Browsing by Subject "Gold"
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Item Assembly of colloidal nanocrystals into phospholipid structures and photothermal materials(2012-08) Rasch, Michael; Korgel, Brian Allan, 1969-There has been growing interest in developing colloidal metal and semiconductor nanocrystals as biomedical imaging contrast agents and therapeutics, since light excitation can cause the nanocrystals to fluoresce or heat up. Recent advances in synthetic chemistry produced fluorescent 2-4 nm diameter silicon and 1-2 nm diaemeter CuInSSe nanocrystals, as well as 16 nm diameter copper selenide (Cu₂₋[subscript x]Se) nanocrystals exhibiting strong absorbance of near infrared light suitable for biomedical applications. However, the syntheses yield nanocrystals that are stabilized by an adsorbed layer of hydrocarbons, making the nanocrystals hydrophobic and non-dispersible in aqueous solution. Encapsulating these nanocrystals in amphiphilic polymer micelles enables the nanocrystals to disperse in water. Subsequently, the Si nanocrystals were injected into tissue to demonstrate fluorescence imaging, the photothermal transduction efficiency of copper selenide nanocrystals was characterized in water, and the copper selenide nanocrystals were used enhance the photothermal destruction of cancer cells in vitro. The polymer-encapsulated copper selenide nanocrystals were found to have higher photothermal transduction efficiency than 140 nm diameter Au nanoshells, which have been widely investigated for photothermal therapy. Combining the optical properties of metal and semiconductor nanocrystals with the drug-carrying capability of lipid vesicles has received attention lately since it may create a nanomaterial capable of performing simultaneous drug delivery, optical contrast enhancement, and photo-induced therapy. Hydrophobic, dodecanethiol-coated Au nanocrystals were dispersed in water with phosphatidylcholine lipids and characterized using cryo transmission electron microscopy. 1.8 nm diameter Au nanocrystals completely load the bilayer of unsaturated lipid vesicles when the vesicles contain residual chloroform, and without chloroform the nanocrystals do not incorporate into the vesicle bilayer. 1.8 nm Au nanocrystals dispersed in water with saturated lipids to form lipid-coated nanocrystal agglomerates, which sometimes adhered to vesicles, and the shape of the agglomerates varied from linear nanocrystal chains, to flat sheets, to spherical clusters as the lipid fatty acid length was increased from 12 to 18 carbons. Including squalene formed lipid-stabilized emulsion droplets which were fully loaded with the Au nanocrystals. Results with 4.1 nm Au and 2-3 nm diameter Si nanocrystals were similar, but these nanocrystals could not completely load the bilayers of unsaturated lipids.Item Catalytic chemistry of Pd−Au bimetallic surfaces(2015-08) Yu, Wen-Yueh; Mullins, C. B.; Henkelman, Graeme; Hwang, Gyeong S.; Korgel, Brian A.; Sitz, Greg O.Catalyst development is important to the contemporary world as suitable catalysts can allow chemical processes to proceed with reduced energy consumption and waste production. In order to design catalysts with improved performance, the fundamental studies that correlate catalytic properties with surface structures are essential as they can provide mechanistic insights into the reaction mechanism. Pd−Au bimetallic catalysts have shown exceptional performance for a number of chemical reactions, however, the interplay between the reactive species and surface properties are still unclear at the molecular level. In this dissertation, the catalytic chemistry of Pd−Au surfaces was investigated via model catalyst studies under ultrahigh vacuum conditions. A range of Pd−Au model surfaces were generated by annealing Pd/Au(111) surfaces and characterized/tested by surface science techniques. The findings in this dissertation may prove useful to enhance the fundamental understanding of structure-reactivity relation of Pd−Au catalysts in associated reactions.Item Controlled assembly of biodegradable gold nanoclusters for in vivo imaging(2015-12) Stover, Robert John; Johnston, Keith P., 1955-; Truskett, Thomas M; Fan, Donglei; Korgel, Brian; Sokolov, KonstantinGold nanoparticles are of interest in biomedical imaging applications due to their inert nature and ability to exhibit surface plasmon resonance. These phenomena can result in high near-infrared extinction (NIR) due to asymmetry or close interparticle spacings within gold structures, making these materials ideal for photoacoustic imaging. Using this imaging modality, these materials allow for high contrast compared to the body’s tissues which exhibit a transparent “window” between 700-1100 nm, making them perfect for early cancer detection. However many gold structures designed for this application fail to achieve high NIR-absorbance at the <5 nm sizes which are required for efficient kidney clearance. Therefore, we designed a system which assembles ~4 nm primary gold particles into closely-spaced clusters of controlled size using a biodegradable, weakly adsorbing polymer and balance of colloidal attractive and repulsive forces. Thus, when the polymer degrades in acidic environments – such as within cells – the residual charge on the primary particles leads to dissociation of the clusters back to renal-clearable constituents. Since proteins in the blood and cells can increase the diameter of the primary particles above the 5 nm threshold, nanoparticle surfaces were designed to have a mixture of charged and zwitterionic molecules to limit protein interactions through buried charges and increased particle hydration. Strongly-bound, zwitterionic thiol-containing ligands were also investigated to resist the intracellular exchange of biomolecules which could compromise the clearable nature of the particles. These decorated nanoparticles were then assembled into clusters through one of two methods which varied either gold and polymer concentrations through evaporation, or particle charge via electrolyte addition prior to quenching by dilution in DI water. Once assembled, clusters assembled with polymer showed dissociation behavior after incubation in pH 5 acidic solutions to mimic the cellular pH environment. In other cases, sintering of the gold nanoparticle clusters prevented such dissociation. This thesis demonstrates the ability to not only create biocompatible nanoparticle surfaces, but to establish control size control over nanocluster assemblies which are capable of being used as NIR contrast agents.Item Gold-catalyzed alcohol oxidation reactions : insights from surface science and classical catalysis studies(2016-12) Mullen, Gregory Michael; Mullins, C. B.; Henkelman, Graeme; Humphrey, Simon; Hwang, Gyeong; Korgel, BrianCatalysts play an extremely important role in shaping the world around us. Foods, plastics, fuels, medicines, and countless other materials that are integral to our way of life rely on catalysts for their production. Despite their importance, to this day catalysts are still mysterious materials with active sites and reaction mechanisms that often remain unknown despite decades of investigation. In this dissertation, we investigate the use of gold catalysts for selective oxidation of alcohols, an important class of reaction used in the agrochemical, pharmaceutical, and fine chemicals industries. Using surface science and classical catalysis techniques, we demonstrate that water plays important and previously undiscovered roles in these processes, altering reaction mechanisms and influencing the selectivity exhibited by the catalysts for primary and secondary oxidation pathways. Additionally, we show that the structure and the composition of the support material both influence the activity and selectivity of gold catalysts for alcohol oxidation. Our results highlight the complexity that catalytic reaction mechanisms can exhibit and the structure-function relationships that can dictate their behavior. Knowledge of these factors is extremely valuable optimizing the design and implementation of catalytic processes. By leveraging knowledge like this, we will be able to mitigate the generation of industrial waste make better use of our natural resources.Item Gold-surface-mediated hydrogenation chemistry(2013-05) Pan, Ming, active 2013; Mullins, C. B.High surface area catalysts have been studied and applied in a wide range of chemical reactions and processes. The related microscopic details of surface chemistry are important and can be effectively explored employing surface science techniques. My dissertation focuses on investigations of catalytic properties of gold, primarily using vacuum molecular beam techniques, temperature programmed desorption (TPD) measurements, reflection-absorption infrared spectroscopy (RAIRS), and density functional theory (DFT) calculations. I conducted fundamental studies of hydrogenation reactions on a H atoms pre-covered Au(111) single crystal surface with co-adsorption of various chemical compounds, including acetaldehyde (CH₃CHO), acetone (CH₃COCH₃), propionaldehyde (CH₃CH₂CHO), water (H₂O), and nitrogen dioxide (NO₂). These studies allow better understanding of hydrogenative conversions facilitated by gold catalysts, which show great promise in hydrogenation applications but for which relevant fundamental studies are lacking. The experimental results unravel the unique and remarkable catalytic activity of gold in hydrogenation reactions: i) H atoms weakly absorb on the Au(111) surface and have a low desorption activation energy of ~ 28 kJ/mol; ii) acetaldehyde can be hydrogenated to ethanol at a low temperature of < 200 K; iii) propionaldehyde can be hydrogenated to 1-proponal (CH₃CH₂CH₂OH) on H pre-covered Au(111) whereas 2-propanol (CH₃CH(OH)CH₃) cannot be formed in the reaction of acetone with hydrogen atoms; iv) a coupling reaction of aldehyde-aldehyde or aldehyde-alcohol is observed on the H pre-covered Au(111) surface at temperatures lower than 200 K and this reaction can produce various ethers (symmetrical or unsymmetrical) from aldehydes and alcohols with the corresponding chain length; v) co-adsorbed H atoms have a strong interaction with water on the gold model surface and induce the dissociation of the O-H bond in water, which cannot be dissociated on the clean surface; vi) we observed a facile reaction of NO₂ reduction on H covered Au(111) and NO is produced at 77 K, yielding high NO₂ (100 %) conversion and selectivity towards NO (100 %) upon heating the surface to ~ 120 K. These studies indicate the exceptional catalytic activity of gold and enhance the understanding of surface chemistry of classical supported Au-based catalysts at the molecular scale.Item Growth, structure, and chemistry of 1B metal nanoclusters supported on TiO₂(110)(2006) Pillay, Devina; Hwang, Gyeong S.Cu, Ag, and Au nanoclusters dispersed on TiO2(110) surfaces are utilized in a wide variety of applications ranging from microelectronics to heterogeneous catalysis. The unique chemical reactivity of these clusters is largely dependent on their size, shape, spatial distribution, and interfacial interaction with the oxide support. This implies that atomic level control of these properties can offer great opportunities in the development of novel devices based on supported metal nanoclusters. It is therefore necessary to understand how formation and restructuring of these clusters alter their geometric and electronic characteristics. This thesis involves the development of a theoretical foundation for studying the growth, structure, and chemistry of Cu, Ag, and Au on TiO2(110) surfaces. Using density functional theory calculations, we have identified factors that control the chemical reactivity of these supported metal nanoclusters. First we investigated the electronic and geometric structures of the stoichiometric and reduced rutile TiO2(110) surfaces. Then we examined the surface chemistry of TiO2 towards gaseous CO and O2, as well as the structure and growth of 1B metal nanoclusters on TiO2(110). We also examined how the electronic and geometric properties of mixed metal nanoclusters, CuAun(n≤ 3), differ versus their single metal counterparts, Cum and Aum (m ≤ 4). Finally, we considered CO oxidation reactions on TiO2(110)-supported small Au clusters. While current experimental techniques are limited to providing complementary atomic-level real space information, first principles-based atomic level simulations greatly contribute to elucidating the fundamental behavior and properties of Cu, Ag, and Au nanoclusters on TiO2(110). First principles modeling has paved the way for new catalyst development by investigating how the geometric, electronic, and chemical properties of TiO2-supported 1B metal nanoclusters vary with surface defects, adsorbates, and metal dopants before valuable time and manpower is invested in experimental synthesis and characterization.Item Localized surface plasmon resonance spectroscopy of gold and silver nanoparticles and plasmon enhanced fluorescence(2011-12) Vokac, Elizabeth Anne; Willets, Katherine A.; Brodbelt, Jennifer S.This thesis presents spectroscopic studies of metallic nanoparticle localized surface plasmons and plasmon enhanced fluorescence. We investigated the dielectric sensitivity of silver nanoprisms to an external electric field and gold nanorods to the formation of a self-assembled surface monolayer. Dark field microscopy was used to image plasmonic scattering from single nanoparticles, and a liquid crystal tunable filter was used to construct corresponding spectra. The plasmon resonances of silver nanoprisms displayed both reversible red shifts and irreversible blue shifts along with drastic intensity changes upon exposure to an applied bias. The plasmon resonances of gold nanorods showed sensitivity to the presence of alkanethiol molecules adhered to the particle surface by a moderate red shift. An increase in the effective external dielectric caused a shift toward longer wavelengths. We imaged plasmon enhanced fluorescence in order to optimize experimental parameters for a developing project that can characterize nanoparticle structure on sub-wavelength dimensions. Preliminary controls were performed to account for the effect of O₂ plasma treatment, solvent and alkanethiol monolayer formation on surface plasmon resonances. We found that O₂ plasma treatment for different time intervals did not result in a plasmon shift compared to untreated nanoparticles exposed to N₂; however when exposed to solvent the surface plasmons of the treated particles shifted five times as far toward the red. Interestingly, the solvent effect only resulted in a plasmon shift when the particles were N₂ dried after solvent incubation. Gold nanorods incubated in ethanol showed no wavelength maximum shift in pure solvent over time, but shifted moderately to the red after incubation in a solution of alkanethiol molecules. Conditions for the plasmon enhanced fluorescence study were optimized using a dye conjugate of the same alkanethiol molecule used previously by formation from solution in a monolayer on the gold nanorod surface. The appropriate synthesis for dye functionalization, molecular concentrations, solvents and optical settings were determined.Item Loss compensation in a plasmonic nanoparticle array(2013-05) Miller, Shannon Marie; Alú, AndreaThe problem of heavy material and radiative losses in plasmonic devices has held back their implementation for compact and high-speed data storage and interconnects. One of the most interesting solutions to this problem currently under exploration is the addition of a gain material in close proximity to the metallic nanostructures for loss compensation. Here the physics of light transport in a nanoparticle array, and the operation of gain media in contact with the structure, are described and analytically modeled. A two-dimensional array of closely spaced gold nanoparticles has been fabricated by focused ion beam milling, and its electromagnetic response in the presence or absence of a dye coating has been simulated in preparation for pump-probe optical testing. The compensation of losses via a fluorophore coating has been proven for the first time in this geometry, for a physically realized sample.Item Magneto-plasmonic nanoparticle platform for detection of rare cells and cell therapy(2014-08) Wu, Chun-Hsien, active 21st century; Sokolov, Konstantin V. (Associate professor); Dunn, Andrew; Emelianov, Stanislav; Yeh, Hsin-Chih; Zal, TomaszMagnetic and plasmonic properties combined in a single nanostructure provide a synergy that is advantageous in a number of biomedical applications, such as contrast enhancement in multimodal imaging, simultaneous capture and detection of circulating tumor cells, and photothermal therapy of cancer. These applications have stimulated significant interest in development of magneto-plasmonic nanoparticles with optical absorbance in the near-infrared region and a strong magnetic moment. In this dissertation, we addressed this need to create a novel immunotargeted magneto-plasmonic nanoparticle platform. The nanostructures were synthetized by self-assembly of primary 6 nm iron oxide core-gold shell particles, resulting in densely packed spherical nanoclusters. The close proximity of the primary particles in the nanoclusters generates a greatly improved response to an external magnetic field and strong near-infrared plasmon resonances. A procedure for antibody conjugation and PEGylation to the hybrid nanoparticles was developed for biomedical applications which require molecular and biocompatible targeting. Furthermore, we presented two biomedical applications based on the immunotargeted hybrid nanoparticle platform, including circulating tumor cell (CTC) detection and cell-based immunotherapy of cancer. In the CTC detection assays, rare cancer cells were specifically targeted by antibody-conjugated nanoparticles and efficiently separated from normal blood cells by a magnetic force in a microfluidic chamber. The experiments in whole blood showed capture efficiency greater than 90% for a variety of cancers. We also explored photoacoustic imaging to detect nanoparticle-labeled CTCs in whole blood. The results showed excellent sensitivity to delineate the distribution of hybrid nanoparticles on the cancer cells. Thus, these works paves the way for a novel CTC detection approach which utilizes immunotargeted magneto-plasmonic nanoclusters for a simultaneous magnetic capture and photoacoustic detection of CTCs. In another application, we introduced a novel approach to label cytotoxic T cells using the magnetic nanoparticles with an expectation to enhance T cell recruitment in tumor under external magnetic stimulus. A series of in vitro experiments demonstrated highly controllable manipulation of labeled T cells. Thus, these results highlight the promise of using our nanoparticle platform as a multifunctional probe to manipulate and track immune cells in vivo and further improve the efficacy of cell-based cancer immunotherapy.Item Model catalyst studies of the CO oxidation reaction on Titania supported gold nanoclusters(2004) Stiehl, James Daniel; Mullins, C. B.The chemical nature of gold has been determined to be much richer than previously thought. Recent discoveries that properly prepared gold catalysts (i.e. gold particle diameters in 2 – 5 nm size range) can catalyze the CO oxidation reaction at low temperature have spurned a renewed interest in the chemistry of gold. Despite the extensive research that has been performed regarding CO oxidation on Au based catalysts, many issues still remain unresolved. The origin of the particle size dependence of the reaction is not well understood. Also, details concerning the reaction mechanism, specifically identification of the active oxygen species, remain unresolved. In the following studies, ultra high vacuum, molecular beam, surface science techniques are used to study the CO oxidation reaction on titania supported gold nanoclusters (Au/TiO2). Using a radio frequency generated plasma-jet, it is possible to simultaneously populate the Au/TiO2 samples with atomically adsorbed and molecularly chemisorbed oxygen species, allowing for the opportunity to investigate the reactivity of each respective species. The reaction of CO with atomically adsorbed oxygen has been studied over a range of temperatures from 65 – 250 K as a function of gold coverage and oxygen coverage. The reaction is observed to be a strong function of both of the sample temperature and the oxygen coverage. The reaction is also relatively independent of the gold coverage on the sample, in contrast to findings for the reaction employing gas-phase reactants under moderate pressures. The formation and reactivity of molecularly chemisorbed oxygen on the samples following exposure to the plasma-jet was also investigated. Evidence is presented showing that some molecularly chemisorbed oxygen is formed as a result of recombination of impinging atoms on the model catalyst surface. Evidence is also presented showing that adsorption of an oxygen atom on the sample influences the chemisorption of molecular species from the gas phase. Finally, evidence is presented showing that the molecularly chemisorbed oxygen species can participate in the CO oxidation reaction at 77 K. This finding reveals a reaction channel for CO oxidation on Au/TiO2 model catalysts that does not require the dissociation of oxygen.Item Molecular beam studies of low temperature CO oxidation on gold(2005) Kim, Tae Sang; Mullins, C. B.Item New chemistry with gold-nitrogen complexes: synthesis and characterization of tetra-, tri-, and dinuclear gold(I) amidinate complexes. Oxidative-addition to the dinuclear gold(I) amidinate(2009-06-02) Abdou, Hanan ElsayedNitrogen ligands have been little studied with gold(I) and almost no chemistry has been described using anionic bridging nitrogen ligands. This dissertation concerns the impact of the bridging ligands amidinate, ArNHC(H)NAr, on the chemistry of gold(I) and, in particular, the effect of substituents on the molecular arrangement. The electronic vs. steric effect of the substituents on the molecular arrangement of gold(I) amidinates complexes is studied in detail. Tetra-, tri-, and dinuclear gold(I) amidinate complexes are synthesized and characterized using X-ray diffraction. Spectroscopic and electrochemical studies of the amidinate complexes are described. Catalytic studies suggest that gold amidinates and related gold nitrogen complexes are the best catalyst precursors for CO oxidation on TiO2 surface reported to date (87% conversion). The dinuclear gold(I) amidinate complex with a Au? ?Au distance of 2.711(3) ? is rare. To our knowledge, there is only one other example of a symmetrical dinuclear gold(I) nitrogen complex. Oxidative-addition reactions to the dinuclear gold(I) complex, [Au2(2,6-Me2-form)2] are studied in detail and result in the formation of gold(II) complexes. The gold(II) amidinate complexes are the first formed with nitrogen ligands. The complexes are stable at room temperature. Mixed ligand tetranuclear gold(I) clusters and tetranuclear mixed Au-Ag metal clusters of pyrazolate and amidinate ligands are synthesized and characterized using Xray diffraction.Item Oxidative chemistry on gold : unraveling molecular transformations at surfaces(2009-05) Gong, Jinlong, 1979-; Mullins, C. B.Gold has been considered catalytically inert due to its resistance to oxidation and corrosion. However, decades ago, it was discovered that gold nano-particles (<5nm) on metal oxides demonstrate superior chemical activity towards many reactions. These seminal findings spurred considerable interest in investigations of the mechanistic details of oxidative reactions on gold-based catalysts. However, the active site and structure of supported Au nanoclusters as well as the active oxygen species remains elusive. Achieving high selectivity toward partial oxidation products also remains a challenge. In this dissertation, an oxygen-covered Au(111) crystal under ultra vacuum conditions was used as a model system to gain insights into oxidative reactions in gold-based catalysis. I have been able to demonstrate that (i) surface-bound oxygen atoms are metastable at low temperature; (ii) the oxygen atoms participate in surface reactions as a Brønsted base or a nucleophilic base; and (iii) the acid-base reactions that have been observed on silver and copper may also occur on gold. Low temperature CO oxidation and the associated mechanistic aspects are investigated. CO reacts with hydroxyls formed from water-oxygen interactions to produce CO₂ on Au(111) populated with atomic oxygen at low temperatures. Directing an ¹⁶O beam toward C¹⁸O₂ pre-adsorbed Au(111), the formation of carbonate is significantly enhanced. This reaction is suggested to follow a hot-precursor-mediated mechanism. The identification of reaction pathways in oxidation of N-containing molecules such as ammonia and propylamine is presented. Abstraction of hydrogen from ammonia or propylamine by O atoms is the initial step in the surface decomposition of NHx (or RNHx-1) on Au(111). Atomic oxygen or hydroxyl-assisted dehydrogenation steps have lower barriers than the recombination steps under relevant conditions. 100% selectivity of N₂ or propionitrile can be obtained if the oxygen coverage is below the stoichiometric value. The surface oxidative chemistry of alcohols on Au(111) is also investigated. Except for methanol that is fully oxidized, alcohols initially undergo O-H bond cleavage (producing alcoxides) followed by selective β-C-H bond activation to form aldehydes or ketones. This finding reveals that the interaction of Au with the metal oxide support might not be essential to facilitate the reactions if active oxygen species are readily present, particularly at low temperatures.Item Reaction controlled kinetic assembly of small gold nanoclusters with high NIR extinction(2011-08) Willsey, Brian William; Johnston, Keith P., 1955-; Milner, Thomas ENanoclusters with sizes of ~50nm with high NIR extinction at wavelengths beyond 800 nm are of interest in various fields including biomedical optical imaging, microelectronics, plasmonic sensors, and catalysis. Herein we report gold nanoclusters with hydrodynamic diameters of ~50 nm composed of ~10 nm primary particles. The kinetically controlled assembly of clusters occurs simultaneously with the reaction to synthesize the primary particles. The clustering is induced by attractive van der Waals forces that dominate over the steric and electrostatic repulsive forces present. Stability is provided using a single, biocompatible polysaccharide in either carboxymethyl dextran or dextran. High NIR shifts of the surface Plasmon resonance are achieved through close interparticle spacings of primary particles, deviations in morphology from that of a sphere of primaries, and the surface roughness that results from the clustering process. The cluster size is mediated by controlling the relative nucleation and growth rates of primary particles using a moderate reducing agent in NH2OH and glucose at pH 8.7. It will be shown that cluster size is also dependent on Au concentrations in solution. Maintaining low Au concentrations will allow for smaller clusters. In particular, the small size and high NIR extinction at longer wavelengths (800-1100 nm) makes these particles of interest for optical imaging applications in biology, as particles with a hydrodynamic diameter of ~50 nm have long blood lifetimes.Item Simulation tools for predicting the atomic configuration of bimetallic catalytic surfaces(2012-12) Stephens, John Adam; Hwang, Gyeong S.Transition metal alloys are an important class of materials in heterogeneous catalysis due in no small part to the often greatly enhanced activity and selectivity they exhibit compared to their monometallic constituents. A host of experimental and theoretical studies have demonstrated that, in many cases, these synergistic effects can be attributed to atomic-scale features of the catalyst surface. Realizing the goal of designing -- rather than serendipitously discovering -- new alloy catalysts thus depends on our ability to predict their atomic configuration under technologically relevant conditions. This dissertation presents original research into the development and use of computational tools to accomplish this objective. These tools are all based on a similar strategy: For each of the alloy systems examined, cluster expansion (CE) Hamiltonians were constructed from the results of density functional theory (DFT) calculations, and then used in Metropolis Monte Carlo (MC) simulations to predict properties of interest. Following a detailed description of the DFT+CE+MC simulation scheme, results for the AuPd/Pd(111) and AuPt/Pt(111) surface alloys are presented. These two systems exhibit considerably different trends in their atomic arrangement, which are explicable in terms of their interatomic interactions. In AuPd, a preference for heteronuclear, Au-Pd interactions results in the preferential formation of Pd monomers and other small ensembles, while in AuPt, a preference for homonuclear interactions results in the opposite. AuPd/Pd(100) and AuPt/Pt(100) were similarly examined, revealing not only the effects of the same heteronuclear/homonuclear preferences in this facet, but also a propensity for the formation of second nearest-neighbor pairs of Pd monomers, in close agreement with experiment. Subsequent simulations of the AuPd/Pd(100) surface suggest the application of biaxial compressive strain as a means increasing the population of this catalytically important ensemble of atoms. A method to incorporate the effects of subsurface atomic configuration is also presented, using AuPd as an example. This method represents several improvements over others previously reported in the literature, especially in terms of its simplicity. Finally, we introduce the dimensionless scaled pair interaction, whereby the finite-temperature atomic configuration of any bimetallic surface alloy may be predicted from a small number of relatively inexpensive calculations.Item Synthesis and anticancer activity of water soluble porphyrin(2015-12) Lammer, Aaron David; Sessler, Jonathan L.; Anslyn, EricAs resistance to traditional chemotherapies increases, there is a concurrent need for novel therapies. Much work has been devoted the development of gold(III) treatments, however much of this work has been hampered by the propensity of gold(III) to reduce to gold(I) under physiological conditions. Porphyrins have previously been used to stabilize reactive metals, due to being a strongly chelating multi-dentate ligand. Although this stabilization is offset by poor solubility in aqueous or physiological conditions. Synthesis of porphyrins with multiple hydroxyl substituents has greatly increased the aqueous solubility of the ligand, and any metals chelated to it. By combining this water soluble porphyrin with gold(III) was have synthesized novel gold(III) complex. In this work we report the synthesis and anticancer activity of this gold(III) complex.Item Textured thin metal shells on metal oxide nanoparticles with strong NIR absorbance and high magnetization for imaging and therapy(2010-12) Ma, Li, doctor of chemical engineering; Feldman, Marc David; Johnston, Keith P., 1955-; Milner, Thomas E.; Sokolov, Konstantin V.; Mullins, C. B.; Hwang, Gyeong S.The ability of sub 100 nm nanoparticles to target and modulate the biology of cells will enable major advancements in cellular imaging and therapy in cancer and atherosclerosis. A key challenge is to load an extremely high degree of targeting, imaging, and therapeutic functionality into small, yet stable particles. A general mechanism is presented for thin autocatalytic growth on nanoparticle substrates (TAGS), as demonstrated for a homologous series of < 5 nm textured Au coatings on < 42 nm iron oxide cluster cores. Very low Au supersaturation levels are utilized to prevent commonly encountered excessive autocatalytic growth that otherwise produce thick shells. The degree of separation of nucleation to form the seeds from growth is utilized to control the morphology and uniformity of the thin Au coatings. The thin and asymmetric Au shells produce strong near infrared (NIR) absorbance with a cross section of ~10⁻¹⁴ m², whereas the high magnetic content per particles provides strong r2 spin-spin magnetic relaxivity of 200 mM⁻¹s⁻¹. TAGS may be generalized to a wide variety of substrates and high energy coatings to form core-shell nanoparticles of interest in a variety of applications as diverse as catalysis and bionanotechnology. High uptake of the nanoclusters by macrophages is facilitated by the dextran coating, producing intense NIR contrast both in cell culture and an in vivo rabbit model of atherosclerosis. A novel conjugation technique further allows covalent binding of anti-epidermal growth factor receptor (EGFR) monoclonal antibody (Ab) to the nanoclusters for highly selective targeting to EGFR over expressing cancer cells. AlexaFluor 488 tagged Ab nanocluster conjugates were prepared to correlate the number of conjugated Abs with the hydrodynamic diameter. The high targeting efficacy was evaluated by dark field reflectance imaging and atomic absorbance spectrometry (AAS). Colocalization of the nanoparticles by dual mode in-vitro imaging with dark field and fluorescence microscopy demonstrates the Abs remained attached to the Au surfaces. The extremely high curvature of the Au shells with features below 5 nm influence the spacing and orientations of the Abs on the surface, which has the potential to have a marked effect on biological pathways within cells. These targeted small multifunctional nanoclusters may solve some key molecular imaging challenges for cancer and atherosclerosis.Item Ultra-precise manipulation and assembly of nanoparticles using three fundamental optical forces(2012-12) Demergis, Vassili; Florin, Ernst-Ludwig; Shubeita, George T; Fink, Manfred; Makarov, Dmitrii E; Korgel, Brian AThe invention of the laser in 1960 opened the door for a myriad of studies on the interactions between light and matter. Eventually it was shown that highly focused laser beams could be used to con fine and manipulate matter in a controlled way, and these instruments were known as optical traps. However, challenges remain as there is a delicate balance between object size, precision of control, laser power, and temperature that must be satisfied. In Part I of this dissertation, I describe the development of two optical trapping instruments which substantially extend the allowed parameter ranges. Both instruments utilize a standing wave optical field to generate strong optical gradient forces while minimizing the optical scattering forces, thus dramatically improving trapping efficiency. One instrument uses a cylinder lens to extend the trapping region into a line focus, rather than a point focus, thereby confining objects to 1D motion. By translation of the cylinder lens, lateral scattering forces can be generated to transport objects along the 1D trapping volume, and these scattering forces can be controlled independently of the optical gradient forces. The second instrument uses a collimated beam to generate wide, planar trapping regions which can con fine nanoparticles to 2D motion. In Part II, I use these instruments to provide the first quantitative measurements of the optical binding interaction between nanoparticles. I show that the optical binding force can be over 20 times stronger than the optical gradient force generated in typical optical traps, and I map out the 2D optical binding energy landscape between a pair of gold nanoparticles. I show how this ultra-strong optical binding leads to the self-assembly of multiple nanoparticles into larger contactless clusters of well de ned geometry. I nally show that these clusters have a geometry dependent coupling to the external optical field.