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Structure and Dynamics of Biolmolecules in the Gas Phase Using Vibrationally and Rotationally Resolved Electronic Spectroscopy

Thomas, Jessica Anne (2011) Structure and Dynamics of Biolmolecules in the Gas Phase Using Vibrationally and Rotationally Resolved Electronic Spectroscopy. Doctoral Dissertation, University of Pittsburgh.

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    Abstract

    Rotationally resolved electronic spectroscopy is used to determine the rotational constants of small aromatic molecules. These rotational constants, when compared to calculated low energy structures, provide a precise description of the structure of the molecule. In addition, by comparing rotational constants for the structure in the ground and excited electronic states, as well as those associated with various vibronic transitions, an understanding of the dynamics of the molecule can be obtained. In this work, molecules containing double rings, including 1,3-benzodioxole, coumaran, and 1-phenylpyrrole, were studied using rotationally resolved electronic spectroscopy to determine their structures, low frequency vibrational motions, and changes in electronic distribution upon electronic excitation. Laser ablation, a technique used to produce gas phase samples of moderately sized biomolecules with significantly less decomposition than with thermal vaporization, was used to obtain gas phase samples of short peptide sequences. These molecules were studied using a IR/UV double resonance technique which enabled the collection of IR spectra with resolved transitions in the amide A and OH stretch regions. Specifically, several short sequences found in a folding nucleus of β-lactoglobulin were compared to calculated structures in order to identify intramolecular interactions that stabilize the structures.


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    Item Type: University of Pittsburgh ETD
    ETD Committee:
    ETD Committee TypeCommittee MemberEmail
    Committee ChairPratt, David Wpratt@pitt.edu
    Committee MemberChong, Lillianltchong@pitt.edu
    Committee MemberMons, Michelmichel.mons@cea.fr
    Committee MemberSaxena, Sunilsksaxena@pitt.edu
    Title: Structure and Dynamics of Biolmolecules in the Gas Phase Using Vibrationally and Rotationally Resolved Electronic Spectroscopy
    Status: Unpublished
    Abstract: Rotationally resolved electronic spectroscopy is used to determine the rotational constants of small aromatic molecules. These rotational constants, when compared to calculated low energy structures, provide a precise description of the structure of the molecule. In addition, by comparing rotational constants for the structure in the ground and excited electronic states, as well as those associated with various vibronic transitions, an understanding of the dynamics of the molecule can be obtained. In this work, molecules containing double rings, including 1,3-benzodioxole, coumaran, and 1-phenylpyrrole, were studied using rotationally resolved electronic spectroscopy to determine their structures, low frequency vibrational motions, and changes in electronic distribution upon electronic excitation. Laser ablation, a technique used to produce gas phase samples of moderately sized biomolecules with significantly less decomposition than with thermal vaporization, was used to obtain gas phase samples of short peptide sequences. These molecules were studied using a IR/UV double resonance technique which enabled the collection of IR spectra with resolved transitions in the amide A and OH stretch regions. Specifically, several short sequences found in a folding nucleus of β-lactoglobulin were compared to calculated structures in order to identify intramolecular interactions that stabilize the structures.
    Date: 30 June 2011
    Date Type: Completion
    Defense Date: 01 April 2011
    Approval Date: 30 June 2011
    Submission Date: 17 April 2011
    Access Restriction: No restriction; Release the ETD for access worldwide immediately.
    Patent pending: No
    Institution: University of Pittsburgh
    Thesis Type: Doctoral Dissertation
    Refereed: Yes
    Degree: PhD - Doctor of Philosophy
    URN: etd-04172011-105721
    Uncontrolled Keywords: high resolution; serine; Stark effect; tryptophan; tyrosine
    Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
    Date Deposited: 10 Nov 2011 14:38
    Last Modified: 08 May 2012 13:48
    Other ID: http://etd.library.pitt.edu/ETD/available/etd-04172011-105721/, etd-04172011-105721

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