This work describes several research projects aimed towards developing new instruments and novel methods for high throughput chemical and biological analysis. Approaches are taken in two directions. The first direction takes advantage of well-established semiconductor fabrication techniques and applies them to miniaturize instruments that are workhorses in analytical laboratories. Specifically, the first part of this work focused on the development of micropumps and microvalves for controlled fluid delivery. The mechanism of these micropumps and microvalves relies on the electrochemically-induced surface tension change at a mercury/electrolyte interface. A miniaturized flow injection analysis device was integrated and flow injection analyses were demonstrated. In the second part of this work, microfluidic chips were also designed, fabricated, and tested. Separations of two fluorescent dyes were demonstrated in microfabricated channels, based on an open-tubular liquid chromatography (OT LC) or an electrochemically-modulated liquid chromatography (EMLC) format. A reduction in instrument size can potentially increase analysis speed, and allow exceedingly small amounts of sample to be analyzed under diverse separation conditions. The second direction explores the surface enhanced Raman spectroscopy (SERS) as a signal transduction method for immunoassay analysis. It takes advantage of the improved detection sensitivity as a result of surface enhancement on colloidal gold, the …

This dissertation has involved the exploration of a new effect in photoelectron emission, multi-atom resonant photoemission (MARPE), as well as the development of new software, data analysis techniques, and detectors of general use in such research. We present experimental and theoretical results related to MARPE, in which the photoelectron intensity from a core level on one atom is influenced by a core-level absorption resonance on another. We point out that some of our and others prior experimental data has been strongly influenced by detector non-linearity and that the effects seen in new corrected data are smaller and of different form. Corrected data for the MnO(001) system with resonance between the O 1s and Mn 2p energy levels are found to be well described by an extension of well-known intraatomic resonant photoemission theory to the interatomic case, provided that interactions beyond the usual second-order Kramers-Heisenberg treatment are included. This theory is also found to simplify under certain conditions so as to yield results equivalent to a classical x-ray optical approach, with the latter providing an accurate and alternative, although less detailed and general, physical picture of these effects. Possible future applications of MARPE as a new probe of near-neighbor identities and …

The ability to model wave propagation in circular cylindrical bars of finite length numerically or analytically has many applications. In this thesis the capability of an explicit finite element method to model longitudinal waves in cylindrical rods with circular cross-sections is explored. Dispersion curves for the first four modes are compared to the analytical solution to determine the accuracy of various element sizes and time steps. Values for the time step and element size are determined that retain accuracy while minimizing computational time. The modeling parameters are validated by calculating a signal propagated with a broadband input force. Limitations on the applicability are considered along with modeling parameters that should be applicable to more general geometries.

In 1934 Fermi postulated a theory for weak interactions containing a dimensionful coupling with a size of roughly 250 GeV. Only now are we finally exploring this energy regime. What arises is an open question: supersymmetry and large extra dimensions are two possible scenarios. Meanwhile, other experiments will begin providing definitive information into the nature of neutrino masses and CP violation. In this paper, we explore features of possible theoretical scenarios, and study the phenomenological implications of various models addressing the open questions surrounding these issues.

A spin glass is a magnetic ground state in which ferromagnetic and antiferromagnetic exchange interactions compete, thereby creating frustration and a multidegenerate state with no long range order. An Ising system is a system where the spins are constrained to lie parallel or antiparallel to a primary axis. There has been much theoretical interest in the past ten years in the effects of applying a magnetic field transverse to the primary axis in an Ising spin glass at low temperatures and thus study phase transitions at the T=0 limit. The focus of this study is to search for and characterize a new Ising spin glass system. This is accomplished by site diluting yttrium for terbium in the crystalline material TbNi{sub 2}Ge{sub 2}. The first part of this work gives a brief overview of the physics of rare earth magnetism and an overview of experimental characteristics of spin glasses. This is followed by the methodology used to manufacture the large single crystals used in this study, as well as the measurement techniques used. Next, a summary of the results of magnetic measurements on across the dilution series from pure terbium to pure yttrium is presented. This is followed by detailed measurements …

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An externally air-cooled low-flow torch has been constructed and successfully demonstrated for applications in inductively coupled plasma mass spectrometry (ICP-MS). The torch is cooled by pressurized air flowing at {approximately}70 L/min through a quartz air jacket onto the exterior of the outer tube. The outer gas flow rate and operating RF forward power are reduced considerably. Although plasmas can be sustained at the operating power as low as 400 W with a 2 L/min of outer gas flow, somewhat higher power and outer gas flows are advisable. A stable and analytical useful plasma can be obtained at 850 W with an outer gas flow rate of {approximately}4 L/min. Under these conditions, the air-cooled plasma produces comparable sensitivities, doubly charged ion ratios, matrix effects and other analytical merits as those produced by a conventional torch while using significantly less argon and power requirements. Metal oxide ion ratios are slightly higher with the air-cooled plasma but can be mitigated by reducing the aerosol gas flow rate slightly with only minor sacrifice in analyte sensitivity. A methodology to alleviate the space charge and matrix effects in ICP-MS has been developed. A supplemental electron source adapted from a conventional electron impact ionizer is added …

In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-{sigma} bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active …

The UV photolysis of hexanes solutions containing the complexes M(CO){sub 6} (M=Cr, Mo, W) or CpMn(CO){sub 3} (Cp={eta}{sup 5}-C{sub 5}H{sub 5}) and excess thiophene (T{sup *}) (T{sup *}=2,5-dimethylthiophene (2,5-Me{sub 2}T), benzothiophene (BT), and dibenzothiophene (DBT)) produces the {eta}{sup 1}(S)-T{sup *} complexes (CO){sub 5}M({eta}{sup 1}(S)-T{sup *}) 1-8 or Cp(CO){sub 2}Mn({eta}{sup 1}(S)-T{sup *})9-11, respectively. However, when T{sup *}=DBT, and M=Mo, a mixture of two products result which includes the {eta}{sup 1}(S)-DBT complex (CO){sub 5}Mo({eta}{sup 1}(S)-DBT) 4a and the unexpected {pi}-complex (CO){sub 3}Mo({eta}{sup 6}-DBT) 4b as detected by {sup 1}H NMR. The liability of the {eta}{sup 1}(S)-T{sup *} ligands is illustrated by the rapid displacement of DBT in the complex (CO){sub 5}W({eta}{sup 1}(S)-DBT) (1) by THF, and also in the complexes (CO){sub 5}Cr({eta}{sup 1}(S)-DBT) (5) and CpMn(CO){sub 2}({eta}{sup 1}(S)-DBT) (9) by CO (1 atm) at room temperature. Complexes 1-11 have been characterized spectroscopically ({sup 1}H NMR, IR) and when possible isolated as analytically pure solids (elemental analysis, EIMS). Single crystal, X-ray structural determinations are reported for (CO){sub 5}W({eta}{sup 1}(S)-DBT) and Cp(CO){sub 2}Mn({eta}{sup 1}(S)-DBT).

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It is very important to find the best conditions for some enzymes to do the best catalysis in current pharmaceutical industries. Based on the results above, we could say that this set-up could be widely used in finding the optimal condition for best enzyme activity of a certain enzyme. Instead of looking for the best condition for enzyme activity by doing many similar reactions repeatedly, we can complete this assignment with just one run if we could apply enough conditions.

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Theoretical simulations and ultrafast pump-probe laser spectroscopy experiments were used to study photosynthetic pigment-protein complexes and antennae found in green sulfur bacteria such as Prosthecochloris aestuarii, Chloroflexus aurantiacus, and Chlorobium tepidum. The work focused on understanding structure-function relationships in energy transfer processes in these complexes through experiments and trying to model that data as we tested our theoretical assumptions with calculations. Theoretical exciton calculations on tubular pigment aggregates yield electronic absorption spectra that are superimpositions of linear J-aggregate spectra. The electronic spectroscopy of BChl c/d/e antennae in light harvesting chlorosomes from Chloroflexus aurantiacus differs considerably from J-aggregate spectra. Strong symmetry breaking is needed if we hope to simulate the absorption spectra of the BChl c antenna. The theory for simulating absorption difference spectra in strongly coupled photosynthetic antenna is described, first for a relatively simple heterodimer, then for the general N-pigment system. The theory is applied to the Fenna-Matthews-Olson (FMO) BChl a protein trimers from Prosthecochloris aestuarii and then compared with experimental low-temperature absorption difference spectra of FMO trimers from Chlorobium tepidum. Circular dichroism spectra of the FMO trimer are unusually sensitive to diagonal energy disorder. Substantial differences occur between CD spectra in exciton simulations performed with and without realistic …

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Inclusive transverse momentum spectra of photons and {pi}{sup 0}s at mid-rapidity are studied as a function of collision centrality for {sup 197}Au+ {sup 197}Au collisions at {radical}s{sub NN} = 130 GeV. Photon pair conversions have been reconstructed from charged tracks measured by the main Time Project Chamber of the STAR experiment at the RHIC heavy ion facility. The transverse momentum resolution of photons with this method is estimated to be {Delta}p{sub t}/p{sub t} = 2% at 0.125 GeV/c and 5% at 2.5 GeV/c. Photon spectra were measured up to a transverse momentum of 2.4 GeV/c between {+-} 0.5 units of rapidity. The dominant photon production mechanism, the {pi}{sup 0} {yields} {gamma}{gamma} decay, was measured between 0.25-2.5 GeV/c and {+-} 1 units of rapidity. Spectra are reported for the top 11%, 11-34% and 34-85% centrality classes. It was observed that in mid-central and central collisions the relative contribution of the {pi}{sup 0} {yields} {gamma}{gamma} decay to the inclusive photon spectrum decreases above a transverse momentum of 1.65 GeV/c. In central collisions the magnitude of the decrease from p{sub t} = 1.65 GeV/c to 2.4 GeV/c is 20%. It is unlikely that contributions from other {pi}{sup 0} decay channels and other particle …

Exposure to airborne particles is detrimental to human health and indoor exposures dominate total exposures for most people. The accidental or intentional release of aerosolized chemical and biological agents within or near a building can lead to exposures of building occupants to hazardous agents and costly building remediation. Particle deposition in heating, ventilation and air-conditioning (HVAC) systems may significantly influence exposures to particles indoors, diminish HVAC performance and lead to secondary pollutant release within buildings. This dissertation advances the understanding of particle behavior in HVAC systems and the fates of indoor particles by means of experiments and modeling. Laboratory experiments were conducted to quantify particle deposition rates in horizontal ventilation ducts using real HVAC materials. Particle deposition experiments were conducted in steel and internally insulated ducts at air speeds typically found in ventilation ducts, 2-9 m/s. Behaviors of monodisperse particles with diameters in the size range 1-16 {micro}m were investigated. Deposition rates were measured in straight ducts with a fully developed turbulent flow profile, straight ducts with a developing turbulent flow profile, in duct bends and at S-connector pieces located at duct junctions. In straight ducts with fully developed turbulence, experiments showed deposition rates to be highest at duct floors, …

The first five chapters of this thesis focus on studies of band anticrossing (BAC) effects in highly electronegativity- mismatched semiconductor alloys. The concept of bandgap bowing has been used to describe the deviation of the alloy bandgap from a linear interpolation. Bowing parameters as large as 2.5 eV (for ZnSTe) and close to zero (for AlGaAs and ZnSSe) have been observed experimentally. Recent advances in thin film deposition techniques have allowed the growth of semiconductor alloys composed of significantly different constituents with ever- improving crystalline quality (e.g., GaAs{sub 1-x}N{sub x} and GaP{sub 1-x}N{sub x} with x {approx}< 0.05). These alloys exhibit many novel and interesting properties including, in particular, a giant bandgap bowing (bowing parameters > 14 eV). A band anticrossing model has been developed to explain these properties. The model shows that the predominant bowing mechanism in these systems is driven by the anticrossing interaction between the localized level associated with the minority component and the band states of the host. In this thesis I discuss my studies of the BAC effects in these highly mismatched semiconductors. It will be shown that the results of the physically intuitive BAC model can be derived from the Hamiltonian of the many-impurity …

The penetration of ambient air pollutants into the indoor environment is of concern owing to several factors: (1) epidemiological studies have shown a strong association between ambient fine particulate pollution and elevated risk of human mortality; (2) people spend most of their time in indoor environments; and (3) most information about air pollutant concentration is only available from ambient routine monitoring networks. A good understanding of ambient air pollutant transport from source to receptor requires knowledge about pollutant penetration across building envelopes. Therefore, it is essential to gain insight into particle penetration in infiltrating air and the factors that affect it in order to assess human exposure more accurately, and to further prevent adverse human health effects from ambient particulate pollution. In this dissertation, the understanding of air pollutant infiltration across leaks in the building envelope was advanced by performing modeling predictions as well as experimental investigations. The modeling analyses quantified the extent of airborne particle and reactive gas (e.g., ozone) penetration through building cracks and wall cavities using engineering analysis that incorporates existing information on building leakage characteristics, knowledge of pollutant transport processes, as well as pollutant-surface interactions. Particle penetration is primarily governed by particle diameter and by the …

The size-dependent optical and electronic properties of semiconductor nanocrystals have drawn much attention in the past decade, and have been very well understood for spherical ones. The advent of the synthetic methods to make rod-like CdSe nanocrystals with wurtzite structure has offered us a new opportunity to study their properties as functions of their shape. This dissertation includes three main parts: synthesis of CdSe nanorods with tightly controlled widths and lengths, their optical and dielectric properties, and their large-scale assembly, all of which are either directly or indirectly caused by the uniaxial crystallographic structure of wurtzite CdSe. The hexagonal wurtzite structure is believed to be the primary reason for the growth of CdSe nanorods. It represents itself in the kinetic stabilization of the rod-like particles over the spherical ones in the presence of phosphonic acids. By varying the composition of the surfactant mixture used for synthesis we have achieved tight control of the widths and lengths of the nanorods. The synthesis of monodisperse CdSe nanorods enables us to systematically study their size-dependent properties. For example, room temperature single particle fluorescence spectroscopy has shown that nanorods emit linearly polarized photoluminescence. Theoretical calculations have shown that it is due to the crossing …

A one-tenth dimensionally scaled version of a final focus sub-system design for a heavy ion fusion driver is built and tested. By properly scaling the physics parameters that relate particle energy and mass, beam current, beam emittance, and focusing field, the transverse dynamics of a driver scale final focus are replicated in a small laboratory beam. The experiment uses a 95 {micro}A beam of 160 keV Cs{sup +} ions to study the dynamics as the beam is brought to a ballistic focus in a lattice of six quadrupole magnets. Diagnostic stations along the experiment track the evolution of the transverse phase space of the beam. The measured focal spot size is consistent with calculations and the report of the design on which the experiment is based. By uniformly varying the strengths of the focusing fields in the lattice, the chromatic effect of a small energy deviation on the spot size can be reproduced. This is done for {+-}1% and {+-}2% shifts and the changes in the focus are measured. Additionally, a 400 {micro}A beam is propagated through the experiment and partially neutralized after the last magnet using electrons released from a hot tungsten filament. The increase in beam current allows …

The risk of accidental detonation is present whenever any type of high explosives processing activity is performed. These activities are typically carried out indoors to protect processing equipment from the weather and to hide possibly secret processes from view. Often, highly strengthened reinforced concrete buildings are employed to house these activities. These buildings may incorporate several design features, including the use of lightweight frangible blowout panels, to help mitigate blast effects. These panels are used to construct walls that are durable enough to withstand the weather, but are of minimal weight to provide overpressure relief by quickly moving outwards and creating a vent area during an accidental explosion. In this study the behavior of blowout panels under various blast loading conditions was examined. External loadings from explosions occurring in nearby rooms were of primary interest. Several reinforcement systems were designed to help blowout panels resist failure from external blast loads while still allowing them to function as vents when subjected to internal explosions. The reinforcements were studied using two analytical techniques, yield-line analysis and modal analysis, and the hydrocode AUTODYN. A blowout panel reinforcement design was created that could prevent panels from being blown inward by external explosions. This design …

Plasma based accelerators are capable of producing electron sources which are ultra-compact (a few microns) and high energies (up to hundreds of MeVs) in much shorter distances than conventional accelerators. This is due to the large longitudinal electric field that can be excited without the limitation of breakdown as in RF structures.The characteristic scale length of the accelerating field is the plasma wavelength and for typical densities ranging from 1018 - 1019 cm-3, the accelerating fields and scale length can hence be on the order of 10-100GV/m and 10-40 mu m, respectively. The production of quasimonoenergetic beams was recently obtained in a regime relying on self-trapping of background plasma electrons, using a single laser pulse for wakefield generation. In this dissertation, we study the controlled injection via the beating of two lasers (the pump laser pulse creating the plasma wave and a second beam being propagated in opposite direction) which induce a localized injection of background plasma electrons. The aim of this dissertation is to describe in detail the physics of optical injection using two lasers, the characteristics of the electron beams produced (the micrometer scale plasma wavelength can result in femtosecond and even attosecond bunches) as well as a …

This thesis presents two-dimensional hydrodynamic disk simulations with embedded protoplanets, emphasizing the non-linear dynamics in the co-orbital region. In particular, it demonstrates how a protoplanetary disk responds to embedded low mass planets at the inviscid limit. Since the potential vorticity (PV) flow is not conserved, due to the spiral shocks and possibly boundary layer effects emanating from the planet, the PV profile develops inflection points which eventually render the flow unstable. Vortices are produced in association with the potential vorticity minima. Born in the separatrix region, these vortices experience close encounters with the planet, consequently exerting strong torques on the planet. The existence of these vortices, if confirmed, have important implications on planetary migration rates. The formation of vortices is discussed in more detail and a key parameter is found which depends solely on planet mass and sound speed. With this key parameter, one can predict the disk evolution, PV growth rates, and threshold conditions for forming vortices in the co-orbital region. An analytical estimate for the change of PV due to shocks is compared to the actual change in PV in the hydrodynamic simulations. They match well except in the inner region where vortices form. In addition, extensive resolution …