Throughout the United States, there are a large number of groundwater systems contaminated by chlorinated organic compounds. Of these compounds, carbon tetrachloride (CT) is one of the most frequently encountered due to its past, widespread industrial use. In anaerobic groundwater environments, CT has been shown to be susceptible to degradation by both biotic and abiotic processes. One abiotic process that has been researched extensively is the reduction of CT by iron metal and associated iron oxides and hydroxides. Magnetite, an iron oxide, is a ubiquitous component of many subsurface environments and has been investigated as a potential groundwater remediation technology. One beneficial characteristic of magnetite is the capability to be synthetically produced in various sizes and shapes - including particles within the nanoscale range. Nanoscale particles have been shown to be more reactive towards contaminants than larger sized particles due to their large surface areas and high surface reactivity. This project was designed to characterize the behavior of synthetic magnetite in the presence of carbon tetrachloride under anaerobic conditions. / Master of Science

The ability of uniquely functional thermoelectric materials to convert waste heat directly into electricity is critical considering the global energy economy. Profitable, energy-efficient thermoelectrics possess thermoelectric figures of merit ZT ≥ 1. We examined the effect of metal nanoparticle – oxide film interfaces on the thermal conductivity κ and Seebeck coefficient α in bilayer and multilayer thin film oxide thermoelectrics in an effort to improve the dimensionless figure of merit ZT. Since a thermoelectric's figure of merit ZT is inversely proportional to κ and directly proportional to α, reducing κ and increasing α are key strategies to optimize ZT. We aim to reduce κ by phonon scattering due to the inclusion of metal nanoparticles in the bulk of thermoelectric thin films deposited by Pulsed Laser Deposition. XRD, AFM, XPS, and TEM analyses were carried out for structural and compositional characterization. The electrical conductivities of the samples were measured by a four-point probe apparatus. The Seebeck coefficients were measured in-plane, varying the temperature from 100K to 310K. The thermal conductivities were measured at room temperature using Time Domain Thermoreflectance. / Master of Science

This thesis is on molecular dynamics studies of drying suspensions of bidisperse nanoparticle mixtures. I first use an explicit solvent model to investigate how the structure of the dry film depends on the evaporation rate of the solvent and the initial volume fractions of the nanoparticles. My simulation results show that the particle mixtures stratify according to their sizes when the suspensions are quickly dried, consistent with the prediction of recent theories. I further show that stratification can be controlled using thermophoresis induced by a thermal gradient imposed on the drying suspension. To model larger systems on longer time scales, I explore implicit solvent models of drying particle suspensions in which the solvent is treated as a uniform viscous background and the liquid-vapor interface is replaced by a potential barrier that confines all the solutes in the solution. Drying is then modeled as a process in which the location of the confining potential is moved. In order to clarify the physical foundation of this moving interface method, I analyze the meniscus on the outside of a circular cylinder and apply the results to understand the capillary force experienced by a spherical particle at a liquid-vapor interface. My analyses show that the capillary force is approximately linear with the displacement of the particle from its equilibrium location at the interface. An analytical expression is derived for the corresponding spring constant that depends on the surface tension and lateral span of the interface and the particle radius. I further show that with a careful mapping, both explicit and implicit solvent models yield similar stratification behavior for drying suspensions of bidisperse particles. Finally, I apply the moving interface method based on an implicit solvent to study the drying of various soft matter solutions, including a solution film of a mixture of polymers and nanoparticles, a suspension droplet of bidisperse nanoparticles, a solution droplet of a polymer blend, and a solution droplet of diblock copolymers. / PHD / Drying is a ubiquitous phenomenon. In this thesis, I use molecular dynamics methods to simulate the drying of a suspension of a bidisperse mixture of nanoparticles that have two different radii. First, I use a model in which the solvent is included explicitly as point particles and the nanoparticles are modeled as spheres with finite radii. Their trajectories are generated by numerically solving the Newtonian equations of motion for all the particles in the system. My simulations show that the bidisperse nanoparticle mixtures stratify according to their sizes after drying. For example, a “small-on-top” stratified film can be produced in which the smaller nanoparticles are distributed on top of the larger particles in the drying film. I further use a similar model to demonstrate that stratification can be controlled by imposing a thermal gradient on the drying suspension. I then map an explicit solvent system to an implicit one in which the solvent is treated as a uniform viscous background and only the nanoparticles are kept. The physical foundation of this mapping is clarified. I compare simulations using the explicit and implicit solvent models and show that similar stratification behavior emerge in both models. Therefore, the implicit solvent model can be applied to study much larger systems on longer time scales. Finally, I apply the implicit solvent model to study the drying of various soft matter solutions, including a solution film of a mixture of polymers and nanoparticles, a droplet of a bidisperse nanoparticle suspension, a solution droplet of a polymer blend, and a droplet of a diblock copolymer solution.

With the development of controlled and predictable nanoparticle fabrication, assembling multiple nano-objects into larger functional nanostructure has attracted increasing attention. As the most basic structure, assembly of one-dimensional (1D) structures is a good model for investigating the assembly mechanism of a nanostructure's formation from individual particles. In this dissertation, the dynamics and the growth mechanism of anisotropic 1D nanostructures is investigated. In our first study, we demonstrate a simple method for assembling superparamagnetic nanoparticles (SPIONs) into structure-controlled 1D chains in a rotating magnetic field. The length of the SPION chains can be well described by an exponential distribution, as is also seen in SPION chains in a static field. In addition, the maximum chain length is limited by the field's rotational speed, as is seen in micro-sized beads forming chains in a rotating field. However, due to a combination of thermal fluctuations and hydrodynamic forces, the chain length in our case is shorter than either limit. In addition to chain length, the disorder of chains was also studied. Because of the friction between particles, kinetic potential traps prevent relaxation to the global free energy minimum. The traps are too deep to be overcome through thermal fluctuations, and assemblies captured by the kinetic traps therefore form disordered chains. We demonstrate that this disorder gradually heals over a timescale of tens of minutes and that the healing process can be promoted by increasing particle concentration or solution ionic strength, suggesting that the chain growth process provides the energy required to overcome the kinetic trapping. Next, we introduce a novel optical technique we term Quantitative Optical Anisotropy Imaging (QOAI). A fast and precise single-particle characterizing technique for anisotropic nanostructures, QOAI allows real-time tracking of particle orientation as well as the spectroscopic characterization of polarizabilities of nanoparticles on a microsecond timescale. The abilities of QOAI are demonstrated by the detection and the characterization of single gold nanorods. We also show that single particle diffusions and the process of particle binding to a wall can be tracked through QOAI. The rotational diffusivities of gold nanorods near the wall were determined by autocorrelation analysis, which shows that the diffusivity in the polar direction is slightly smaller than in the azimuthal direction. This result demonstrates that a detailed correlation analysis with QOAI may provide the opportunity to analyze both the translational and rotational motion of particles simultaneously, enabling true 3-dimensional orientation tracking. Finally, optical methods including QOAI are applied to the investigation of magnetic assembly, demonstrating that optical anisotropy is generated during particle binding, which can be used as a probe of the magnetic assembly process. QOAI is employed to track the dynamics of magnetic clusters in real time, attempting to capture insights on the self-assembly of the magnetic nanoparticles. By turning the external magnetic field on and off, the processes of combining superparamagnetic colloidal nanoparticle clusters into chain assemblies are monitored along with the chain growth. This fast and orientation-sensitive single-particle measurement opens the door to detailed studies of self-assembly away from equilibrium. / Doctor of Philosophy / Nanotechnology is the study and application of phenomena at the nanoscale, which is between 1 and 100 nm. Due to quantum effects, nanomaterials exhibit many interesting properties that cannot be found in bulk materials and are highly influenced by the shape of the nanostructures. One of the most promising strategies for forming complex nanostructures is to use smaller nanoparticles as building blocks. Therefore, significant efforts have been spent on the studies of the fabrication and modeling of the assembly of nanostructures. As a good starting point for analyzing the mechanism of self-assembly, we focus on the most basic structure, one-dimensional (1D) nanowires and chains. First, we demonstrate a simple method to fabricate one-dimensional magnetic chains from spherical magnetic nanoparticles in a rotating magnetic field. The growth mechanism of the nanochains is investigated, indicating the theory developed for chains formed with larger beads is not applicable at the nanoscale, and additional factors, such as the effect of temperature, need to be considered. Second, we introduce a fast, sensitive optical technique for characterizing anisotropic nanostructures. Because of their unique optical properties, gold nanorods are used to demonstrate the capabilities of the optical system. Not only static properties (orientation, aspect ratio), but also dynamics properties (rotational motion), of single gold nanorods are characterized quantitatively. Finally, this optical technique is extended to preliminary work on characterizing magnetic chain assembly. The processes of magnetic cluster binding and dissociation in a magnetic field are monitored and analyzed.

Inorganic mercury (Hg) is converted to potential neurotoxic methylmercury (MeHg) by a natural process called Hg methylation. MeHg can be biomagnified in the food chain, thus the consumption of Hg-contaminated fish contributes to harmful human health issues. Selenium (Se) inhibits the Hg bioavailability to the methylating bacteria by forming mercuric selenide (HgSe). Pseudodesulfovibrio mercurii, a type of sulfate-reducing bacteria (SRB) cultures were grown in anaerobic environments using an estuarine sulfate lactate growth medium to evaluate the effects of Hg concentrations, bacterial growth phase, and sodium selenate in the Hg methylation process. Bacterial cultures contained two types of mercuric (II) nitrate, dissolved and nanoparticles with 1 nM, 2 nM, and 3 nM concentrations in anoxic conditions. In a different experimental batch, various concentrations of sodium selenate (VI) were added to the Hg-contained medium to evaluate the effect of Se in the Hg methylation process. Dissolved Hg produced higher net MeHg than nanoparticulate Hg throughout the incubation period in the culture medium. Bacterial culture medium stressed with high-level Hg concentrations showed increased MeHg production (pM) but decreased Hg methylation rate (%) for the dissolved Hg. During the methylation process in the presence of Se, net MeHg production was reduced significantly compared to the culture medium solely exposed to Hg. The significant reduction of MeHg generation suggests an interference in the Hg methylation process due to the presence of 50-, 75-, and 100-fold higher Se than Hg. This study reassures the antagonistic effect between Hg and Se at the molecular level. Moreover, this study represents a novel approach when the antagonistic effect of nanoparticulate Hg and selenate is observed at the bacterial level. These interactions between Hg and Se are crucial for a better understanding of the Hg methylation process. This research will help to provide a solid foundation for a better understanding of MeHg generation in anaerobic aquatic conditions.

Yes / Magnetic nanoparticles and surface-enhanced Raman scattering (SERS) active nanoparticles were coated with short chain DNA tags. These were then used to identify a target bacterial DNA sequence. The tags function as primers in a standard PCR with the reverse primers and forward primers on the SERS nanoparticles and magnetic nanoparticles, respectively. During the PCR cycles, a composite nanostructure is formed that is both magnetically responsive and SERS active. After magnetic trapping, the intensity of the SERS signal can be related back to the concentration of the target DNA. A test assay was performed that showed a detection limit (based on the signal to noise ratio) of less than 3 zeptomole (41 pg/L). For comparison, a PCR assay based on the standard SYBR Green method was performed. This used the same primers and target DNA and had a detection limit of 10 attomoles (138 ng/L), 3,000 times less sensitive. The work documents the proof of principle study and shows for the first time the use of SERS-NP labels in the quantification of nucleic acid amplification tests and PCR.

Yes / Glioblastoma (GBM) has a dismal prognosis. Evidence from preclinical tumor models and human trials indicates the role of GBM initiating cells (GIC) in GBM drug resistance. Here, we propose a new treatment option with tumor enzyme-activatable, combined therapeutic and diagnostic (theranostic) nanoparticles, which caused specific toxicity against GBM tumor cells and GICs. The theranostic cross-linked iron oxide nanoparticles (CLIO) were conjugated to a highly potent vascular disrupting agent (ICT) and secured with a matrix-metalloproteinase (MMP-14) cleavable peptide. Treatment with CLIO-ICT disrupted tumor vasculature of MMP-14 expressing GBM, induced GIC apoptosis and significantly impaired tumor growth. In addition, the iron core of CLIO-ICT enabled in vivo drug tracking with MR imaging. Treatment with CLIO-ICT plus temozolomide achieved tumor remission and significantly increased survival of human GBM bearing mice by more than 2 fold compared to treatment with temozolomide alone. Thus, we present a novel therapeutic strategy with significant impact on survival and great potential for clinical translation. / Heike E Daldrup-Link, NIH, R21CA176519 and R21CA190196; Sanjiv Sam Gambhir, NIH, 1U54CA199075; Jessica Klockow, NCI training grant, T32CA118681, Robert A. Falconer, University of Bradford, UoB-66031

Surface plasmon resonance has become a widely investigated phenomenon in the past few years. Initially descriptive of light interactions with metallic films, research has branched out to encompass the nanoparticles as well. Generation of the maximum surface plasmon resonance for nanostructures is based on the resonance condition that the oscillatory behavior of the 'free' electrons on the surface of the particle become equivalent to the frequency of the excitation light; for films this required a specific geometry. Metallic nanoparticles have also interested researchers because of their unique optical properties. Depending on the metal, observations of quenching as well as fluorescence enhancement have been reported. Based on the phenomenon of surface plasmon resonance as well as the properties of metallic nanoparticles, this research reports the interaction of gold and silver nanoparticles in an aqueous dye solution. Our research is the basis for developing an optical sensor used for water treatment centers as an alarm mechanism. Due to the inefficiency of the fluorophore used in similar optodes, sufficient fluorescence was not obtained. With the addition of the nanoparticles, we hoped to observe the transfer of energy from the nanoparticle to the fluorophore to increase the overall intensity, thereby creating a sufficient signal. Using the excitation theories discovered by Raman, Mie, and Forster and Dexter as our foundation, we mixed a strongly fluorescent dye with gold nanoparticles and aagain with silver nanoparticles. After taken measurements via fluorescence spectroscopy, absorption spectroscopy, and photoluminescence excitation, we observed that the silver nanoparticles seemed to enhance the fluorescence of the dye while the gold nanoparticles quenched the fluorescence. / Master of Science

An experimental investigation was conducted to evaluate the possible use of highly-charged spherical nanoparticles to stabilize an aqueous dispersion of weakly-charged microspheres. At low pH values, the surface of silica is weakly charged, which leads to flocculation of colloidal suspensions of silica microspheres. Binary solutions of weakly charged silica microspheres and highly charged polystyrene latex nanoparticles result in adsorption of the nanoparticles onto the surface of the silica microspheres. This effectively "recharges" the silica spheres, with effective zeta potentials increased to the range that is unfavorable for flocculation of microspheres in a silica-only solution. However, this does not guarantee stability, and comparisons between positively charged amidine latex nanoparticles and negatively charged sulfate latex nanoparticles indicate that the degree of coverage plays an important role in the restabilization. The sulfate latex nanoparticles do not cover the surface sufficiently, and though they seemingly provide sufficient charge, the weakly charged patches of the exposed silica substrate can lead to flocculation. The amidine latex nanoparticles, on the other hand, cover the surface more completely, and effectively prevent flocculation of the silica microspheres. The mechanisms responsible for this different adsorption and stabilizing behavior are not entirely understood, as both the amidine and sulfate latex nanoparticles are of similar size and the magnitude of the zeta potentials of the different particle types are comparable. / Master of Science

This dissertation describes the development of the fiberoptic microneedle device (FMD), a microneedle technology platform for fluid and light delivery, from general engineering characterization to specific applications in treating bladder and brain cancers. The central concept of the FMD is physical modification of silica fiberoptics and capillary tubes into sharp microneedles capable of penetrating a tissue's surface, enabling light and fluid delivery into the interstitial spaces. Initial studies sought to characterize the mechanical penetration and optical delivery of multimode fiberoptics and capillary tubes modified through a custom, CO2 laser melt-drawing technique. Additional work with multimode fibers investigated using an elastomeric lateral support medium to ensure robust penetration of small diameter fibers. These early experiments laid an engineering foundation for understanding the FMD technology. Subsequent studies focused on developing the FMD to treat specific diseases. The first such investigation sought to leverage the high aspect ratio nature of FMDs made from long capillary tubes as a therapy delivery device deployable through the instrument channel of a urological cystoscope. The therapeutic strategy was to infuse single-walled carbon nanohorns (SWNHs), a carbon-based nanoparticle allowing surface modification and drug encapsulation, into the infiltrating front of later stage bladder tumors. The SWNHs primarily serve as exogenous chromophores, enabling a fluid-based control of photothermal heat generation created when the SWNHs interacted with laser energy from an interstitial FMD or a light-emitting fiber in the bladder's interior. The study described here primarily sought to characterize the dispersal of the infused SWNHs and the photothermal response of the particles when heated with a 1064 nm laser. The FMD was also developed as a platform capable of conducting convection-enhanced delivery (CED), a therapeutic approach to treat invasive tumors of the central nervous system such as malignant glioma (MG). Intracranial CED involves the placement of small catheters local to the tumor site and slow infusion of a chemotherapeutic over long timeframes (12-72 hours). A primary challenge of this treatment approach is infused chemotherapeutics not dispersing sufficiently to reach the infiltrating cells in the tumor's margins. The hypothetical improvement provided by the FMD technology is using sub-lethal photothermal heating to sufficiently increase the diffusive and convective transport of an infusate to reach infiltrative cells in the tumor's periphery. Initial experiments sought to demonstrate and characterize a heat-mediated increase of volumetric dispersal in Agarose tissue phantoms and ex vivo tissue. Subsequent studies with in vivo rodent models determined the best laser parameters to achieve the desired levels of diffuse, sub-lethal heat generation and then demonstrated the hypothesis of increasing the rate of volumetric dispersal though concurrent local hyperthermia. This research was the first demonstration of photothermal augmentation of an interstitially infused fluid's dispersal rate, which may have uses outside of the CED approach to brain cancer exhibited here. Taken in sum, this manuscript describes the potency and versatility of the FMD technology platform through its development in various biomedical applications. / Ph. D.