title: Substitution pattern reverses the fluorescence response of coumarin glycoligands upon coordination with silver (I).
abstract: Development of sugar-based fluorescence (FL) chemo-probes is of much interest since sugars are biocompatible, water-soluble and structurally rigid natural starting materials. We report here that fluorescent glycoligands with two triazolyl coumarin moieties installed onto the different positions of an identical glucosyl nucleus exert completely reversed optical response to a metal ion. C3,4-, C2,3- and C4,6-di-substituted coumarin glucosides synthesized by a click reaction similarly showed a selective FL variation in the presence of silver (I) among a range of metal cations in an aqueous solution. However, the variation was determined to be converse: the FL of the C3,4-ligand was quenched whereas that of the C2,3/C4,6-ligand tangibly enhanced. FL and NMR titrations suggested that this divergence was due to the distinct complexation modes of the conformationally constrained ligands with the ion. The optimal motifs of the ligand-ion complexation were predicted by a computational simulation. Finally, the C2,3-ligand was determined to be of low cytotoxicity and applicable in the FL imaging of silver ions internalized by live cells.
authors.affiliation: Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China.
authors.forename: De-Tai
authors.initials: DT
authors.lastname: Shi
authors.affiliation: 1] Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China [2] National Center for Drug Screening, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 189 Guo Shoujing Rd., Shanghai 201203, P. R. China.
authors.forename: Xiao-Li
authors.initials: XL
authors.lastname: Wei
authors.affiliation: Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China.
authors.forename: Yayun
authors.initials: Y
authors.lastname: Sheng
authors.affiliation: National Center for Drug Screening, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 189 Guo Shoujing Rd., Shanghai 201203, P. R. China.
authors.forename: Yi
authors.initials: Y
authors.lastname: Zang
authors.affiliation: Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China.
authors.forename: Xiao-Peng
authors.initials: XP
authors.lastname: He
authors.affiliation: PPSM, Institut d'Alembert, ENS de Cachan, CNRS UMR 8531, 61 Avenue du Pt Wilson, F-94235 Cachan, France.
authors.forename: Juan
authors.initials: J
authors.lastname: Xie
authors.affiliation: Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China.
authors.forename: Guixia
authors.initials: G
authors.lastname: Liu
authors.affiliation: Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China.
authors.forename: Yun
authors.initials: Y
authors.lastname: Tang
authors.affiliation: National Center for Drug Screening, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 189 Guo Shoujing Rd., Shanghai 201203, P. R. China.
authors.forename: Jia
authors.initials: J
authors.lastname: Li
authors.affiliation: Key Laboratory for Advanced Materials & Institute of Fine Chemicals, and Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Rd., Shanghai 200237, PR China.
authors.forename: Guo-Rong
authors.initials: GR
authors.lastname: Chen
mesh_terms: D003287:Contrast Media / Q000138:chemical synthesis*; D003374:Coumarins / Q000737:chemistry*; D006003:Glycogen / Q000737:chemistry*; D056945:Hep G2 Cells; D006801:Humans; D008024:Ligands; D008856:Microscopy, Fluorescence / Q000379:methods*; D012834:Silver / Q000737:chemistry*; D013347:Subcellular Fractions / Q000648:ultrastructure*
chemical_list: D003287:Contrast Media; D003374:Coumarins; D008024:Ligands; D012834:Silver; D006003:Glycogen; C030123:coumarin