Document Server@UHasselt >
Research >
Research publications >

Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/2317

Title: Identifiability analysis of models for reversible intermolecular two-state excited-state processes coupled with species-dependent rotational diffusion monitored by time-resolved fluorescence depolarization
Authors: SZUBIAKOWSKI, Jacek
DALE, Robert
Boens, N
Issue Date: 2004
Citation: JOURNAL OF CHEMICAL PHYSICS, 121(16). p. 7829-7839
Abstract: A deterministic identifiability analysis of the kinetic model for a reversible intermolecular two-state excited-state process with species-dependent rotational diffusion described by Brownian reorientation is presented. The cases of both spherically and cylindrically symmetric rotors, with no change in the principal axes of rotation on interconversion in the latter case, are specifically considered. The identifiability analysis is carried out in terms of compartmental modeling based on the S(t)=I-parallel to(t)+2I(perpendicular to)(t) and D(t)=I-parallel to(t)-I-perpendicular to(t) functions, where I-parallel to(t) and I-perpendicular to(t) are the delta-response functions for fluorescence, polarized, respectively, parallel and perpendicular to the electric vector of linearly polarized excitation. It is shown that, from polarized time-resolved fluorescence data collected at two concentrations of coreactant and three appropriately chosen emission wavelengths, (a) a unique set of rate constants for the overall excited-state process is always obtained by making use of polarized measurements and (b) the rotational diffusion constants and geometrical factors associated with the different anisotropy decay components can be uniquely determined and assigned to each species. The geometrical factors are determined by the absorption and emission transitions in the two rotating species. For spherical rotors, these factors depend directly on the relative orientations of the transition moments, while for cylindrically symmetric rotors they depend on the orientations with respect to each other and to the symmetry axis. (C) 2004 American Institute of Physics.
Notes: Transnatl Univ Limburg, Sch Life Sci, Limburgs Univ Centrum, Biomed Onderzoeksinst, B-3590 Diepenbeek, Belgium. Univ Warmia & Masuria Olsztyn, Dept Phys & Comp Methods, PL-10561 Olsztyn, Poland. Univ London Kings Coll, GKT Sch Biomed Sci, Randall Div Cell & Mol Biophys, London SE1 1UL, England. Katholieke Univ Leuven, Dept Chem, B-3001 Heverlee, Belgium. Nicholas Copernicus Univ, Aleksander Jablonski Inst Phys, PL-87100 Torun, Poland. Christie Hosp NHS Trust, Paterson Inst Canc Res, Manchester M20 4BX, Lancs, England.Ameloot, M, Transnatl Univ Limburg, Sch Life Sci, Limburgs Univ Centrum, Biomed Onderzoeksinst, B-3590 Diepenbeek, Belgium.marcel.ameloot@luc.ac.be
URI: http://hdl.handle.net/1942/2317
DOI: 10.1063/1.1798972
ISI #: 000224456500035
ISSN: 0021-9606
Category: A1
Type: Journal Contribution
Validation: ecoom, 2005
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.