A novel core-shell silica based antimicrobial nanoparticle was synthesized. The Stöber silica shell has been engineered to accommodate copper. Synthesis of the core-shell Cu-silica nanoparticle (C-S CuSiNP) involves preparation of base-hydrolyzed Stöber silica “seed” particles first, followed by the acid-catalyzed seeded growth of the Cu-silica shell layer around the core. Scanning electron microscopy and transmission electron microscopy showed monodispersed, spherical shaped nanoparticles with smooth surface morphology. Characterization of particle size distribution in solution by the Dynamic Light Scattering (DLS) technique was fairly consistent with the electron microscopy results. Loading of Cu to nanoparticles was confirmed by the SEM-Energy Dispersive X-Ray Spectroscopy (EDS) and Atomic Absorption Spectroscopy (AAS). Antibacterial efficacy of C-S CuSiNP was evaluated against E.coli and B.subtilis using Cu hydroxide (“Insoluble” Cu compound) and copper sulfate as positive control and silica “seed” particles (without Cu loading) as negative control. Minimum Inhibitory Concentration (MIC) of C-S CuSiNP was evaluated by measuring the fluorescent intensity of resorufin to determine the decrease in viable cells with increase in copper concentration in C-S CuSiNP. The MIC value of C-S CuSiNP against both E.coli and B.subtilis was estimated to be 4.9 ppm. Bac-light fluorescence microscopy based assay was used to count relative population of the live and dead bacteria cells. Antibacterial study clearly shows that C-S CuSiNP is more effective than insoluble Cu hydroxide particles and copper sulfate at equivalent metallic Cu concentration, suggesting more soluble Cu in C-S CuSiNP material due to its coreshell design.

学位プログラム名: 京都大学大学院思修館 / 京都大学 / 新制・課程博士 / 博士(総合学術) / 甲第23346号 / 総総博第19号 / 新制||総総||3(附属図書館) / 京都大学大学院総合生存学館総合生存学専攻 / (主査)教授 寶 馨, 教授 内本 喜晴, 特定教授 橋本 道雄 / 学位規則第4条第1項該当 / Doctor of Philosophy / Kyoto University / DFAM

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<p>Differences in the wavelengths of the surface plasmon band of gold nanoparticles (AuNP) – before and after particle aggregation – are widely used in bioanalytical assays. However, the gold surfaces in such bioassays can suffer from exchange and desorption of non-covalently bound ligands and from non-specific adsorption of bio-molecules. Silica shells on the surfaces of the gold can extend the available surface chemistries for bioconjugation and potentially avoid these issues. Therefore, silica was grown on gold surfaces primed with polyvinylpyrrolidone (PVP) using either hydrolysis/condensation of tetraethyl orthosilicate under basic conditions or diglycerylsilane at neutral pH. The former precursor permitted slow, controlled growth of shells from about 1.7 to 4.3 nm thickness. By contrast, silica shells formed within an hour using diglyceroxysilane; the thickness was insensitive to changes in silane concentration and incubation time and could be tuned using different molecular weight PVP to prime the particles. The control over shell thickness is discussed with respect to the PVP interface, the electrical double layer, and interpenetrating organic-inorganic hybrid structures. Within the range of shell thicknesses synthesized, the presence of a silica shell on the gold nanoparticles did not significantly affect the absorbance maximum (~ 5 nm) of unaggregated particles. However, the change in absorbance wavelength upon aggregation of the particles was highly dependent on the thickness of the shell. With silica shells coating the AuNP, there was a significant decrease in the absorbance maximum of the aggregated particles, from ~578 to ~536 nm, as the shell thicknesses increased from ~1.7 to ~4.3 nm, due to increased distance between adjacent gold cores. These studies provide guidance for the iv development of colorimetric assays using silica coated AuNP. Such particles also show potential for application in 2D and 3D nanostructured assemblies.</p> / Master of Science (MSc)

Magnets play a major role in our rapidly developing world of technology. Electric motors and generators, transformers, data storage devices, MRI machines, cellphones, and NMR are some of the many applications for magnets. However, almost all the magnets currently being used have rare-earth heavy metals in them. Despite their high-energy product, the presence of rare-earth metals increases the cost significantly. Also, the processes involved in the mining of rare-earth metals are hazardous to the environment, and to all life forms. In the past few decades, oxide based magnets have gained a lot of attention as potential replacements for the rare-earth magnets. Oxide based magnetic nanocrystals are attracting a lot of attention as a potential replacement for rare-earth magnets. They are stable in ambient condition and their manufacturing cost is very low when compared to the rare-earth magnets. My work deals with the synthesis of core-shell magnetic structure for high frequency applications (Chapter 1) and the synthesis of high energy product magnetic nanocrystals (Chapter 2) and the synthesis of soft magnetic nanocrystals for high frequency measurement. NiZn ferrite, a soft oxide based magnet cannot be directly implied at high frequencies as they fail at the frequency which over the MHz range. On the other hand, BaZn ferrite is a Y-type magnets, which is robust at higher frequencies. Therefore, using the latter magnet as a protective shell for core material, made of former magnet, enables us to manufacture a cheap solution to the rare-earth magnets used in our cell phones and other devices that work on high frequency signals. On the other hand, successful coating of a very soft magnetic material on a hard-magnetic core increases the total energy product of the magnetic composite, which enhances its versatility. / Mechanical Engineering