Turn-on fluorescence sensing of nucleoside polyphosphates using a xanthene-based Zn(II) complex chemosensor.
Fluorescence sensing with small molecular chemosensors is a versatile technique for elucidation of function of various biological substances. We now report a new fluorescent chemosensor for nucleoside polyphosphates such as ATP using metal-anion coordination chemistry. The chemosensor 1-2Zn(II) is comprised of the two sites of 2,2'-dipicolylamine (Dpa)-Zn(II) as the binding motifs and xanthene as a fluorescent sensing unit for nucleoside polyphosphates. The chemosensor 1-2Zn(II) selectively senses nucleoside polyphosphates with a large fluorescence enhancement (F/F(o) > 15) and strong binding affinity (K(app) approximately = 1 x 10(6) M(-1)), whereas no detectable fluorescence change was induced by monophosphate species and various other anions. The 'turn-on,' fluorescence of 1-2Zn(II) is based on a new mechanism, which involves the binding-induced recovery of the conjugated form of the xanthene ring from its nonfluorescent deconjugated state which was formed by an unprecedented nucleophilic attack of zinc-bound water. The selective and highly sensitive ability of 1-2Zn(II) to detect nucleoside polyphosphates enables its bioanalytical applications in fluorescence visualization of ATP particulate stores in living cells, demonstrating the potential utility of 1-2Zn(II).
Ojida
Akio
A
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura Campus, Nishikyo-ku, Kyoto, 615-8510, Japan.
Takashima
Ippei
I
Kohira
Takahiro
T
Nonaka
Hiroshi
H
Hamachi
Itaru
I
D000255:Adenosine Triphosphate / Q000032:analysis; D015374:Biosensing Techniques / Q000379:methods; D005456:Fluorescent Dyes / Q000138:chemical synthesis / Q000737:chemistry*; D006801:Humans; D019169:Jurkat Cells; D009711:Nucleotides / Q000032:analysis*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013050:Spectrometry, Fluorescence / Q000379:methods*; D013601:T-Lymphocytes / Q000737:chemistry; D014966:Xanthenes / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
D005456:Fluorescent Dyes; D009711:Nucleotides; D009942:Organometallic Compounds; D014966:Xanthenes; D000255:Adenosine Triphosphate; D015032:Zinc