title: Kinetics study of the photocleavage of (coumarin-4-yl)methyl esters.
abstract: Photolabile coumarinylmethyl esters of biomolecules (caged compounds) are new tools for studying spatial and time-dependent aspects of signal transduction in living cells. Herein we describe a fluoresence spectroscopic method for the determination of the rate constants of the photolysis steps of such caged compounds using (6.7-dimethoxycoumarin-4-yl)methyl diethyl phosphate (DMCM-DEP) and sodium (6,7-dimethoxycoumarin-4-yl)methyl sulfate (DMCM-S). DMCM-DEP and DMCM-S are caged compounds which photorelease a proton, the corresponding acid anion, and the strongly fluorescent alcohol DMCM-OH upon excitation. The results of stationary and time-resolved measurements of the photochemistry and the luminescence of both caged compounds indicate that DMCM-OH is produced already during the excitation pulse. The quantitative analysis of the data demonstrates that the first step of the reaction--heterolytic bond cleavage of the coumarinylmethyl ester leading to the ion pair of a DMCM cation and an acid anion--is very fast with a rate constant of k1 approximately 2 x 10(10) s(-1). Recombination of the ion pair occurs with a rate constant of k(rec) approximately 2.3 x 10(9) s(-1) and is about 10 times faster than the competing hydrolysis reaction of the DMCM cation yielding DMCM-OH and a proton. Thus, both caged compounds belong to the fastest phototriggers known.
authors.affiliation: Institute of Physical and Theoretical Chemistry, J. W. Goethe-University, Marie-Curie-Str. 11, D60439 Frankfurt am Main, Germany.
authors.forename: Reinhard
authors.initials: R
authors.lastname: Schmidt
authors.forename: Daniel
authors.initials: D
authors.lastname: Geissler
authors.forename: Volker
authors.initials: V
authors.lastname: Hagen
authors.forename: Jürgen
authors.initials: J
authors.lastname: Bendig
mesh_terms: D003374:Coumarins / Q000737:chemistry* / Q000528:radiation effects; D004952:Esters / Q000737:chemistry* / Q000528:radiation effects; D007700:Kinetics; D015394:Molecular Structure; D010782:Photolysis; D012996:Solutions; D013050:Spectrometry, Fluorescence; D014466:Ultraviolet Rays; D014867:Water / Q000737:chemistry
chemical_list: D003374:Coumarins; D004952:Esters; D012996:Solutions; D014867:Water