Design, synthesis and photophysical studies of an emissive, europium based, sensor for zinc.

The synthesis of the probe complex . and photophysical studies in aqueous media are described. . is designed to be luminescently responsive to Zn(II) in the presence of a competitive ionic mixture at pH 7.4. The structure of the complex is based upon a carboxylate functionalized azamacrocycle and possesses a chromophoric bis-picolyl unit for binding Zn(II). The effect on both ligand fluorescence and Eu(III) phosphorescence was investigated in the presence and absence of Zn(II). The study revealed that binding Zn(II) increased the intensity of ligand fluorescence and modulated the inner sphere hydration number of Eu(III) (q increases from 0 to 2). This modulation in coordination environment induced pronounced changes in the form of the steady state spectra allowing the presence of Zn(II) to be signalled by both changes in emission intensity and lifetime.

[1]  J. Bünzli,et al.  Lanthanide luminescent mesomorphic complexes with macrocycles derived from diaza-18-crown-6 , 2005 .

[2]  Thorfinnur Gunnlaugsson,et al.  The Selectivity of Reversible Oxy-Anion Binding in Aqueous Solution at a Chiral Europium and Terbium Center: Signaling of Carbonate Chelation by Changes in the Form and Circular Polarization of Luminescence Emission , 2000 .

[3]  David Parker,et al.  Luminescent lanthanide sensors for pH, pO2 and selected anions , 2000 .

[4]  B. Imperiali,et al.  Derivatives of 8-hydroxy-2-methylquinoline are powerful prototypes for zinc sensors in biological systems. , 2001, Journal of the American Chemical Society.

[5]  Stephen Faulkner,et al.  Lanthanide Complexes for Luminescence Imaging Applications , 2005 .

[6]  A. M. Glazer,et al.  A nitrogen‐gas‐stream cryostat for general X‐ray diffraction studies , 1986 .

[7]  T. Gunnlaugsson,et al.  Responsive lanthanide luminescent cyclen complexes: from switching/sensing to supramolecular architectures. , 2005, Chemical communications.

[8]  C. Fahrni,et al.  Aqueous Coordination Chemistry of Quinoline-Based Fluorescence Probes for the Biological Chemistry of Zinc , 1999 .

[9]  T. Gunnlaugsson,et al.  Reversible anion binding in aqueous solution at a cationic heptacoordinate lanthanide centre: selective bicarbonate sensing by time-delayed luminescence , 1998 .

[10]  T. Gunnlaugsson,et al.  Selective signalling of zinc ions by modulation of terbium luminescence , 2000 .

[11]  T. Gunnlaugsson,et al.  A model system using modulation of lanthanide luminescence to signal Zn2+ in competitive aqueous media , 2000 .

[12]  J. Bünzli,et al.  Taking advantage of luminescent lanthanide ions. , 2005, Chemical Society reviews.

[13]  J. Williams,et al.  Luminescent sensors for pH, pO2, halide and hydroxide ions using phenanthridine as a photosensitiser in macrocyclic europium and terbium complexes , 1998 .

[14]  T. Gunnlaugsson.  Luminescent europium tetraazamacrocyclic complexes with wide range pH sensitivity , 1998 .

[15]  David Parker,et al.  Taking advantage of the pH and pO2 sensitivity of a luminescent macrocyclic terbium phenanthridyl complex , 1998 .

[16]  W. H. Betts,et al.  Complexation of zinc(II) and other divalent metal ions by the fluorophore 2-methyl-8-(toluene-p-sulfonamido)-6-quinolyloxyacetic acid in 50% aqueous ethanol , 1997 .

[17]  Y. Urano,et al.  Development of a zinc ion-selective luminescent lanthanide chemosensor for biological applications. , 2004, Journal of the American Chemical Society.

[18]  J. Williams,et al.  Luminescent chemosensors for pH, halide and hydroxide ions based onkinetically stable, macrocyclic europium–phenanthridiniumconjugates , 1997 .

[19]  D. Parker,et al.  Chemoselective signalling of selected phospho-anions using lanthanide luminescence. , 2004, Chemical communications.

[20]  R. Kataky,et al.  Narrow-range optical pH sensors based on luminescent europium and terbium complexes immobilized in a sol gel glass. , 2001, Inorganic chemistry.

[21]  Yasunori Hayashi,et al.  ZP8, a neuronal zinc sensor with improved dynamic range; imaging zinc in hippocampal slices with two-photon microscopy. , 2004, Inorganic chemistry.

[22]  S. Faulkner,et al.  Long wavelength sensitizers for europium(III) luminescence based on acridone derivatives , 2002 .

[23]  S. Lis,et al.  Energy transfer in solution of lanthanide complexes , 2002 .

[24]  Y. Urano,et al.  Highly Zinc-Selective Fluorescent Sensor Molecules Suitable for Biological Applications , 2000 .

[25]  Roger Y. Tsien,et al.  A New Cell-Permeable Fluorescent Probe for Zn2+ , 2000 .

[26]  Massimo Guardigli,et al.  Luminescent lanthanide complexes as photochemical supramolecular devices , 1993 .

[27]  Christopher J. Chang,et al.  A tautomeric zinc sensor for ratiometric fluorescence imaging: application to nitric oxide-induced release of intracellular zinc. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[28]  K. Kikuchi,et al.  Zinc sensing for cellular application. , 2004, Current opinion in chemical biology.

[29]  T. Gunnlaugsson,et al.  The Formation of Luminescent Supramolecular Ternary Complexes in Water: Delayed Luminescence Sensing of Aromatic Carboxylates Using Coordinated Unsaturated Cationic Heptadentate Lanthanide Ion Complexes , 2003 .

[30]  J. Bünzli,et al.  Luminescence-detected phase transitions in lanthanide-containing liquid crystals. , 2003, Chemical communications.

[31]  Terence E. Rice,et al.  Proton‐Controlled Switching of Luminescence in Lanthanide Complexes in Aqueous Solution: pH Sensors Based on Long‐Lived Emission , 1996 .

[32]  R. Mahajan,et al.  Anion receptor functions of lanthanide tris(beta-diketonate) complexes: naked eye detection and ion-selective electrode determination of Cl- anion. , 2003, Chemical communications.

[33]  Vincenzo Balzani,et al.  ANTENNA EFFECT IN LUMINESCENT LANTHANIDE CRYPTATES: A PHOTOPHYSICAL STUDY , 1990 .

[34]  A. Beeby,et al.  pH Dependence of the energy transfer mechanism in a phenanthridine-appended ytterbium complex , 2002 .

[35]  D. Parker.  Excitement in f block: structure, dynamics and function of nine-coordinate chiral lanthanide complexes in aqueous media. , 2004, Chemical Society reviews.

[36]  Horst Puschmann,et al.  Being excited by lanthanide coordination complexes: aqua species, chirality, excited-state chemistry, and exchange dynamics. , 2002, Chemical reviews.

[37]  T. Gunnlaugsson,et al.  Delayed lanthanide luminescence sensing of aromatic carboxylates using heptadentate triamide Tb(III) cyclen complexes: the recognition of salicylic acid in water. , 2002, Chemical communications.

[38]  S. Bhattacharya,et al.  First report of Zn2+ sensing exclusively at mesoscopic interfaces. , 2003, Chemical communications.