential CO<sub>2</sub> AdsorbentsEsam, Odette, Zhou, Guannan, Vasiliev, Aleksey 01 June 2015 (has links)
Abstract: Mesoporous amino-functionalized adsorbents for post-combustion CO2 capture were synthesized by grafting and sol–gel methods. The silsesquioxane obtained by polycondensation of bis[3-(trimethoxysilyl)-propyl]amine without a cross-linker had the highest amount of surface amino groups. Their content was 8.4 times higher than in the grafted material prepared with the same precursor. All obtained materials were tested in CO2 reversible adsorption from a gas stream. The bridged silsesquioxane adsorbent had the adsorption capacity 4.7 times higher than the grafted sample obtained from the same precursor. Porosity study of this material revealed wide pore size distribution with notable fraction of macropores. The nature of adsorbed species was determined from the FTIR spectrum after adsorption. It was found that CO2 formed carbamate and bicarbonate species on the surface.
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Giant Shape Amphiphiles Based on Polyoxometalates (POMs)-Polyhedra Oligomeric Silsesquioxane (POSS) Hybrids: Synthesis and CharacterizationJiang, Jing 07 June 2013 (has links)
No description available.
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