Matching Items (9)

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Protein-mediated Synthesis of Gold Nanoparticles

Description

Gold nanoparticles are valuable for their distinct properties and nanotechnology applications. Because their properties are controlled in part by nanoparticle size, manipulation of synthesis method is vital, since the chosen

Gold nanoparticles are valuable for their distinct properties and nanotechnology applications. Because their properties are controlled in part by nanoparticle size, manipulation of synthesis method is vital, since the chosen synthesis method has a significant effect on nanoparticle size. By aiding mediating synthesis with proteins, unique nanoparticle structures can form, which open new possibilities for potential applications. Furthermore, protein-mediated synthesis favors conditions that are more environmentally and biologically friendly than traditional synthesis methods. Thus far, gold particles have been synthesized through mediation with jack bean urease (JBU) and para mercaptobenzoic acid (p-MBA). Nanoparticles synthesized with JBU were 80-90nm diameter in size, while those mediated by p-MBA were revealed by TEM to have a size between 1-3 nm, which was consistent with the expectation based on the black-red color of solution. Future trials will feature replacement of p-MBA by amino acids of similar structure, followed by peptides containing similarly structured amino acids.

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Date Created
  • 2018-05

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Generation of macromolecule-templated gold nanoparticles by ionizing radiation

Description

Ionizing radiation, such as gamma rays and X-rays, are becoming more widely used. These high-energy forms of electromagnetic radiation are present in nuclear energy, astrophysics, and the medical field. As

Ionizing radiation, such as gamma rays and X-rays, are becoming more widely used. These high-energy forms of electromagnetic radiation are present in nuclear energy, astrophysics, and the medical field. As more and more people have the opportunity to be exposed to ionizing radiation, the necessity for coming up with simple and quick methods of radiation detection is increasing. In this work, two systems were explored for their ability to simply detect ionizing radiation. Gold nanoparticles were formed via radiolysis of water in the presence of Elastin-like polypeptides (ELPs) and also in the presence of cationic polymers. Gold nanoparticle formation is an indicator of the presence of radiation. The system with ELP was split into two subsystems: those samples including isopropyl alcohol (IPA) and acetone, and those without IPA and acetone. The samples were exposed to certain radiation doses and gold nanoparticles were formed. Gold nanoparticle formation was deemed to have occurred when the sample changed color from light yellow to a red or purple color. Nanoparticle formation was also checked by absorbance measurements. In the cationic polymer system, gold nanoparticles were also formed after exposing the experimental system to certain radiation doses. Unique to the polymer system was the ability of some of the cationic polymers to form gold nanoparticles without the samples being irradiated. Future work to be done on this project is further characterization of the gold nanoparticles formed by both systems.

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Created

Date Created
  • 2012

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Shear-zone hosted gold and silver deposits in the Sierra Cacachilas, Baja California Sur, Mexico

Description

The historic Cacachilas mining district is located in Baja California Sur, approximately 20 kilometers east of La Paz, and has a series of gold- and silver-hosted veins, faults, and shear

The historic Cacachilas mining district is located in Baja California Sur, approximately 20 kilometers east of La Paz, and has a series of gold- and silver-hosted veins, faults, and shear zones within Cretaceous granodioritic plutons. The remote geographic location and past political events within Mexico left the district essentially unexplored after the late 1800s, when the Mexican Revolution began. More recent discovery of gold deposits along the Baja peninsula instigated a renewed interest in mineralization in the Sierra Cacachilas. The area lacks detailed previous geologic data, so this study focused on characterizing the controls of mineralization and the locations of mineralized trends of deposits within the northeastern Sierra Cacachilas, with a goal toward helping assess economic viability of the deposits. I mapped surficial geologic data, such as outcrop locations, alteration assemblages, limonite intensities, and structural measurements. I then synthesized these into geologic maps and cross sections. I combined field data with geochemical assays and structural plots to better characterize individual historic district trends and newly located trends to understand the distribution of mineralization at surface and at depth. Lastly, I synthesized geology of the Sierra Cacachilas with other gold and silver deposits located in the southern Baja peninsula to better characterize the mineralization and deposit style of the Cacachilas district.

Mineralization in the northeastern Sierra Cacachilas is mainly restricted to steeply dipping quartz veins, faults, and brittle-ductile shear zones that trend generally northeast. Some veins are en-echelon within the mineralized zones, implying some lateral movement along the zones. Veins are dominated by milky to clear quartz with trace sulfides, abundant limonite (after sulfides), and local open-space textures. Mineralization is interpreted to be intermediate between classic epithermal and mesothermal veins. Within mineralized trends and commonly associated with mineralization are greisen-like zones that are defined by intense sericitic to muscovitic overprint, trend northeast, and are with or without sulfides. The intensity of sulfide abundance and limonitic alteration after sulfides within and near mineralized zones is overall a good guide to mineralization. Based on past reports and on my recent studies, the Cacachilas district has very promising potential for relatively small, high-grade deposits.

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Created

Date Created
  • 2015

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A comparative study of gold bonding via electronic spectroscopy

Description

The bonding and electrostatic properties of gold containing molecules are highly influenced by relativistic effects. To understand this facet on bonding, a series of simple diatomic AuX (X=F, Cl, O

The bonding and electrostatic properties of gold containing molecules are highly influenced by relativistic effects. To understand this facet on bonding, a series of simple diatomic AuX (X=F, Cl, O and S) molecules, where upon bond formation the Au atom donates or accepts electrons, was investigated and discussed in this thesis.

First, the optical field-free, Stark, and Zeeman spectroscopic studies have been performed on AuF and AuCl. The simple polar bonds between Au and typical halogens (i.e. F and Cl) can be well characterized by the electronic structure studies and the permanent electric dipole moments, el. The spectroscopic parameters have been precisely determined for the [17.7]1, [17.8]0+ and X1+ states of AuF, and the [17.07]1, [17.20]0+ and X1+ states of AuCl. The el have been determined for ground and excited states of AuF and AuCl. The results from the hyperfine analysis and Stark measurement support the assignments that the [17.7]1 and [17.8]0+ states of AuF are the components of a 3 state. Similarly, the analysis demonstrated the [19.07]1 and [19.20]0+ states are the components of the 3 state of AuCl.

Second, my study focused on AuO and AuS because the bonding between gold and sulfur/oxygen is a key component to numerous established and emerging technologies that have applications as far ranging as medical imaging, catalysis, electronics, and material science. The high-resolution spectra were record and analyzed to obtain the geometric and electronic structural data for the ground and excited states. The electric dipole moment, el, and the magnetic dipole moment, m, has been the precisely measured by applying external static electric and magnetic fields. el andm are used to give insight into the unusual complex bonding in these molecules.

In addition to direct studies on the gold-containing molecules, other studies of related molecules are included here as well. These works contain the pure rotation measurement of PtC, the hyperfine and Stark spectroscopic studies of PtF, and the Stark and Zeeman spectroscopic studies of MgH and MgD.

Finally, a perspective discussion and conclusion will summarize the results of AuF, AuCl, AuO, and AuS from this work (bond lengths, dipole moment, etc.). The highly quantitative information derived from this work is the foundation of a chemical description of matter and essential for kinetic energy manipulation via Stark and Zeeman interactions. This data set also establishes a synergism with computation chemists who are developing new methodologies for treating relativistic effects and electron correlation.

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Created

Date Created
  • 2017

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Electromigration in gold interconnects

Description

Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization

Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.

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Created

Date Created
  • 2013

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Organic carbon in hydrothermal systems: from phototrophy to aldehyde transformations

Description

Hydrothermal environments are important locales for carbon cycling on Earth and elsewhere in the Universe. Below its maximum temperature (~73 °C), microbial photosynthesis drives primary productivity in terrestrial hydrothermal ecosystems,

Hydrothermal environments are important locales for carbon cycling on Earth and elsewhere in the Universe. Below its maximum temperature (~73 °C), microbial photosynthesis drives primary productivity in terrestrial hydrothermal ecosystems, which is thought to be performed by bacterial phototrophs in alkaline systems and eukaryotic algae in acidic systems, yet has received little attention at pH values intermediate to these extremes. Sequencing of 16S and 18S rRNA genes was performed at 12 hot springs with pH values 2.9-5.6 and revealed that cyanobacteria affiliated with the genus Chlorogloeopsis and algae of the order Cyanidiales coexisted at 10 of the sites. Cyanobacteria were present at pH values as low as 2.9, which challenges the paradigm of cyanobacteria being excluded below pH 4. Presence of the carotenoid β-cryptoxanthin in only 2 sites and quantitative PCR data suggest that algae were inactive at many of the sites when sampled. Spatial, but perhaps not temporal, overlap in the habitat ranges of bacterial and eukaryal microbial phototrophs indicates that the notion of a sharp transition between these lineages with respect to pH is untenable.

In sedimentary basins, biosphere-derived organic carbon is subjected to abiotic transformations under hydrothermal conditions. Benzaldehyde was experimentally evaluated as a model to assess the chemistry of aldehydes under these conditions. It was first demonstrated that gold, a traditional vessel material for hydrothermal experiments, caused catalysis of benzaldehyde degradation. Experiments in silica tubes were performed at 250, 300, and 350 °C yielding time-dependent data at several starting concentrations, which confirmed second-order kinetics. Therefore, disproportionation was expected as a major reaction pathway, but unequal yields of benzoic acid and benzyl alcohol were inconsistent with that mechanism. Consideration of other products led to development of a putative reaction scheme and the time dependencies of these products were subjected to kinetic modeling. The model was able to reproduce the observed yields of benzoic acid and benzyl alcohol, indicating that secondary reactions were responsible for the observed ratios of these products. Aldehyde disproportionation could be an unappreciated step in the formation of carboxylic acids, which along with hydrocarbons are the most common organic compounds present in natural systems.

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Date Created
  • 2016

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Synthesis of Acetylenic Carbon Molecules via Pulsed Laser Ablation in Ethanol

Description

New forms of carbon are being discovered at a rapid rate and prove to be on the frontier of cutting edge technology. Carbon possesses three energetically competitive forms of orbital

New forms of carbon are being discovered at a rapid rate and prove to be on the frontier of cutting edge technology. Carbon possesses three energetically competitive forms of orbital hybridization, leading to exceptional blends of properties unseen in other materials. Fascinating properties found among carbon allotropes, such as, fullerenes, carbon nanotubes, and graphene have led to new and exciting advancement, with recent applications in defense, energy storage, construction, and electronics. Various combinations of extreme strength, high electrical and thermal conductivity, flexibility, and light weight have led to new durable and flexible display screens, optoelectronics, quantum computing, and strength enhancer coating. The quest for new carbon allotropes and future application persists.

Despite the advances in carbon-based technology, researchers have been limited to sp3 and sp2 hybridizations. While sp3 and sp2 hybridizations of carbon are well established and understood, the simplest sp1 hybridized carbon allotrope, carbyne, has been impossible to synthesize and remains elusive. This dissertation presents recent results in characterizing a new sp1 carbon material produced from using pulsed laser ablation in liquid (PLAL) to ablate a gold surface that is immersed in a carbon rich liquid. The PLAL technique provides access to extremely non-thermal environmental conditions where unexplored chemical reactions occur and can be explored to access the production of new materials. A combination of experimental and theoretical results suggests gold clusters can act as stabilizing agents as they react and adsorb onto the surface of one dimensional carbon chains to form a new class of materials termed “pseudocarbynes”. Data from several characterization techniques, including Raman spectroscopy, UV/VIS spectroscopy, and transmission electron microscopy (TEM), provide evidence for the existence of pseudocarbyne. This completely new material may possess outstanding properties, a trend seen among carbon allotropes, that can further scientific advancements.

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Date Created
  • 2018

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Polymer-gold composite particles: synthesis, characterization, application, and beyond

Description

Polymer-gold composite particles are of tremendous research interests. Contributed by their unique structures, these particles demonstrate superior properties for optical, catalytic and electrical applications. Moreover, the incorporation of “smart” polymers

Polymer-gold composite particles are of tremendous research interests. Contributed by their unique structures, these particles demonstrate superior properties for optical, catalytic and electrical applications. Moreover, the incorporation of “smart” polymers into polymer-gold composite particles enables the composite particles synergistically respond to environment-stimuli like temperature, pH and light with promising applications in multiple areas.

A novel Pickering emulsion polymerization route is found for synthesis of core-shell structured polymer-gold composite particles. It is found that the surface coverage of gold nanoparticles (AuNP) on a polystyrene core is influenced by gold nanoparticle concentration and hydrophobicity. More importantly, the absorption wavelength of polystyrene-gold composite particles is tunable by adjusting AuNP interparticle distance. Further, core-shell structured polystyrene-gold composite particles demonstrate excellent catalyst recyclability.

Asymmetric polystyrene-gold composite particles are successfully synthesized via seeded emulsion polymerization, where AuNPs serve as seeds, allowing the growth of styrene monomers/oligomers on them. These particles also demonstrate excellent catalyst recyclability. Further, monomers of “smart” polymers, poly (N-isopropylacrylamide) (PNIPAm), are successfully copolymerized into asymmetric composite particles, enabling these particles’ thermo-responsiveness with significant size variation around lower critical solution temperature (LCST) of 31°C. The significant size variation gives rise to switchable scattering intensity property, demonstrating potential applications in intensity-based optical sensing.

Multipetal and dumbbell structured gold-polystyrene composite particles are also successfully synthesized via seeded emulsion polymerization. It is intriguing to observe that by controlling reaction time and AuNP size, tetrapetal-structured, tripetal-structured and dumbbell-structured gold-polystyrene are obtained. Further, “smart” PNIPAm polymers are successfully copolymerized into dumbbell-shaped particles, showing significant size variation around LCST. Self-modulated catalytic activity around LCST is achieved for these particles. It is hypothesized that above LCST, the significant shrinkage of particles limits diffusion of reaction molecules to the surface of AuNPs, giving a reduced catalytic activity.

Finally, carbon black (CB) particles are successfully employed for synthesis of core- shell PNIPAm/polystyrene-CB particles. The thermo-responsive absorption characteristics of PNIPAm/polystyrene-CB particles enable them potentially suitable to serve as “smart” nanofluids with self-controlled temperature. Compared to AuNPs, CB particles provide desirable performance here, because they show no plasmon resonance in visible wavelength range, whereas AuNPs’ absorption in the visible wavelength range is undesirable.

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Created

Date Created
  • 2015

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Timing and structural control of gold mineralization, Santa Gertrudis, Sonora, Mexico

Description

The Santa Gertrudis Mining District of Sonora, Mexico contains more than a dozen purported Carlin-like, sedimentary-hosted, disseminated-gold deposits. A series of near-surface, mostly oxidized gold deposits were open-pit mined from

The Santa Gertrudis Mining District of Sonora, Mexico contains more than a dozen purported Carlin-like, sedimentary-hosted, disseminated-gold deposits. A series of near-surface, mostly oxidized gold deposits were open-pit mined from the calcareous and clastic units of the Cretaceous Bisbee Group. Gold occurs as finely disseminated, sub-micron coatings on sulfides, associated with argillization and silicification of calcareous, carbonaceous, and siliciclastic sedimentary rocks in structural settings. Gold occurs with elevated levels of As, Hg, Sb, Pb, and Zn. Downhole drill data within distal disseminated gold zones reveal a 5:1 ratio of Ag:Au and strong correlations of Au to Pb and Zn. This study explores the timing and structural control of mineralization utilizing field mapping, geochemical studies, drilling, core logging, and structural analysis. Most field evidence indicates that mineralization is related to a single pulse of moderately differentiated, Eocene intrusives described as Mo-Cu-Au skarn with structurally controlled distal disseminated As-Ag-Au.

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Agent

Created

Date Created
  • 2011