This dissertation focuses on techniques for (1) increasing ethanol yields from saccharification and fermentation of cellulose using immobilized cellulase, and (2) the characterization and classification of lignocellulosic feedstocks, and quantification of useful parameters such as the syringyl/guaiacyl (S/G) lignin monomer content using 1064 nm dispersive multichannel Raman spectroscopy and chemometrics.

This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.

Organic semiconductors devices, such as, organic solar cells (OSCs), organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs) have drawn increasing interest in recent decades. As organic materials are flexible, light weight, and potentially low-cost, organic semiconductor devices are considered to be an alternative to their inorganic counterparts. This dissertation will focus mainly on OSCs and OLEDs. As a clean and renewable energy source, the development of OSCs is very promising. Cells with 9.2% power conversion efficiency (PCE) were reported this year, compared to < 8% two years ago. OSCs belong to the so-called third generation solar cells and are still under development. While OLEDs are a more mature and better studied field, with commercial products already launched in the market, there are still several key issues: (1) the cost of OSCs/OLEDs is still high, largely due to the costly manufacturing processes; (2) the efficiency of OSCs/OLEDs needs to be improved; (3) the lifetime of OSCs/OLEDs is not sufficient compared to their inorganic counterparts; (4) the physics models of the behavior of the devices are not satisfactory. All these limitations invoke the demand for new organic materials, improved device architectures, low-cost fabrication methods, and better understanding of device physics. For …

Concurrency levels in large-scale, distributed-memory supercomputers are rising exponentially. Modern machines may contain 100,000 or more microprocessor cores, and the largest of these, IBM's Blue Gene/L, contains over 200,000 cores. Future systems are expected to support millions of concurrent tasks. In this dissertation, we focus on efficient techniques for measuring and analyzing the performance of applications running on very large parallel machines. Tuning the performance of large-scale applications can be a subtle and time-consuming task because application developers must measure and interpret data from many independent processes. While the volume of the raw data scales linearly with the number of tasks in the running system, the number of tasks is growing exponentially, and data for even small systems quickly becomes unmanageable. Transporting performance data from so many processes over a network can perturb application performance and make measurements inaccurate, and storing such data would require a prohibitive amount of space. Moreover, even if it were stored, analyzing the data would be extremely time-consuming. In this dissertation, we present novel methods for reducing performance data volume. The first draws on multi-scale wavelet techniques from signal processing to compress systemwide, time-varying load-balance data. The second uses statistical sampling to select a small …

Homeland security relies heavily on analytical chemistry to identify suspicious materials and persons. Traditionally this role has focused on attribution, determining the type and origin of an explosive, for example. But as technology advances, analytical chemistry can and will play an important role in the prevention and preemption of terrorist attacks. More sensitive and selective detection techniques can allow suspicious materials and persons to be identified even before a final destructive product is made. The work presented herein focuses on the use of commercial and novel detection techniques for application to the prevention of terrorist activities. Although drugs are not commonly thought of when discussing terrorism, narcoterrorism has become a significant threat in the 21st century. The role of the drug trade in the funding of terrorist groups is prevalent; thus, reducing the trafficking of illegal drugs can play a role in the prevention of terrorism by cutting off much needed funding. To do so, sensitive, specific, and robust analytical equipment is needed to quickly identify a suspected drug sample no matter what matrix it is in. Single Particle Aerosol Mass Spectrometry (SPAMS) is a novel technique that has previously been applied to biological and chemical detection. The current work …

This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformation which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to …

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed to view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. In this thesis examples of studies of lithium battery electrodes and liquid systems using soft x-ray emission spectroscopy will be presented. Monochromatized synchrotron radiation has been used to accomplish selective excitation, in terms of energy and polarization. The electronic structure of graphite electrodes has been studied, before and after lithium intercalation. Changes in the electronic structure upon lithiation due to transfer of electrons into the graphite …

In core-collapse supernovae, strong blast waves drive interfaces susceptible to Rayleigh-Taylor (RT), Richtmyer-Meshkov (RM), and Kelvin-Helmholtz (KH) instabilities. In addition, perturbation growth can result from material expansion in large-scale velocity gradients behind the shock front. Laser-driven experiments are designed to produce a strongly shocked interface whose evolution is a scaled version of the unstable hydrogen-helium interface in core-collapse supernovae such as SN 1987A. The ultimate goal of this research is to develop an understanding of the effect of hydrodynamic instabilities and the resulting transition to turbulence on supernovae observables that remain as yet unexplained. In this dissertation, we present a computational study of unstable systems driven by high Mach number shock and blast waves. Using multi-physics radiation hydrodynamics codes and theoretical models, we consider the late nonlinear instability evolution of single mode, few mode, and multimode interfaces. We rely primarily on 2D calculations but present recent 3D results as well. For planar multimode systems, we show that compressibility effects preclude the emergence of a regime of self-similar instability growth independent of the initial conditions (IC's) by allowing for memory of the initial conditions to be retained in the mix-width at all times. The loss of transverse spectral information is demonstrated, …

Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO{sub 2} films] revealed that MnO{sub 2} film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO{sub 2} films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO{sub 2} films showed that the Fe(III)-doped RuO{sub 2}-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO{sub 2} films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H{sub 2}O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb{sub 10}Sn{sub 20}Ti{sub …

The underlying theme of this thesis is the use of polymeric materials in bioapplications. Chapters 2-5 either develop a fundamental understanding of current materials used for bioapplications or establish protocols and procedures used in characterizing and synthesizing novel materials. In chapters 6 and 7 these principles and procedures are applied to the development of materials to be used for gene therapy and drug delivery. Chapter one is an introduction to the ideas that will be necessary to understand the subsequent chapters, as well as a literature review of these topics. Chapter two is a paper that has been published in the ''Journal of Controlled Release'' that examines the mechanism of drug release from a polymer gel, as well as experimental design suggestions for the evaluation of water soluble drug delivery systems. Chapter three is a paper that has been published in the ''Journal of Pharmaceutical Sciences'' that discusses the effect ionic salts have on properties of the polymer systems examined in chapter two. Chapter four is a paper published in the Materials Research Society Fall 2000 Symposium Series dealing with the design and synthesis of a pH-sensitive polymeric drug delivery device. Chapter five is a paper that has been published …

A new technique for in situ imaging and screening heterogeneous catalysts by using multiplexed capillary electrophoresis with absorption detection was developed. By bundling the inlets of a large number of capillaries, an imaging probe can be created that can be used to sample products formed directly from a catalytic surface with high spatial resolution. In this work, they used surfaces made of platinum, iron or gold wires as model catalytic surfaces for imaging. Various shapes were recorded including squares and triangles. Model catalytic surfaces consisting of both iron and platinum wires in the shape of a cross were also imaged successfully. Each of the two wires produced a different electrochemical product that was separated by capillary electrophoresis. Based on the collected data they were able to distinguish the products from each wire in the reconstructed image.

The results of magnetic x-ray resonant exchange scattering (XRES) experiments are important to the development of an understanding of magnetic interactions in materials. The advantages of high Q resolution, polarization analysis, and the ability to study many different types of materials make it a vital tool in the field of condensed matter physics. Though the concept of XRES was put forth by Platzman and Tzoar in 1970, the technique did not gain much attention until the work of Gibbs and McWhan et al. in 1988. Since then, the technique of XRES has grown immensely in use and applicability. Researchers continue to improve upon the procedure and detection capabilities in order to study magnetic materials of all kinds. The XRES technique is particularly well suited to studying the rare earth metals because of the energy range involved. The resonant L edges of these elements fall between 5-10 KeV. Resonant and nonresonant x-ray scattering experiments were performed in order to develop an understanding of the magnetic ordering in GdCo{sub 2}Ge{sub 2} and NdCo{sub 2}Ge{sub 2}.

In this work, the authors have undertaken a theoretical approach to the complex problem of modeling the flow of electromagnetic waves in photonic crystals. The focus is to address the feasibility of using the exciting phenomena of photonic gaps (PBG) in actual applications. The authors start by providing analytical derivations of the computational electromagnetic methods used in their work. They also present a detailed explanation of the physics underlying each approach, as well as a comparative study of the strengths and weaknesses of each method. The Plane Wave expansion, Transfer Matrix, and Finite Difference time Domain Methods are addressed. They also introduce a new theoretical approach, the Modal Expansion Method. They then shift the attention to actual applications. They begin with a discussion of 2D photonic crystal wave guides. The structure addressed consists of a 2D hexagonal structure of air cylinders in a layered dielectric background. Comparison with the performance of a conventional guide is made, as well as suggestions for enhancing it. The studies provide an upper theoretical limit on the performance of such guides, as they assumed no crystal imperfections and non-absorbing media. Next, they study 3D metallic PBG materials at near infrared and optical wavelengths. The main …

Industrial synthesis of sulfur-containing organic chemicals basically focuses on the broad categories of mercaptans (thiols), alkylsulfides (thioethers), polysulfides, and thiophenes. Of the organo-sulfur compounds produced, by far the most important in terms of quantities produced is methyl mercaptan (methanethiol or MeSH), which is produced mainly for the downstream production of methionine and methanesulfonyl chloride. Higher thiols are also used in the manufacture of rubber and plastics as polymerization regulators, chain transfer agents, or initiators. Other important organosulfur chemicals are dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), both of which are used extensively for presulfiding of industrial hydroprocessing catalysts, and substituted thiophenes which are used as intermediates for production of agrochemicals, dyes, and pharmaceuticals. Thiols are produced commercially at the rate of about 10{sup 4} ton/yr from hydrogen sulfide (H{sub 2}S) and alcohols or olefins, using homogeneous free-radical synthesis, or heterogeneous catalysts based on solid acids or supported metal oxides and/or sulfides. Despite this large production rate, and the industrial importance of the organosulfur compounds, only limited research has been devoted to the development of new catalytic materials for their synthesis. Additionally, for most organosulfur catalytic reactions, only limited information exists about reaction mechanisms, active sites, adsorbed surface species, and especially …

Magnetic flux leakage (MFL) is a technique used widely in non-destructive testing (NDT) of natural gas and petroleum transmission pipelines. This inspection method relies on magnetizing the pipe-wall in axial direction. The MFL inspection tool is equipped with an array of Hall sensors located around the circumference of the pipe, which registers the flux leakage caused by any defects present in the pipe-wall. Currently, the tool magnetizes the pipewall in axial direction making it largely insensitive to axially oriented defects. One type of defect, which is of a growing concern in the gas and petroleum industry is the stress corrosion crack (SCC). The SCCs are a result of aging, corrosion, fatigue and thermal stresses. SCCs are predominantly axially oriented and are extremely tight, which makes them impossible to be detected using current inspection technology. A possible solution to this problem is to utilize the remote field eddy current (RFEC) effect to detect axially oriented defects. The RFEC method has been widely used in industry in the inspection of tubular products. The method uses a pair of excitation and pick-up coils. The pick-up coil located in the remote field region, usually two, three pipe-diameters away from the excitation coil. With RFEC …

With the recent discovery of the giant magnetocaloric effect and the beginning of extensive research on the properties of Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4}, a necessity has developed for a better understanding of the microstructure and crystal structure of this family of rare earth compounds with startling phenomenological properties. The aim of this research is to characterize the microstructure of the Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4}, with X {approx_equal} 2 and its phase change by using both transmission and electron microscopes. A brief history of past work on Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4} is necessary to understand this research in its proper context.

Capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC) are widely used analytical separation techniques with many applications in chemical, biochemical, and biomedical sciences. Conventional analyte identification in these techniques is based on retention/migration times of standards; requiring a high degree of reproducibility, availability of reliable standards, and absence of coelution. From this, several new information-rich detection methods (also known as hyphenated techniques) are being explored that would be capable of providing unambiguous on-line identification of separating analytes in CE and HPLC. As further discussed, a number of such on-line detection methods have shown considerable success, including Raman, nuclear magnetic resonance (NMR), mass spectrometry (MS), and fluorescence line-narrowing spectroscopy (FLNS). In this thesis, the feasibility and potential of combining the highly sensitive and selective laser-based detection method of FLNS with analytical separation techniques are discussed and presented. A summary of previously demonstrated FLNS detection interfaced with chromatography and electrophoresis is given, and recent results from on-line FLNS detection in CE (CE-FLNS), and the new combination of HPLC-FLNS, are shown.

The focus of this thesis was first to characterize and improve the applicability of Fe(III) and Bi(V) doped PbO{sub 2} film electrodes for use in anodic O-transfer reactions of toxic and waste organic compounds, e.g. phenol, aniline, benzene, and naphthalene. Further, they investigated the use of alternative solution/electrode interfacial excitation techniques to enhance the performance of these electrodes for remediation and electrosynthetic applications. Finally, they have attempted to identify a less toxic metal oxide film that may hold promise for future studies in the electrocatalysis and photoelectrocatalysis of O-transfer reactions using metal oxide film electrodes.

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performance both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol …

Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al succeeded in the re-hydrogenation of NaAlH{sub 4} below 70 atm. They achieved 4 wt.% H{sub 2} reversible capacity by doping NaAlH{sub 4} with Ti and/or Fe organo-metallic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr{sub 27}Ti{sub 9}Ni{sub 38}V{sub 5}Mn{sub 16}Cr{sub 5}, LaNi{sub 4.85}Sn{sub 0.15}, Al{sub 3}Ti, and PdCl{sub 2} were combined with LiAlH{sub 4} by ball-milling to study whether or not LiAlH{sub 4} is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH{sub 4} and Li{sub 3}AlH{sub 6} by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.

The goal of this thesis is to develop a new Channel Interface device for the MPICH Implementation of the MPI (Message Passing Interface) standard using MP{_}Lite. MP{_}Lite is a lightweight message-passing library that is not a full MPI implementation, but offers high performance MPICH (Message Passing Interface CHameleon) is a full implementation of the MPI standard that has the p4 library as the underlying communication device for TCP/IP networks. By integrating MP{_}Lite as a Channel Interface device in MPICH, a parallel programmer can utilize the full MPI implementation of MPICH as well as the high bandwidth offered by MP{_}Lite. There are several layers in the MPICH library where one can tie a new device. The Channel Interface is the lowest layer that requires very few functions to add a new device. By attaching MP{_}Lite to MPICH at the lowest level, the Channel Interface, almost all of the performance of the MP{_}Lite library can be delivered to the applications using MPICH. MP{_}Lite can be implemented either as a blocking or a non-blocking Channel Interface device. The performance was measured on two separate test clusters, the PC and the Alpha miniclusters, having Gigabit Ethernet connections. The PC cluster has two 1.8 GHz …

In a cellular array, a range of primary spacing is found to be stable under given growth conditions. Since a strong coupling of solute field exists between the neighboring cells, primary spacing variation should also influence other microstructure features such as cell shape and cell length. The existence of multiple solutions is examined in this study both theoretically as well as experimentally. A theoretical model is developed that identifies and relates four important microstructural lengths, which are found to be primary spacing, tip radius, cell width and cell length. This general microstructural relationship is shown to be valid for different cells in an array as well as for other cellular patterns obtained under different growth conditions. The unique feature of the model is that the microstructure correlation does not depend on composition or growth conditions since these variables scale microstructural lengths to satisfy the relationship obtained in this study. Detailed directional solidification experimental studies have been carried out in the succinonitrile-salol system to characterize and measure these four length scales. Besides the validation of the model, experimental results showed additional scaling laws to be present. In the regime where only a cellular structure is formed, the shape of the cell, …

Astrocytes, a subtype of glial cell, have recently been shown to exhibit Ca{sup 2+} elevations in response to neurotransmitters. A Ca{sup 2+} elevation can propagate to adjacent astrocytes as a Ca{sup 2+} wave, which allows an astrocyte to communicate with its neighbors. Additionally, glutamate can be released from astrocytes via a Ca{sup 2+}-dependent mechanism, thus modulating neuronal activity and synaptic transmission. In this dissertation, the author investigated the roles of another endogenous signal, nitric oxide (NO), in astrocyte-neuron signaling. First the author tested if NO is generated during astrocytic Ca{sup 2+} signaling by imaging NO in purified murine cortical astrocyte cultures. Physiological concentrations of a natural messenger, ATP, caused a Ca{sup 2+}-dependent NO production. To test the roles of NO in astrocytic Ca{sup 2+} signaling, the author applied NO to astrocyte cultures via addition of a NO donor, S-nitrosol-N-acetylpenicillamine (SNAP). NO induced an influx of external Ca{sup 2+}, possibly through store-operated Ca{sup 2+} channels. The NO-induced Ca{sup 2+} signaling is cGMP-independent since 8-Br-cGMP, an agonistic analog of cGMP, did not induce a detectable Ca{sup 2+} change. The consequence of this NO-induced Ca{sup 2+} influx was assessed by simultaneously monitoring of cytosolic and internal store Ca{sup 2+} using fluorescent Ca{sup 2+} …

Low temperature Nonphotochemical Hole Burning (NPHB) Spectroscopy of the dye rhodamine 800 (MF680) was applied for the purpose of discerning differences between cultured normal and carcinoma ovarian surface epithelial (OSE) cells. Both the cell lines were developed and characterized at the Mayo Clinic (Rochester, MN), with the normal cell line having been transfected with a strain of temperature sensitive Simian Virus 40 Large T Antigen (SV40) for the purpose of extending the life of the cell culture without inducing permanent changes in the characteristics of the cell line. The cationic lipophilic fluorophore rhodamine 800 preferentially locates in in situ mitochondria due to the high lipid composition of mitochondria and the generation of a large negative membrane potential (relative to the cellular cytoplasm) for oxidative phosphorylation. Results presented for NPHB of MF680 located in the cells show significant differences between the two cell lines. The results are interpreted on the basis of the NPHB mechanism and characteristic interactions between the host (cellular mitochondrial) and the guest (MF680) in the burning of spectral holes, thus providing an image of the cellular ultrastructure. Hole growth kinetics (HGK) were found to differ markedly between the two cell lines, with the carcinoma cell line burning …