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Physical Sciences and Mathematics Commons

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Physical Chemistry

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Open Access Dissertations

2015

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Full-Text Articles in Physical Sciences and Mathematics

Mass Spectrometric Characterization Of Peptide Radical Ions And Implication For Radical Chemistry, Lei Tan Apr 2015

Mass Spectrometric Characterization Of Peptide Radical Ions And Implication For Radical Chemistry, Lei Tan

Open Access Dissertations

Gas-phase radical ion chemistry has attracted increasing research interest from the mass spectrometry (MS) society because it provides new capabilities in bio-analysis which often complements traditional MS methods developed from even-electron ions. Fundamental studies of biomolecule related radical species are essential to broadening the scope of radical chemistry and pushing the frontiers of its analytical applications. This dissertation mainly discusses the gas-phase chemistry of peptide sulfinyl radicals (-SO·), which has been rarely studied before. In order to establish an effective research approach, a method that can generate site-specific peptide sulfinyl radical ion has been developed. This method is based on …


Quantification Of Molecular Aggregation Equilibria Using Spectroscopic Measurements And Random Mixing Modeling, Blake M. Rankin Apr 2015

Quantification Of Molecular Aggregation Equilibria Using Spectroscopic Measurements And Random Mixing Modeling, Blake M. Rankin

Open Access Dissertations

Molecular aggregation equilibria, such as the binding of ligands to a central solute molecule, are prevalent throughout biological processes and energy storage devices. However, both the sign and magnitude of hydrophobic and ionic interactions remains a subject of theoretical debate, and has yet to be experimentally determined. Here, Raman vibrational spectroscopy is combined with multivariate curve resolution (Raman-MCR) to experimentally quantify both the number of hydrophobic contacts between alcohol molecules in water and the affinity of ions for molecular hydrophobic interfaces. Furthermore, a generalized theoretical model is developed based on random statistics in which it is assumed that the concentration …