Heavy metals have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Silver and copper in particular have been used for millennia to control bacterial and fungal contamination. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties due to their increased surface area and localized release of metal ions when attached to pathogens. In the current studies, metal and metalhalide nanoparticles including silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles were evaluated for their antibacterial efficacy against two common bacterial pathogens. All of the nanoparticles significantly reduced bacterial numbers within 24 hours of exposure and were more effective against the Gram-negative Pseudomonas aeruginosa than the Gram-positive Staphylococcus aureus. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log₁₀ within 15 minutes at 60 ppm Cu. CuI nanoparticles were selected for further evaluation against a range of microorganisms to determine their broad spectrum efficacy. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; PVP) were tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes of exposure (>5.09-log₁₀). The Gram-positive bacterial species were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. Likewise, C. albicans was also more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to the CuI-SDS than the CuI-PVP nanoparticle solutions (2.54-log₁₀ vs. 3.80-log₁₀ after 30 minutes). Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum. M. fortuitum was more resistant to both CuI nanoparticle solutions than any of the other organisms tested, requiring longer exposure times to achieve comparable reductions (~4.15 log₁₀ after 24 hours). As an example of a real world antimicrobial application, polymer surface coatings with embedded CuI nanoparticles were investigated to determine their potential use as self-disinfecting surfaces. Brushed polyurethane, spincoated acrylic, and powder coated polyester-epoxy coatings containing various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were superior to the other coatings in terms of uniformity and stability under moist conditions and displayed antimicrobial properties against both organisms (>4.92 log₁₀) after six hours at 0.25% Cu. Polyester-epoxy coatings were selected for more rigorous testing under adverse conditions. These surfaces were negatively impacted when tested under dry conditions with high organic content, with organic content appearing to have a greater impact on antimicrobial efficacy. At 0.25% Cu, the antibacterial activity of the powder coatings was not impacted by washing with several commercial cleaners; however, at concentrations of 0.05% Cu, antibacterial activity was reduced by multiple washings with water, Windex®, and Pine Sol®. Additionally, ultrasonic cleaning of the coatings appeared to decrease their antimicrobial efficacy. Despite this, CuI nanoparticles were found in all studies to have great potential as a new class of fast-acting, broad-spectrum antimicrobial.

Pastarąjį dešimtmetį, intensyviai vystantis nanotechnologijoms, ženkliai išaugo technologinių metodų, įgalinančių suformuoti darinius, kuriuose elementų dydžiai būtų tarp 1 ir 100 nm, paieška. Šiai specifinei nanostruktūrinių medžiagų grupei skiriamas ypatingas dėmesys dėl naujų fizikinių reiškinių ir ypač - praktinių taikymų, kuriuos atveria šie dariniai. Šiame darbe aptariamos elektrocheminės technologijos, skirtos kontroliuojamos morfologijos porėtojo silicio formavimui. Suformuoti hibridiniai por-Si dariniai su metalais. Sukurta biomolekulių įterpimo į porėtuosius silicio darinius technologija bei tirta biomolekulių sąveika su kietakūniais padėklais. Nagrinėjami GaP nanodarinių formavimo elektrocheminio ėsdinimo būdu dėsningumai bei jų taikymo galimybės dujų sensoriuose. Įsisavinta nanoporėtųjų dielektrinių terpių ir hibridinių nanodarinių formavimo technologija bei tirtos jų savybės. / Over the past decade, the intensive development of nanotechnology was made to increase significantly the number of methods to form the structures of a size between 1 and 100 nm. It should be emphasized that nanostructured materials are interesting both because of perspectives in practical applications and new physical phenomena. In this work the electrochemical technique for the control of morphology of porous silicon matrix developed. Hybrid por-Si structures with metals were made. The method for infiltration of biomolecules into the porous silicon structures was developed and the interaction between silicon and bio-molecules was investigated. GaP nanostructures were formed by electrochemical etching and the possibilities of their application for gas sensors were estimated. Nanoporous and Fe-doped silica films on Si were made and the developed structures were characterized by their structural, optical or magnetic properties.

Over the past decade, the intensive development of nanotechnology was made to increase significantly the number of methods to form the structures of a size between 1 and 100 nm. It should be emphasized that nanostructured materials are interesting both because of perspectives in practical applications and new physical phenomena. In this work the electrochemical technique for the control of morphology of porous silicon matrix developed. Hybrid por-Si structures with metals were made. The method for infiltration of biomolecules into the porous silicon structures was developed and the interaction between silicon and bio-molecules was investigated. GaP nanostructures were formed by electrochemical etching and the possibilities of their application for gas sensors were estimated. Nanoporous and Fe-doped silica films on Si were made and the developed structures were characterized by their structural, optical or magnetic properties. / Pastarąjį dešimtmetį, intensyviai vystantis nanotechnologijoms, ženkliai išaugo technologinių metodų, įgalinančių suformuoti darinius, kuriuose elementų dydžiai būtų tarp 1 ir 100 nm, paieška. Šiai specifinei nanostruktūrinių medžiagų grupei skiriamas ypatingas dėmesys dėl naujų fizikinių reiškinių ir ypač - praktinių taikymų, kuriuos atveria šie dariniai. Šiame darbe aptariamos elektrocheminės technologijos, skirtos kontroliuojamos morfologijos porėtojo silicio formavimui. Suformuoti hibridiniai por-Si dariniai su metalais. Sukurta biomolekulių įterpimo į porėtuosius silicio darinius technologija bei tirta biomolekulių sąveika su kietakūniais padėklais. Nagrinėjami GaP nanodarinių formavimo elektrocheminio ėsdinimo būdu dėsningumai bei jų taikymo galimybės dujų sensoriuose. Įsisavinta nanoporėtųjų dielektrinių terpių ir hibridinių nanodarinių formavimo technologija bei tirtos jų savybės.

The research presented in this thesis firstly concerns the use of electrochemical techniques to develop approaches to wool processing which have a lower impact on the environment than conventional chemical methods. Wool is a sulfur rich substrate and current methods used in wool processing often rely on sulfur-based reducing agents such as metabisulfite. However, due to increasing concern over the environmental impacts of metabisulfite, alternative methods are of interest. Electrochemical techniques have been applied to the process of wool setting in the presence of thiol setting agents. Wool disulfide bonds are reduced during this process and the thiol setting agent is converted to the disulfide. Efficient conversion of the disulfide back to the thiol setting agent would allow catalytic amounts of thiols to be used in wool setting. The electroreduction of cystine and 2-hydroxyethyl disulfide has been examined at a range of metal and carbon electrodes to find efficient methods of generating the corresponding thiols, cysteine and 2-mercaptoethanol respectively. Gold and silver were identified as the most efficient electrode materials. In industrial wool processing, the use of large-scale metal electrodes is expensive and therefore, high surface area gold and silver nanoparticle electrodes were fabricated by electrochemically depositing the metals onto low-cost carbon substrates. The most efficient electrochemical system for generating the thiol setting agent involved the electroreduction of cystine at the gold nanoparticle electrode and this system was used to successfully demonstrate that wool setting can be achieved using relatively low concentrations of cysteine. Further research was carried out to investigate methods for the controlled preparation of metal nanoparticle electrodes and their utility for detecting hydrogen peroxide was examined. A simple and versatile approach for the preparation of tethered gold nanoparticle assemblies was developed by exploiting electrostatic interactions between citrate-capped gold nanoparticles and amine tether layers attached to carbon surfaces. The nanoparticle assemblies were optimised for the detection of hydrogen peroxide by selecting the size and density of electrostatically assembled nanoparticles. The number of amine functionalities on the surface and the assembly conditions controlled the nanoparticle density. Nanostructured palladium electrodes fabricated using vapour deposition methods to immobilise palladium nanoparticles directly onto carbon substrates were also examined for the electroanalysis of hydrogen peroxide.

This thesis describes the synthesis, characterisation and catalytic testing of multifunctional immobilised metal nanoparticle in metal-organic framework (MOF) materials. Combining the activity of metal nanoparticles with the porosity and Lewis acidity of metal-organic frameworks provides a single catalytic material which can perform multi-step reactions. Strategies to immobilise the metal nanoparticles within the metal-organic frameworks have been investigated. Immobilisation has been achieved by applying three different methodologies. First, deposition of metal nanoparticle precursors within mesoporous MOFs is discussed. Chapter 3 shows the effectivity of the double solvents deposition technique to achieve dispersed and small nanoparticles of around 2.7 nm. The best system combined Pd nanoparticles with MIL-101(Cr). This system was further investigated in tandem reductive amination catalysis, discussed in Chapter 4, to investigate the activity and selectivity provided by these multifunctional catalysts. Another immobilisation technique was performed by coating Pd decorated SiO2 spheres with a MOF layer. Using this technique, MOF was grown cyclically in solution, providing tuneable shell thicknesses of MOF on the metal nanoparticle decorated oxide spheres. While the homogeneity of the MOF shell needs more optimisation, it was determined that the surface charge on the spheres played an important role in the growth of MOF in the desired location. Finally, the third immobilisation technique is the core-shell growth of MOF on colloidal metal nanoparticles. Polymer-capped metal nanoparticles with well-defined shapes were synthesised and characterised. From here, the optimisation of conditions for core-shell growth of UiO-66 and MIL-100(Sc) were investigated. Conditions which provided the desired core-shell morphology were found for both MOF types. These materials were then subsequently used in tandem reductive amination catalysis and a more straightforward styrene hydrogenation. It was shown that the metal nanoparticles remain active catalysts within either MOF shell and the MOF shell stabilises the metal nanoparticle and acts as a Lewis acid catalyst.

No description available.

La modification du TiO₂ P25 par un ou deux métaux a connu un intérêt considérable ces dernières années, car ils constituent des catalyseurs et photocatalyseurs très actifs à la fois sous lumière UV et visible. Des nanostructures à un ou deux métaux, comme Au, Ag, Ag@CuO et CuO déposés sur le TiO₂ P25 ont la capacité d’absorber la lumière visible sur un large domaine de longueurs d’onde. Le TiO₂ modifié par des nanoparticules métalliques (comme, Cu, Au ou Ag) absorbe la lumière visible grâce à la résonance de plasmon de surface localisée (LSPR) des métaux. Dans le cas d’une hétérojonction de semi-conducteurs, la lumière visible est absorbée grâce à l’énergie du gap plus faible du second semi-conducteur (par rapport à celle du TiO₂ P25). La modification par une ou deux nanoparticules métallique induit une plus grande activité photocaralytique sous lumière visible par rapport au TiO₂ P25 pur, par transfert d’électrons vers la bande de conduction du P25. De plus sous lumière UV, la vitesse de capture d’électrons photo-excités peut être améliorée, ce qui inhibe les processus de recombinaison et permet de stocker ces électrons photo-excités.Cette thèse présente une synthèse des récentes avancées dans la préparation de TiO₂ modifié en surface par un ou deux métaux et ses applications environnementales. Des nanoparticules d’or ont été synthétisées par une méthode chimique à partir de chlorure de tetrakis(hydroxymethyl) phosphonium (THPC), des nanoparticules de Ag, Ag@CuO et CuO ont été synthétisées sur TiO₂ par radiolyse. L’effet de nombreux paramètres (comme la taille et la forme des particules ou la quantité de métal déposé) sur l’activité photocatalytique (oxydation du phénol, du 2-propanol et de l’acide acétique et génération d’hydrogène) a été étudié. La dynamique de porteurs de charge a été étudiée par conductivité microonde résolue en temps (TRMC). / The modification of TiO₂-P25 with one or two metal-based nanoparticles, have attracted considerable attention in recent years, as a new class of highly active catalysts and photocatalysts under both UV and visible light irradiation. One or two-metal-based structures, such as Au, Ag, Ag@CuO and CuO deposited on TiO₂-P25 have the ability to absorb visible light in a wide spectral range. Surface modified TiO₂ with metal nanoparticles (such as Cu, Au, Ag) absorb visible light due to the localized surface plasmon resonance (LSPR). In the case of semiconductor heterojunctions, they absorb visible light due to the narrow band gap of the second semiconductor, lower than TiO₂-P25. The modification with one or two metal-based nanoparticles induces a higher activity under visible light compared to pure TiO₂-P25, due to the transfer of electrons to the conduction band of TiO₂-P25. On the other hand, under UV irradiation, the speed of trapping photoexcited electrons can be improved, and inhibit the recombination process and have the capability of the storage of photoexcited electrons.This thesis presents recent advances in the preparation and environmental application of the surface modification of TiO₂-P25 with one or two-metal-based nanoparticles: The Au-NPs were synthesized by chemical method using tetrakis(hydroxymethyl) phosphonium chloride (THPC), and the nanoparticles of Ag, Ag@CuO and CuO-NPs were synthesized by gamma irradiation. Moreover, the effects of various parameters (such as particle size, shape of the nanoparticles and amount of metals) on the photocatalytic activity (phenol, 2-propanol and acetic acid oxidation, as well as hydrogen generation) were also studied. The charge carrier dynamics was studied by time resolve microwave conductivity (TRMC).

京都大学 / 0048 / 新制・課程博士 / 博士(薬科学) / 甲第21713号 / 薬科博第104号 / 新制||薬科||11(附属図書館) / 京都大学大学院薬学研究科薬科学専攻 / (主査)教授 小野 正博, 教授 山下 富義, 教授 髙倉 喜信 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DFAM

This master's thesis deals with growth of germanium nanowires using different catalyst particles. The emphasis is mainly layed on fabrication of specific alloyed catalyst consisting of (AgGa). In the first part of the thesis are mentioned two most common concepts of nanowire growth and the importance of phase diagrams for their interpretation. Method for production of alloyed catalyst is demonstrated and experiments focused on the growth of germanium nanowires using this catalyst were performed. Moreover, method for modification of germanium surface via anisotropic etching is demonstrated as well. Such etched structures are suitable for nanowire growth with the help of different kinds of catalyst particles or for the growth of nanowires made of various materials.

No description available.