title: Rational Design of a Ratiometric Fluorescent Probe Based on Arene-Metal-Ion Contact for Endogenous Hydrogen Sulfide Detection in Living Cells.
abstract: We report the design and development of a fluorescent Cd(II) ion complex that is capable of the ratiometric detection of H2 S in living cells. This probe exploits the metal-ion-induced emission red shift resulting from direct contact between the aromatic ring of a fluorophore and a metal ion (i.e., arene-metal-ion or "AM" contact). The Cd(II) complex displays a large emission blue shift upon interaction with H2 S as the Cd(II) -free ligand is released by the formation of cadmium sulfide. Screening of potential ligands and fluorophores led to the discovery of a pyronine-type probe, 6⋅Cd(II) , that generated a sensitive and rapid ratio value change upon interaction with H2 S, without interference from the glutathione that is abundant in the cell. The membrane-impermeable 6⋅Cd(II) was successfully translocated into live cells by using an oligo-arginine peptide and pyrenebutylate as carriers. As such, 6⋅Cd(II) was successfully applied to the ratiometric detection of both exogenous and endogenous H2 S produced by the enzymes in living cells, thus demonstrating the utility of 6⋅Cd(II) in biological fluorescence analysis.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582 (Japan).
authors.forename: Ryosuke
authors.initials: R
authors.lastname: Kawagoe
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582 (Japan).
authors.forename: Ippei
authors.initials: I
authors.lastname: Takashima
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582 (Japan).
authors.forename: Kazuteru
authors.initials: K
authors.lastname: Usui
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582 (Japan).
authors.forename: Anna
authors.initials: A
authors.lastname: Kanegae
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582 (Japan).
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Ozawa
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582 (Japan). ojida@phar.kyushu-u.ac.jp.
authors.forename: Akio
authors.initials: A
authors.lastname: Ojida
mesh_terms: D002470:Cell Survival; D015195:Drug Design; D005456:Fluorescent Dyes / Q000737:chemistry*; D006367:HeLa Cells; D006801:Humans; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D006862:Hydrogen Sulfide / Q000378:metabolism*; D008024:Ligands; D057054:Molecular Imaging / Q000379:methods*; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D005456:Fluorescent Dyes; D006841:Hydrocarbons, Aromatic; D008024:Ligands; D009942:Organometallic Compounds; D006862:Hydrogen Sulfide
keywords: analytical methods; cadmium; fluorescent probes; hydrogen sulfide; imaging agents; noncovalent interactions