Experimental-design in the global compartmental analysis of intermolecular 2-state excited-state processes
Vandenbergh, V × Kowalczyk, A Boens, Noël Deschryver, Fc #
Amer chemical soc
Journal of physical chemistry vol:98 issue:38 pages:9503-9508
In order to successfully apply global compartmental analysis of fluorescence decay surfaces it is essential to rationally select the experimental conditions. This contribution investigates the experimental design for the case of intermolecular two-state excited-state processes. Analytical calculations and global compartmental analyses of computer-generated decay traces are used to investigate which set of decay traces has to be included in the analysis to yield accurate and precise parameter estimates. The study demonstrates the importance of the appropriate choice of the excitation wavelength and coreactant concentration. The rate constants can be accurately and precisely estimated from the analysis of decays collected in the coreactant concentration range where the decay times vary. To determine the ground-state parameters, decays measured at coreactant concentrations around the ground-state dissociation constant should be added to the previous set of decays and analyzed together. It is critical that both ground-state species are excited to accurately and precisely determine the ground-state parameters. This condition also facilitates the reliable recovery of the rate constants.