title: Rational principles for modulating fluorescence properties of fluorescein.
abstract: Rational design strategies based on practical fluorescence modulation mechanisms would enable us to rapidly develop novel fluorescence probes for target molecules. Here, we present a practical and general principle for modulating the fluorescence properties of fluorescein. We hypothesized that (a) the fluorescein molecule can be divided into two moieties, i.e., the xanthene moiety as a fluorophore and the benzene moiety as a fluorescence-controlling moiety, even though there is no obvious linker structure between them, and (b) the fluorescence properties can be modulated via a photoinduced electron transfer (PeT) process from the excited fluorophore to a reducible benzene moiety (donor-excited PeT; d-PeT). To evaluate the relationship between the reduction potential of the benzene moiety and the fluorescence properties, we designed and synthesized various derivatives in which the reduction potential of the benzene moiety was fine tuned by introducing electron-withdrawing groups onto the benzene moiety. Our results clearly show that the fluorescence properties of fluorescein derivatives were indeed finely modulated depending upon the reduction potential of the benzene moiety. This information provides a basis for a practical strategy for rational design of novel functional fluorescence probes.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Tasuku
authors.initials: T
authors.lastname: Ueno
authors.forename: Yasuteru
authors.initials: Y
authors.lastname: Urano
authors.forename: Ken-Ichi
authors.initials: K
authors.lastname: Setsukinai
authors.forename: Hideo
authors.initials: H
authors.lastname: Takakusa
authors.forename: Hirotatsu
authors.initials: H
authors.lastname: Kojima
authors.forename: Kazuya
authors.initials: K
authors.lastname: Kikuchi
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Tetsuo
authors.initials: T
authors.lastname: Nagano
mesh_terms: D015195:Drug Design; D004563:Electrochemistry; D005452:Fluoresceins / Q000737:chemistry*; D005453:Fluorescence; D005456:Fluorescent Dyes / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D017382:Reactive Oxygen Species / Q000032:analysis / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013329:Structure-Activity Relationship; D013816:Thermodynamics
chemical_list: D005452:Fluoresceins; D005456:Fluorescent Dyes; D017382:Reactive Oxygen Species