title: Ensemble and single-molecule studies on fluorescence quenching in transition metal bipyridine-complexes.
abstract: Beyond their use in analytical chemistry fluorescent probes continuously gain importance because of recent applications of single-molecule fluorescence spectroscopy to monitor elementary reaction steps. In this context, we characterized quenching of a fluorescent probe by different metal ions with fluorescence spectroscopy in the bulk and at the single-molecule level. We apply a quantitative model to explain deviations from existing standard models for fluorescence quenching. The model is based on a reversible transition from a bright to a dim state upon binding of the metal ion. We use the model to estimate the stability constants of complexes with different metal ions and the change of the relative quantum yield of different reporter dye labels. We found ensemble data to agree widely with results from single-molecule experiments. Our data indicates a mechanism involving close molecular contact of dye and quenching moiety which we also found in molecular dynamics simulations. We close the manuscript with a discussion of possible mechanisms based on Förster distances and electrochemical potentials which renders photo-induced electron transfer to be more likely than Förster resonance energy transfer.
authors.affiliation: Cellnetworks Cluster and Institute of Physical Chemistry, Heidelberg University, Heidelberg, Germany.
authors.forename: Dominik
authors.initials: D
authors.lastname: Brox
authors.forename: Alexander
authors.initials: A
authors.lastname: Kiel
authors.forename: Svenja Johanna
authors.initials: SJ
authors.lastname: Wörner
authors.forename: Markus
authors.initials: M
authors.lastname: Pernpointner
authors.forename: Peter
authors.initials: P
authors.lastname: Comba
authors.forename: Bodo
authors.initials: B
authors.lastname: Martin
authors.forename: Dirk-Peter
authors.initials: DP
authors.lastname: Herten
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry*; D004247:DNA / Q000737:chemistry; D008958:Models, Molecular; D012235:Rhodamines / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D012235:Rhodamines; D028561:Transition Elements; D015082:2,2'-Dipyridyl; C005358:tetramethylrhodamine; D004247:DNA