Physical Sciences and Mathematics Commons^™

Instrumentation, Applications And Fundamentals Of Plasma Ionization Of Organic Molecules From Surfaces, Joshua Scott Wiley

Open Access Dissertations

Various aspects of the interaction of low-temperature plasma (LTP) ambient ionization with organic molecules and surfaces are discussed. As an application, LTP-MS has been used for the analysis of pesticides directly from fruits and vegetables revealing low parts per billion limits of detection (LODs). Due to low power and gas requirements, a battery-operated and handheld LTP probe was developed for the point-and-shoot MS analyses. Handheld LTP was compared with large-scale LTP on a benchtop and miniature MS revealing similar LODs for both. Long-distance ion transport up to one meter was also demonstrated with flexible tubing for non-proximate sample interrogation. Fundamentals …

Gas-Phase Covalent And Non-Covalent Ion/Ion Chemistry Of Biological Macromolecules, John Robert Stutzman

Open Access Dissertations

Gas-phase ion/ion chemistry involves the interaction of oppositely charged ions inside of the mass spectrometer. During this gas-phase chemistry, particle transfer (i.e., proton and electron) or synthesis can occur at rapid reaction rates. Particle transfer represents a mature area of ion/ion chemistry, while selective covalent modification represents a fairly new area of gas-phase chemistry. Gas-phase covalent chemistry is based on traditional solution phase organic chemistry.

The work demonstrated in this dissertation greatly involves gas-phase covalent and non-covalent Schiff base chemistry on peptide and protein ions. The reagent dianion, 4-formyl 1,3-benzene disulfonic acid, has been used to covalently modify unprotonated primary …

Top-Down Interrogation And Characterization Of Biological Macromolecules, Yang Gao

Open Access Dissertations

Analytical mass spectrometry has been widely applied in the field of biomolecule identification and characterization. It provides fast, accurate and robust information relevant to the molecular mass, composition and structure of the target analytes.

This thesis is focused on the top-down analysis of various macrobiomolecules, nucleic acids and proteins, in the context of ion/ion reaction and gas-phase unimolecular dissociation. The first part of the thesis deals with gas phase fragmentation behavior of chemically modified oligonucleotides. Factors, such as the observation time-scale, the ion type and the energy deposition method, are explored using a quadrupole/time-of-flight mass spectrometer. Novel fragmentation pathway associated …

Mass Spectrometric Studies On The Primary Products Of Fast Pyrolysis Of Carbohydrates And The Molecular Structures Of Asphaltenes, And The Development Of A Rastering Probe For Laser-Induced Acoustic Desorption Into An Atmospheric Pressure Chemical Ionization Source, Matthew Robert Hurt

Open Access Dissertations

Mass spectrometry (MS) has proven invaluable in the field of mixture analysis and structural elucidation. Tandem mass spectrometry (MS/MS) utilizing collision-activated dissociation (CAD) has become the technique of choice for structural elucidation of unknown analytes in mixtures. When coupled with gas chromatography (GC) or high performance liquid chromatography (HPLC), it allows for trace level analysis of mixture components. In spite of the utility of mass spectrometry in complex mixture analysis, it does have limitations. Traditional GC/MS methods used for the analysis of fast pyrolysis products cannot be used to analyze the primary products, thus limiting the knowledge that can be …

Structural Analysis Of Carbohydrates By Mass Spectrometry, Chiharu Konda

Open Access Dissertations

Protein glycosylation is a highly frequent post-translational modification. Glycosylation is actively involved in intermolecular and intercellular binding events that are important to a wide range of biological functions such as immunity and fertility. The unique functions of glycans are directly related to their structures. In order to fully characterize the structure of an unknown glycan, 5 levels of structural information is needed: sugar unit identity, anomeric configuration, linkage types, sequence, and branching location. One of the grand challenges limiting the advance of glycosciences is the lack of sensitive tools for detailed glycan structural analysis. Tandem mass spectrometry (MS/MS) is a …

Development Of A Field-Portable Miniature Mass Spectrometer Designed For In-Situ Analysis And Ion Trap Miniaturization, Paul Isaac Hendricks

Open Access Dissertations

Chemical analysis by mass spectrometry has become the gold standard due to the sensitivity, selectivity, and short analysis times that are afforded by the method. Advances in miniaturized vacuum systems, mass analyzers, electronics, and ionization sources have allowed for the development of field-portable mass spectrometers. The performance of portable instruments has received much attention for their utility in the detection of illicit drugs, explosives, environmental contaminants, therapeutic drugs, and more recently, biological tissues. Furthermore, detection of the aforementioned compounds can be completed at atmospheric pressures and in the presence of complex matrices and sample surfaces when used in conjunction with …

Structural And Functional Study Of The Diheme Cytochrome C Subunit Of The Cytochrome Bc Complex In Heliobacterium Modesticaldum, Hair Yue

Arts & Sciences Electronic Theses and Dissertations

This dissertation is focused on the structural and functional study of the unique diheme cytochrome c subunit of the cytochrome bc complex in H. modesticaldum, and its application in determining the stoichiometry between H. modesticaldum's cytochrome bc complex and its reaction center. Heliobacterium modesticaldum is a gram positive, anaerobic, anoxygenic photoheterotrophic bacterium. Its cytochrome bc complex (Rieske/cyt b complex) has some similarities to cytochrome b6f complexes from cyanobacteria and chloroplasts, and also shares some characteristics of typical bacterial cytochrome bc1 complexes. One of the unique features of the heliobacterial cytochrome bc complex is the presence of a diheme cytochrome c …

Analyses Of Multivitamins In Nutraceuticals By Reverse Phase Hplc With Dad, Elsd And Ms, Hsiang-Chi Huang

All Theses

ABSTRACT
Vitamins are essential to human beings and support long-term healthy lifestyle. They exist widely in food, but in small amount. Hence, dietary supplements and fortified food products are more and more popular in the nutritional markets. According to the Infant Formula Act of 1980, the range of each of the nutrients should fall within a specific range or above the required minimum, so there is an increasing interest of accurate measurement of vitamins, particularly the B-group vitamins. However, traditional methods for vitamin B analyses are time-consuming and often in poor accuracy. As a result, rapid and reliable analytical methods …

Optimization Of Sample Preparation In Matrix-Assisted Laser Desorption/Ionization (Maldi) Mass Spectrometry Of Macromolecules, Evgenia Akhmetova

Graduate Theses and Dissertations

New method for the matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) and Fourier transform mass spectrometry (MALDI-FTMS) analysis of low molecular weight polyvinyl acetate (PVAc) was developed and then applied to the characterization of commercially available chewing gum. The optimization of MALDI analysis of PVAc was achieved by investigating the influence of sample preparation variables such as the choice of solvent and choice of matrix-analyte ratio. It was demonstrated that the use of ethyl acetate as a solvent and 2,5-Dihydroxybenzoic acid as a matrix yielded the highest signal intensity for the pure polymer sample. The application of TOF technique did not …

Bacterial Spores Remain Viable After Electrospray Charging And Desolvation, Sara Nielson Pratt

Theses and Dissertations

The electrospray survivability of B. subtilis spores and E. coli was tested in atmospheric mobility experiments. E. coli did not survive electrospray charging and desolvation, but B. subtilis did. Experimental conditions ensured that any surviving bacteria were charged, desolvated, and de-agglomerated. B. subtilis was also found to survive both positive and negative electrospray and subsequent introduction into vacuum conditions. Attempts were made to measure the charge distribution of viable B. subtilis spores using electrostatic deflection. From those experiments, it was found that either the spores do not become highly charged under the electrospray conditions used or only spores in a …

Photoionization Mass Spectrometry And Photoelectron-Photoion Coincidence (Pepico) Spectroscopy Studies Of Select Biofuel Molecules, Joseph G. Czekner

Master's Theses

This thesis is the culmination of numerous experiments, performed on two different continents, investigating the spectroscopic and thermodynamic properties of several biofuels and fuel additives. It will start with an introduction about the motivation behind these experiments. The second chapter will outline the experimental details of the apparatus at the Advanced Light Source (ALS) in Berkeley, CA, followed by the Swiss Light Source (SLS) in Villigen, Switzerland. Third, the theoretical concepts and data analysis methods will be discussed in detail.

Chapter 4 will be the start of the newly obtained data. It presents some photoionization mass spectrometry studies on γ-valerolactone …

Binding Energies And Solvation Of Organic Molecular Ions, Reactions Of Transition Metal Ions With, And Plasma Discharge Ionization Of Molecular Clusters, Isaac Kwame Attah

Theses and Dissertations

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and …

Enhanced Detection Strategies Accomplished Through Metal Binding And Miniature Mass Spectrometry, Adam Graichen

Open Access Dissertations

A multiplexed method for performing MS/MS on multiple ions simultaneously in a miniature rectilinear ion trap (RIT) mass spectrometer has been developed. This method uses an ion encoding procedure that relies on the mass bias that exists when ions are externally injected into an RIT operated with only a single phase RF applied to one pair of electrodes. The ion injection profile under such conditions ions is Gaussian-like over a wide range of RF amplitudes, or low mass cutoff (LMCO) values, during ion accumulation. We show that this distribution is related to ion m/z and is likely caused by ions …

Development Of Quantitative Bioanalytical Methods For The Pharmacological Studies Of Anti-Cancer Drugs, Ye Feng

ETD Archive

In the anticancer drug discovery and therapy development, it is essential to understand the pharmacological properties of the drugs. Today, pharmaceutical analysis is employed throughout the whole drug discovery and development process. Pharmacokinetic-pharmacodynamic relationships are playing an increasingly important role in decisions on the rational development and use of new drugs and they can provide a detailed knowledge of the mechanism of the drug and a better understanding of the molecular targets on which they act. Due to the significance of pharmacological analysis, sensitive analytical methods are critically needed for pharmacological studies. Therefore, our long-term goal is to provide guidelines …

Optimization Of Gradient Chromatofocusing For The Protein Separation And Lc-Ms/Ms Determination Of Ngp1-01 In Mouse Serum, Brain, And Retina, Harini Jogiraju

ETD Archive

No abstract provided.

Gradient Chromatofocusing And Reversed Phase Hplc In Protein Analysis And Lc-Ms/Ms Determination Of Thiazolidinedione Nl-1 In Mouse Serum And Brain, Kiran K. Pedada

ETD Archive

No abstract provided.

From Whole-Cell To Compartment- And Class-Specific Analysis Of Rna Post-Transcriptional Modifications, Ryan Quinn

Legacy Theses & Dissertations (2009 - 2024)

The genomic structure of the human immunodeficiency virus type 1 (HIV-1) has proven difficult to examine by traditional high-resolution techniques. Structural probing and in silico modeling have been turned to the task instead. Computer models are only as robust as the data used to create them. A number of techniques were explored in this investigation to expand the utility of in silico modeling as it relates to HIV-1: the study of nucleoside modifications, and the probing of in vivo conformations of the 5'-untranslated region (5'-UTR) by cross-linking and affinity capture.

Laser Ablation Sample Transfer For Mass Spectrometry, Sung-Gun Park

LSU Doctoral Dissertations

In this research, a new ambient sampling technique for mass spectrometry was developed that uses an infrared laser to ablate materials under ambient conditions that are captured in a solvent or on a surface. An infrared optical parametric oscillator (OPO) laser system at 3 μm wavelength was focused onto samples for ablation at atmospheric pressure. The ablated materials were transferred to a solvent or surface. For off-line electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) analysis, the ablated material was captured in a static solvent droplet that was deposited on a MALDI target or flow-injected into a nanoelectrospray source. The …

Detection Of Microorganisms Using Maldi And Ion Mobility Mass Spectrometry, Juaneka Monet Hayes

LSU Doctoral Dissertations

Matrix-assisted laser ablation desorption ionization MALDI and ion mobility (IM) MALDI mass spectrometry (MS) were used for the detection and identification of microorganisms. MALDI MS is an analytical tool that separates ions by their mass-to-charge ratio (m/z) and is routinely used for bioanalysis because of its sensitivity, selectivity, general applicability, and tolerance to impurities. Ion mobility is a gas phase technique that separates ions based on their charge and collision cross-section. In this research, MALDI-TOF MS and MALDI-IM-TOF MS analysis were conducted in parallel to assess the effectiveness of MALDI-IM-TOF MS for microorganism identification. Whole cell bacteria Escherichia coli strain …