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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/3855

Title: KINETICS AND IDENTIFIABILITY OF INTRAMOLECULAR 2-STATE EXCITED-STATE PROCESSES - GLOBAL COMPARTMENTAL ANALYSIS OF THE FLUORESCENCE DECAY SURFACE
Authors: BOENS, N
ANDRIESSEN, R
AMELOOT, Marcel
VAN DOMMELEN, L
DE SCHRYVER, FC
Issue Date: 1992
Publisher: AMER CHEMICAL SOC
Citation: JOURNAL OF PHYSICAL CHEMISTRY, 96(15). p. 6331-6342
Abstract: This report discusses the fluorescence decay analysis of intramolecular two-state excited-state processes in terms of compartments. The kinetic equations specifying the fluorescence decay and the time course of the two excited-state species concentrations are derived in terms of the rate constants k(ij), and the spectroscopic parameters b1 and c1. b1 and c1, are respectively the relative absorbance and the normalized spectral emission weighting factor of species 1. The structural identifiability study demonstrates that at least three parameters of the intramolecular two-state excited-state process must be known in order to recover the relevant information. These three parameters can be (a) two rate constants and one spectroscopic parameter [(1) 2 k(ij) and 1 b1, (2) 2 k(ij) and 1 c1]; (by) one rate constant and two spectroscopic parameters [(3) 1 k(ij), 1 b1, and 1 c1, (4) 1 k(ij) and 2 b1, (5) 1 k(ij) and 2 c1]; and (c) three spectroscopic parameters [(6) 2 b1 and 1 c1, (7) 1 b1 and 2 c1, (8) 3 b1, (9) 3 c1]. The conditions (3), (6), and (7) require that the known (b1,c1) values do not belong to a decay trace where the preexponentials alpha-1,alpha-2 have the same absolute values but opposite signs (alpha-1/alpha-2 = -1) corresponding to (b1,c1) = (1,0) or (0,1). Conditions (6) to (9) indicate that spectroscopic information alone can suffice for the system to be identifiable. Finally, the unknown parameters are estimated from computer-generated fluorescence decay traces. The results confirm the conclusions of the identifiability study.
Notes: LIMBURGS UNIV CENTRUM,B-3590 DIEPENBEEK,BELGIUM.BOENS, N, KATHOLIEKE UNIV LEUVEN,DEPT CHEM,B-3001 HEVERLEE,BELGIUM.
URI: http://hdl.handle.net/1942/3855
DOI: 10.1021/j100194a044
ISI #: A1992JF32600044
ISSN: 0022-3654
Type: Journal Contribution
Appears in Collections: Research publications

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