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  • 1985-1989  (5)
Materialart
Erscheinungszeitraum
Jahr
  • 1
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 6945-6951 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The dispersed fluorescence of the amino acid tryptophan has been measured in the environment of a cold, supersonic free jet. Analysis of the region of the spectrum near the electronic origin indicates that the electronic excitation spectrum contains features which arise from various ground state conformers of tryptophan, confirming our previous assignment of these features. Under the conditions of our experiment the conformers do not interconvert in the excited state during the fluorescence liftime. Analysis of the dispersed emission spectrum of one conformer reveals broad red-shifted fluorescence which exists even when the electronic origin transition is excited. This broad red-shifted fluorescence is produced by the formation of an intramolecular exciplex involving excited state proton transfer to form a zwitterion. Molecules which do not have the ability to form a zwitterion do not exhibit this behavior, and deuterated trytophan shows broad fluorescence in an amount consistent with a slower proton transfer rate. The significance of these results for understanding the excited state photophysics of tryptophan in solution is discussed.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 2534-2541 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The electronic spectrum of the amino acid tryptophan has been measured in the environment of a cold, supersonic molecular beam. The resonantly enhanced two-photon ionization spectrum of tryptophan shows some features characteristic of more volatile indole derivitives, however the region of the spectrum near the origin shows distinctive low frequency structure absent from the simpler indole containing molecules. The power dependence of the spectrum reveals features which can be attributed to several conformers of tryptophan in the molecular beam. One of these conformers shows a nearly harmonic 26 cm−1 vibrational progression which does not appear in the spectra of other indole derivitives, and the intensity pattern of this progression indicates that this particular conformer undergoes a significant geometry change upon electronic excitation. The lack of many extensive vibrational progressions in the electronic spectrum indicates that the excited state conformers of tryptophan are similar to those in the ground electronic state. The identification of a small number of stable tryptophan conformers is important for understanding the photophysics of tryptophan in solution.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 4819-4820 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 6539-6549 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The electronic spectroscopy of four different tryptophan analogs, 3-indole acetic acid, 3-indole propionic acid, tryptamine, and N-acetyltryptophan ethyl ester (NATE) has been studied in a supersonic molecular beam using laser-induced fluorescence and resonantly enhanced two-photon ionization. The electronic transition to the lowest excited singlet state occurs at 35 039, 34 965, 34 918, and 34 881±2 cm−1 for 3-indole acetic acid, 3-propionic acid, tryptamine, and NATE, respectively. The relatively small differences in the electronic origin transition frequencies suggests that the lowest excited singlet state for all of these moelcules is the 1Lb state. The spectra reveal that each of these molecules have stable conformers in the gas phase, analogous to our previously reported studies of tryptophan. A low frequency vibrational mode has been observed in 3-indole propionic acid, tryptamine, NATE, and tryptophan which involves motion of the side chain against the indole ring. We have observed that forming a van der Waals complex between tryptamine and a single methanol molecule causes the spectral features due to different conformers of the free molecule to collapse to a single line, suggesting that one particular conformer becomes the most stable species. This emphasizes the importance of including solvent interactions in any attempt to model the behavior of these molecules in solution.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    s.l. : American Chemical Society
    Journal of the American Chemical Society 107 (1985), S. 277-278 
    ISSN: 1520-5126
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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