Using a variety of techniques including femtosecond transient absorption spectroscopy, optical absorption, atomic force microscopy, the hot electron cooling dynamics of lithographically prepared gold nanoarrays, the effect of the surrounding environment, and the phonon oscillations of gold and silver nano-arrays were investigated. The cooling dynamics of gold nanoarrays on a glass substrate were found to be different from those of either colloidal nanodots in colloidal solution or films on glass substrate. The electron-phonon component of the electronic relaxation in the arrays was found to be longer than that in the dots or the films. The spatially isolated nanoarray particles experience a significantly different environment than the gold nanodots in solution, thus the long phonon-phonon component resulting from the coupling of particles to the medium, is not observed. The catalytic effectiveness of platinum nanoparticles for the hydrogenation of propene was investigated. The system with platinum particles was found to have a slightly lower activation energy than other systems in the literature. The effect of encapsulating the platinum particles in alumina was also investigated and it was found that the activation energy for the reaction was even lower. The effect of adding platinum, palladium, and rhodium particles to the proton exchange membrane of polymer electrolyte fuel cells, on the output power of the cells was also investigated. The effects of pH and precursor salt concentration, and particle composition were also investigated.

No description available.

Nanoparticle toxicity has become a major topic of interest due to the inevitable exposure of these nanomaterials to both humans and the environment. Nanotechnology is a rapidly growing industry with diverse material resources and an extensive market for commercialization and introduction of nanomaterials into consumer products. The problem with this flourishing technology is that it has far outgrown research based on the safety and toxicity of the nanomaterials, which in bulk are generally nontoxic. The need for research in determining the toxic effects on cells and the implications it may have on the environment have grown but the different techniques, cell systems and nanoparticles employed are generally to diverse and conflicting in overall results that determination toxicity is nearly impossible. The need for a universal technique to study the interaction of nanoparticles with cells and decouple the molecular effects (chemical properties) from the“nanospecific" effects (including size, concentration, surface charge, functionality and polarity) is apparent. It is additionally necessary to determine the mechanisms associated with nanoparticle-induced cytotoxicity in order to better understand the problems posed to both human and environmental health and then develop new safer nanoparticles. Therefore, the focus of this study is to determine the nano-specific (physical) properties, including size and functionalization that cause toxicity, specifically through interaction with a cell membrane. A supported lipid bilayer (SLB) composed of L-α-phosphatidylcholine (egg PC) was used as a model cell membrane to test the effects of 2, 5, 10 and 40 nm gold nanoparticles (AuNPs). Given the imminent exposure of nanoparticles to the environment it is important to determine how nanoparticles would behave in the presence of natural organic matter or polymers which are naturally present in environmental systems. Poly(methacrylic acid) (PMA) can be used to represent the polymers normally found in the environment. AuNPs were diluted in PMA in order to simulate fundamental environmental conditions. Analysis was done using a quartz crystal microbalance with dissipation (QCM-D), which measures the frequency (f) and dissipation (D) changes directly associated with mass and conformation changes of the SLB. Different overtones for f and D allow for theoretical interpretation of changes correlated to different layers of the membrane. The 2 and 5 nm particles were found to interact strongly with the lipid bilayer by adsorbing to and/or partially/completely penetrating into the lipid bilayer presumably due to a hydrophobic coating caused by PMA adsorption to the NP surface. The penetration caused a much more rigid membrane due to higher lipid packing caused by nanoparticle addition. The 10 and 40 nm particles interaction with the bilayer were not affected by the presence of PMA. Both AuNP sizes removed mass from the membrane with losses similar in de-ionized water and PMA solution. Removal of membrane mass (lipids/hydration) caused a more flexible membrane. It was determine that sized is the limiting factor for nanoparticle solubilization into the membrane. It can be concluded from the results that size coupled with natural organic matter affects the cytotoxicity of the nanoparticles to the membrane. A study was done with 12 nm functionalized AuNPs in the presence of humic acid, a well-known and more complex and realistic model for natural organic matter. A PC lipid bilayer was used to simulate a model cell membrane and QCM-D techniques were utilized in the determination of toxicity and mechanistic interaction of nanoparticles with a lipid bilayer. Functionalized AuNPs were shown to decrease the rigidity of the lipid bilayer by increasing the dissipation and decreasing the mass associated with the adsorbed film (SLB). The presence of humic acid stabilized the nanoparticles and provided increased electrostatic repulsion which resulted in decreased mass losses from the membrane and much smaller decreases in membrane rigidity. It was concluded that presence of humic acid reduces the effects of functionalized nanoparticle interaction with a lipid bilayer. These results may mean that natural organic matter has the ability to reduce the cytotoxic effects of nanoparticles released into the environment. Overall, the QCM-D was found to provide valuable information regarding the possible toxic properties and mechanisms in which different gold nanoparticle interact with a supported lipid bilayer under environmental conditions. The information provided by the studies performed has shed much light on the interaction of gold nanoparticles with a supported lipid bilayer in the presence of model natural organic matter. The experiments done in this study are the first steps towards developing an assay with the ability to determine the toxic physical properties and mechanisms by which nanoparticles interact with lipid bilayers will greatly aid in development of non-toxic nano-materials. The technology and techniques used in this study will greatly improve the field by solidifying one technique to use in the quantitative approach studying nanoparticle/cell interactions. The use of AFM techniques in conjunction with the QCM-D would be highly beneficial by facilitating better understanding of the exact mechanisms by which nanoparticles induce cytotoxicity.

For more than a decade nanomaterials have attained huge attraction owing to the exceptionally different and excellent characteristics as compared to their bulk form. In the present research, we focus on understanding the properties and performance of nanocomposites in solid and liquid states. There are three major areas involved in this thesis research. Firstly, we will identify effective methods or techniques to evaluate nanomaterials. Conventional and non-conventional techniques will be implied. The second part is to study the interfacial reactions between nanoparticles (NPs) and fluid molecules. This is to obtain basic understanding of nanoparticles and their interactions with matrix materials. Thirdly, we will investigate the mechanical properties of nanocomposites. Experimental results showed that the mechanical properties of nanocomposites measured at macroscale exhibited differences when the shape and size of gold NPs were changed. The morphological characteristics of the material were shown effectively at the nanoscale based on the NPs' shape and size. The properties of NPs influenced the properties of gold colloid. Such changes were the result of the interfacial interaction of gold NPs and the host material.

The analytical utility of gold nanoparticles (AuNPs) for laser desorption/ionization mass spectrometry (LDI-MS) is examined here. An evaluation of the parameters that affect desorption/ionization show that careful treatments of AuNPs is needed, as subtle changes in the solution environment can result in subsequent changes in the mass spectra. A thorough evaluation of the parameters that affect desorption/ionization of peptides is presented here, and these parameters include: (i) AuNP-to-analyte ratio, (ii) AuNP size, (iii) solvent, (iv) AuNP surface composition, (v) pH and buffer effects, (vi) amino acid sequence, and (vii) additives such as fructose or glycerol. Specifically, controlling the AuNP-to-analyte ratio, pH, peptide composition, and AuNP size are important parameters for ionization. Additionally, effects of passivating the AuNP surface with halides or oxyanions was investigated. The presence of NaF, NaCl, NaBr, and NH4X (X = F, Cl, Br, I) were shown to not significantly affect analyte ion abundances, whereas addition of NaI strongly suppressed analyte ion yields. Further physical characterization of the NPs showed that etching had occurred, which suggests that the surface chemistry of the NPs is important for desorption/ionization. Throughout these investigations, questions remain as to what the internal energies of peptides are after the desorption/ionization event, and how energy is deposited. Peptide ion fragmentation is examined under different solution conditions to evaluate the relative internal energies of peptides, and the fragmentation pattern examined for insight into fragmentation mechanisms. The data suggest that radical species are important for fragmentation of peptides when using AuNPs. However, it is likely that multiple processes are actually directing the fragmentation. Finally, based on the data presented in this dissertation, a thermal desorption mechanism of pre-formed ions is proposed. This fundamental research is intended to lay foundations for optimizing the use of nanoparticles in routine LDI-MS analysis as well as giving insight into nanoparticle ionization mechanisms. Since very little work has been done in this area, this dissertation investigates, in detail, many of the subtle characteristics that affect desorption/ionization of biomolecules when using NPs.

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Studies of liquid crystal (LC) /Au nanoparticle (NP) composites have been pursued in columnar and in nematic phases of thermotropic LCs. Using LCs forming a columnar phase, we found that different functionalities on the corona of the Au NPs (hydrophobic vs. hydrophilic) display unique effects on the stability and ordering of the columnar LC phase. Doping nematic LCs with non-chiral or chiral Au NPs causes the formation of textures commonly observed for chiral nematic LCs, i.e., the formation of somewhat uniform stripe textures or patterns separated by areas of homeotropic alignment of LC molecules. Two scenarios are proposed. In the first scenario, the Au NPs form topological chain-like defects and the remaining Au NPs reside at the interface inducing vertical alignment of the LC molecules. In the second scenario, chiral Au NPs transfer chirality to the nematic LC host. Further, induced circular dichroism studies proved the second scenario. Using the same chiral Au NP systems, the origin of chirality of Au NPs has also been studied, and a powerful methodology has been proposed to unravel the puzzle of chirality of chiral ligand-protected Au NPs. Further investigations of these texture phenomena led to the discovery of using metal NPs to control the orientation and alignment of LCs. In due course, a dual alignment and electro-optical switching behaviour was found using alkylthiol-capped Au NPs doped into a nematic LC with positive dielectric anisotropy in planar namatic LC cells. This study was also expanded to Ag and CdTe NPs, which showed the same phenomenon, and all investigated NPs significantly reduced the voltage needed to re-orient the LCs in an electric field (threshold voltage). Starting from basic and moving on to more application-oriented research, we finally also initiated structure-property relationship studies of LC/NP composites.

Studies of liquid crystal (LC) /Au nanoparticle (NP) composites have been pursued in columnar and in nematic phases of thermotropic LCs. Using LCs forming a columnar phase, we found that different functionalities on the corona of the Au NPs (hydrophobic vs. hydrophilic) display unique effects on the stability and ordering of the columnar LC phase. Doping nematic LCs with non-chiral or chiral Au NPs causes the formation of textures commonly observed for chiral nematic LCs, i.e., the formation of somewhat uniform stripe textures or patterns separated by areas of homeotropic alignment of LC molecules. Two scenarios are proposed. In the first scenario, the Au NPs form topological chain-like defects and the remaining Au NPs reside at the interface inducing vertical alignment of the LC molecules. In the second scenario, chiral Au NPs transfer chirality to the nematic LC host. Further, induced circular dichroism studies proved the second scenario. Using the same chiral Au NP systems, the origin of chirality of Au NPs has also been studied, and a powerful methodology has been proposed to unravel the puzzle of chirality of chiral ligand-protected Au NPs. Further investigations of these texture phenomena led to the discovery of using metal NPs to control the orientation and alignment of LCs. In due course, a dual alignment and electro-optical switching behaviour was found using alkylthiol-capped Au NPs doped into a nematic LC with positive dielectric anisotropy in planar namatic LC cells. This study was also expanded to Ag and CdTe NPs, which showed the same phenomenon, and all investigated NPs significantly reduced the voltage needed to re-orient the LCs in an electric field (threshold voltage). Starting from basic and moving on to more application-oriented research, we finally also initiated structure-property relationship studies of LC/NP composites.

Thesis (Ph. D.)--University of Massachusetts Amherst, 2009. / Includes bibliographical references (p. 55-57). Print copy also available.

The mechanism of organothiol (OT) binding to gold has remained controversial for decades. There are three mechanisms proposed for OT binding to gold surfaces. The first is the radical pathway in which the sulfur-bound hydrogen atoms (RS-H) are released as hydrogen atoms which eventually converted into hydrogen gas. Second is the deprotonation pathway in which the sulfur-bound hydrogen atoms leave as protons. Third is direct adsorption in which the RS-H bonds remain intact on the gold surface. This study demonstrates a combined pH and surface enhanced Raman spectroscopic study of organothiol binding to citrate- and borohydride-reduced gold nanoparticles (AuNPs) in polar (water), moderately polar (dichloromethane), and nonpolar (toluene,hexane) solvents. Thiol deprotonation provides a unified pathway for OT binding to AuNPs regardless of solvent polarity of the ligand binding solutions. This work should contribute to resolve the long-standing debate on the fate of the sulfur-bound hydrogen of organothiols self-assembled on gold.