Document Server@UHasselt >
Research publications >
Please use this identifier to cite or link to this item:
|Title: ||Distinction between different competing kinetic models of irreversible intramolecular two-state excited-state processes with added quencher: global compartmental analysis of the fluorescence decay surface|
|Authors: ||van Dommelen, L.|
de Schryver, F.C.
|Issue Date: ||1995|
|Citation: ||Journal of physical chemistry, 99(22). p. 8959-8971|
|Abstract: ||In this report we investigate how, even in the absence of any a priori information, one can distinguish between
competing irreversible intramolecular two-state excited-state processes. Only two different kinetic models
are possible for irreversible intramolecular two-state excited-state processes: (i) one with a unidirectional
excited-state process and (ii) one without an excited-state process. The distinction between these models is
based on the collection of a fluorescence decay surface with at least three quencher concentrations and the
use of standard global biexponential and global compartmental analyses. Standard global biexponential analysis
provides estimates for the preexponential factors and decay times which, together with the steady-state
fluorescence spectrum, allow the construction of decay-associated emission spectra. Two series of global
compartmental analyses have to be performed whereby (i) k01 is kept constant at various preset values while
k12 is held fixed at zero and whereby (ii) k02 is scanned while k21 is held constant at zero. kol denotes the rate
constant of deactivation of excited species i*, klz represents the rate constant of transformation of excited
species 2* into 1*, and k21 describes the opposite process. If negative preexponentials-indicative of a
unidirectional excited-state process-are obtained in the global biexponential analysis, the statistical goodnessof-
fit criteria of the repetitive global compartmental analyses allows one to determine the direction of the
unidirectional excited-state process. When only positive preexponentials are obtained in the global biexponential
analysis, the decay-associated emission spectra should be compared to the species-associated emission spectra.
If both sets of spectra coincide, no excited-state process occurs. Otherwise, two solutions in which one rate
constant of interconversion is zero are mathematically possible. It is impossible to distinguish between these
two nontrivial alternative solutions.|
|Type: ||Journal Contribution|
|Appears in Collections: ||Research publications|
Files in This Item:
There are no files associated with this item.
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.