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Title: The Dead-End Elimination method, tryptophan rotamers, and fluorescence lifetimes
Authors: Hellings, Mario ×
De Maeyer, Marc
Verheyden, Stefan
Hao, Q
Van Damme, EJM
Peumans, WJ
Engelborghs, Yves #
Issue Date: Jan-2003
Publisher: Biophysical society
Series Title: Biophysical Journal vol:85 issue:3 pages:1894-1902
Abstract: The Dead-End Elimination method was used to identify 40 low energy microconformations of 16 tryptophan residues in eight proteins. Single Trp-mutants of these proteins all show a double- or triple-exponential fluorescence decay. For ten of these lifetimes the corresponding rotameric state could be identified by comparing the bimolecular acrylamide quenching constant (k(q)) and the relative solvent exposure of the side chain in that microstate. In the absence of any identifiable quencher, the origin of the lifetime heterogeneity is interpreted in terms of the electron transfer process from the indole Cepsilon3 atom to the carbonyl carbon of the peptide bond. Therefore it is expected that a shorter [Cepsilon3-C=O] distance leads to a shorter lifetime as observed for these ten rotamers. Applying the same rule to the other 30 lifetimes, a link with their corresponding rotameric state could also be made. In agreement with the theory of Marcus and Sutin, the nonradiative rate constant shows an exponential relationship with the [Cepsilon3-C=O] distance for the 40 datapoints.
URI: 
ISSN: 0006-3495
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Biochemistry, Molecular and Structural Biology Section
× corresponding author
# (joint) last author

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