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Perylene quinones

HYPERICIN AND ITS PERYLENE QUINONE ANALOGS PROBING STRUCTURE, DYNAMICS, AND INTERACTIONS WITH THE ENVIRONMENT... [Pg.1]

I. Introduction Excited-State Intramolecular H-Atom Transfer in Hypericin-Like Perylene Quinones... [Pg.1]

B. Are There Multiple H-Atom Transfers in the Perylene Quinones ... [Pg.2]

I. INTRODUCTION EXCITED-STATE INTRAMOLECULAR H-ATOM TRANSFER IN HYPERICINLIKE PERYLENE QUINONES... [Pg.2]

As noted above, a possible objection to our assignment of the excited-state reaction to H-atom transfer in these perylene quinone systems is the observation of mirror image symmetry between the absorption and the emission spectra, which indicates minimal structural changes between the absorbing and the emitting species. Our first attempt to explain this symmetry was to suggest that the... [Pg.7]

OUTSTANDING QUESTIONS REGARDING HYPERICIN LIKE PERYLENE QUINONES 11... [Pg.11]

If subsequent experiments do indeed demonstrate that excited-state H-atom transfer does not occur in hypomycin B, then one may draw the conclusion that multiple transfers (either concerted or stepwise) must occur in these pery-lene quinones and that by frustrating the process in one half of the molecule, the process in the other half is impeded. At this point, such reasoning is speculative and contrary to the growing body of evidence provided by theory and experiment. As indicated above, quantum mechanical calculations indicate that the double-H-atom transfer in hypericin [67] and in the perylene quinone nucleus [75] of hypocrellin is energetically unfavorable compared to the single-transfer event. Experiments for hypericin in which one half of the molecule cannot participate in H-atom transfer owing to protonation of the carbonyl group (or even perhaps complexation with a metal ion) [76] also indicate that the transfer process can still occur. [Pg.17]

As we have discussed in depth elsewhere, despite the similarities in the structures of hypericin and hypocrellin, which are centered about the perylene quinone nucleus, their excited-state photophysics exhibit rich and varied behavior. The H-atom transfer is characterized by a wide range of time constants, which in certain cases exhibit deuterium isotope effects and solvent dependence. Of particular interest is that the shortest time constant we have observed for the H-atom transfer is 10 ps. This is exceptionally long for such a process, 100 fs being expected when the solute H atom does not hydrogen bond to the solvent [62]. That the transfer time is so long in the perylene quinones has been attributed to the identification of the reaction coordinate with skeletal motions of the molecule [48, 50]. [Pg.17]

Our previous results on hypericin indicate that excited-state H-atom transfer occurs even when one of the carbonyls is prohibited from accepting a hydrogen. The presence of such a transfer is apparent under very acidic conditions in AOT reverse micelles and cannot be excluded upon chelation of Tb3+ [76]. There is thus no evidence for a concerted H-atom-transfer mechanism in hypericin. In the present study, contrary to our initial expectations, we are not even able to demonstrate that hypomycin B executes an excited-state H-atom transfer hence our investigation sheds no light on the general question of how many H atoms are transferred in the perylene quinones and whether the transfer is concerted or stepwise. On the other hand, if further investigation reveals that H-atom transfer does not occur in hypomycin B, the result would have considerable implications for an understanding of the reaction coordinate for the H-atom transfer. [Pg.19]

Hypericin and Its Perylene Quinone Analogs Probing Structure,... [Pg.279]

Calphostin C] (perylene quinone) Cladosporium cladosporioides (fungus) PKC [anticancer, antiviral]... [Pg.322]


See other pages where Perylene quinones is mentioned: [Pg.2]    [Pg.2]    [Pg.4]    [Pg.6]    [Pg.8]    [Pg.10]    [Pg.12]    [Pg.14]    [Pg.15]    [Pg.16]    [Pg.17]    [Pg.18]    [Pg.18]    [Pg.20]    [Pg.22]    [Pg.24]    [Pg.26]    [Pg.330]   


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