TY - JOUR A1 - Rurack, Knut A1 - Danel, A. A1 - Rotkiewicz, K. A1 - Grabka, D. A1 - Spieles, Monika A1 - Rettig, W. T1 - 1,3-Diphenyl-1H-pyrazolo[3,4-b]quinoline - A Versatile Fluorophore for the Design of Brightly Emissive Molecular Sensors N2 - The 1,3-diphenyl-1H-pyrazolo[3,4-b]-quinoline chromophore is a versatile building block for the construction of brightly fluorescent molecular sensors. Facile synthetic procedures allow integration of the chromophore into fluorophore-spacer-receptor systems as well as fluoroionophores operating via intramolecular charge transfer. Whereas the former photoinduced electron-transfer probes show strong analyte-induced fluorescence enhancement, the latter exhibit bright ratiometric dual emission. Employing prototype macrocyclic receptors, the favorable signaling features for metal ion recognition are demonstrated. PY - 2002 DO - https://doi.org/10.1021/ol027025i SN - 1523-7060 SN - 1523-7052 VL - 4 IS - 26 SP - 4647 EP - 4650 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2107 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Rettig, W. T1 - ZnII and CdII complexes of 2,2'-bipyridyl-3,3'-diol: discrimination with time-resolved fluorometry PY - 1996 SN - 0179-4159 SP - 459 EP - 460 PB - Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung CY - Berlin AN - OPUS4-2102 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, Yanqin A1 - Bricks, J.L. A1 - Resch-Genger, Ute A1 - Spieles, Monika A1 - Rettig, W. T1 - CT-Operated Bifunctional Fluorescent Probe Based on a Pretwisted Donor-Donor-Biphenyl N2 - Taking into account the structural requirements for TICT-type sensor molecules, a general synthetic route to derive pH and cation-responsive pretwisted donor (D)–donor (D) biphenyls (b) equipped with donor receptors is developed and a first model compound containing a mono aza-15-crown-5 and a DMA receptor is synthesized, see Scheme 1. The spectroscopic properties of this new bifunctional D–D biphenyl are studied in the non-polar and polar solvents cyclohexane, acetonitrile, and methanol. Protonation as well as complexation studies are performed with the representative metal ions Na(I), K(I), Ca(II), Ag(I), Zn(II), Cd(II), Hg(II), and Pb(II) to reveal the potential of this molecule for communication of whether none, only one, or both binding sites are engaged in analyte coordination by spectroscopically distinguishable outputs. The results are compared to those obtained with closely related donor (D)–acceptor (A) substituted biphenyl-type sensor molecules and are discussed within the framework of neutral and ionic D – A biphenyls. KW - Fluorescent probe KW - Biphenyl KW - TICT KW - Photophysics KW - Bifunctional PY - 2006 SN - 1053-0509 SN - 1573-4994 VL - 16 IS - 3 SP - 337 EP - 348 PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-14198 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Rurack, Knut A1 - Rettig, W. T1 - Different binding modes of ZnII and CdII complexes of 2,2'-bipyridyl-3,3'-diol: evidence by time-resolved fluorometry PY - 2000 SN - 0179-4159 SP - 166 EP - 167 PB - Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung CY - Berlin AN - OPUS4-2094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Rettig, W. A1 - Rurack, Knut A1 - Sczepan, M. ED - Valeur, B. ED - Brochon, J.-C. ED - O.S. Wolfbeis, T1 - From cyanines to styryl bases-photophysical properties, photochemical mechanisms, and cation sensing abilities of charged and neutral polymethinic dyes KW - Cyaninfarbstoffe KW - Styrylfarbstoffe KW - Photophysik KW - Photochemie KW - Kationen KW - Sensor PY - 2001 SN - 3-540-67779-8 SN - 1617-1306 N1 - Serientitel: Springer Series on Fluorescence – Series title: Springer Series on Fluorescence VL - 1 SP - 125 EP - 155 PB - Springer CY - Berlin AN - OPUS4-2086 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, Yanqin A1 - Bricks, J. L. A1 - Resch-Genger, Ute A1 - Spieles, Monika A1 - Rettig, W. T1 - Bifunctional Charge Transfer Operated Fluorescent Probes with Acceptor and Donor Receptors. 2. Bifunctional Cation Coordination Behavior of Biphenyl-Type Sensor Molecules Incorporating 2,2':6',2''-Terpyridine Acceptors N2 - Based on donor (D)-acceptor (A) biphenyl (b) type molecules, a family of fluorescent reporters with integrated acceptor receptors and noncoordinating and coordinating donor substituents of varying strength has been designed for ratiometric emission sensing and multimodal signaling of metal ions and protons. In part 2 of this series on such charge transfer (CT) operated mono- and bifunctional fluorescent devices, the cation coordination behavior of the sensor molecules bpb-R equipped with a proton- and cation-responsive 2,2':6',2' '-terpyridine (bp) acceptor and either amino-type donor receptors (R = DMA, A15C5 = monoaza-15-crown-5) or nonbinding substituents (R = CF3, H, OMe) is investigated employing the representative metal ions Na(I), Ca(II), Zn(II), Hg(II), and Cu(II) and steady-state and time-resolved fluorometry. The bpb-R molecules, the spectroscopic behavior and protonation behavior of which have been detailed in part 1 of this series, present rare examples for CT-operated bifunctional fluorescent probes that can undergo consecutive and/or simultaneous analyte recognition. The analyte-mediated change of the probes' intramolecular CT processes yields complexation site- and analyte-specific outputs, i.e., absorption and fluorescence modulations in energy, intensity, and lifetime. As revealed by the photophysical studies of the cation complexes of these fluoroionophores and the comparison to other neutral and charged D-A biphenyls, the spectroscopic properties of the acceptor chelates of bpb-R and A- and D-coordinated bpb-R are governed by CT control of an excited-state barrier toward formation of a forbidden charge transfer state, by the switching between analytically favorable anti-energy and common energy gap law type behavior, and by the electronic nature of the ligated metal ion. This accounts for the astonishingly high fluorescence quantum yields of the acceptor chelates of bpb-R equipped with weak or medium-sized donors and the red emission of D- and A-coordinated bpb-R observed for nonquenching metal ions. PY - 2006 DO - https://doi.org/10.1021/jp062013q SN - 1089-5639 SN - 1520-5215 VL - 110 IS - 38 SP - 10972 EP - 10984 PB - Soc. CY - Washington, DC AN - OPUS4-14207 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute A1 - Li, Yanqin A1 - Bricks, J. L. A1 - Kharlanov, V. A1 - Rettig, W. T1 - Bifunctional Charge Transfer Operated Fluorescent Probes with Acceptor and Donor Receptors - 1. Biphenyl-Type Sensor Molecules with Protonation-Induced Anti-Energy Gap Rule Behavior N2 - On the basis of biphenyl (b) type molecules bpb-R substituted with a 2,2':6',2' '-terpyridine acceptor (bp) and either amino-type donor receptors (R = dimethylamino (DMA), A15C5 = monoaza-15-crown-5) or nonbinding substituents (R = CF3, H, OMe) of various donor strengths, we developed a family of charge transfer (CT) operated monofunctional and bifunctional fluorescent sensors for protons and metal ions. These molecules are designed to communicate the interaction of an analyte with the acceptor and the donor receptor differing in basicity and cation selectivity by clearly distinguishable spectral shifts and intensity modulations in absorption and in emission as well as in fluorescence lifetime. From the dependence of the fluorescence spectra, fluorescence quantum yields, and fluorescence lifetimes of bpb-R on solvent polarity and proton concentration, the photophysics of bpb-R and their protonated analogues can be shown to be governed by the relaxation to a CT state of forbidden nature and by the switching between anti-energy and energy gap law type behaviors. This provides the basis for analytically favorable red shifted emission spectra in combination with comparatively high fluorescence quantum yields. Accordingly, bpb-H and bpb-OMe are capable of ratiometric emission signaling of protons. bpb-DMA reveals a protonation-induced ON-OFF-ON switching of its emission. PY - 2006 DO - https://doi.org/10.1021/jp062010d SN - 1089-5639 SN - 1520-5215 VL - 110 IS - 38 SP - 10956 EP - 10971 PB - Soc. CY - Washington, DC AN - OPUS4-14208 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bricks, J. L. A1 - Slominskii, J. L. A1 - Kudinova, M. A. A1 - Tolmachev, A. I. A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Rettig, W. T1 - Syntheses and photophysical properties of a series of cation-sensitive polymethine and styryl dyes N2 - The syntheses and photophysical properties of 20 cation-sensitive fluoroionophores carrying the tetraoxa monoaza 15-crown-5 receptor are described and discussed. Whereas complexation induces only weak effects for the positively charged hemicyanine probes, the closely related styryl dyes show stronger changes in their photophysical properties upon cation binding in the analytically advantageous near-infrared (NIR) region. The strongest effects in both cation-induced spectral effects and complex stability constants are observed for the uncharged probes of styryl base-type, but these probes usually absorb and emit at shorter wavelengths in the UV/VIS region. For both styryl dyes and styryl bases, in some cases cation-induced fluorescence enhancement or quenching is found. KW - Fluorescence KW - Ionophores KW - Unsymmetrical cyanines KW - Styryl dyes KW - Styryl bases PY - 2000 DO - https://doi.org/10.1016/S1010-6030(00)00208-2 SN - 1010-6030 SN - 1873-2666 VL - 132 IS - 3 SP - 193 EP - 208 PB - Elsevier CY - Lausanne AN - OPUS4-2089 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Dekhtyar, M. A1 - Bricks, J. A1 - Resch-Genger, Ute A1 - Rettig, W. T1 - Quantum yield switching of fluorescence by selectively bridging single and double bonds in chalcones - involvement of two different types of conical intersections N2 - From the fluorescence properties of chalcones as a function of solvent polarity, and by the comparison to derivatives with donors and acceptors and with various selectively bridged bonds, it can be concluded that two emissive and two nonemissive states are needed to describe the fluorescence behavior. Three of these states are connected with bond twisting and lead to species with high or low dipole moment, two of them situated in the proximity of a conical intersection. KW - Fluoreszenz KW - Konische Durchschneidung PY - 1999 DO - https://doi.org/10.1021/jp992878m SN - 1089-5639 SN - 1520-5215 VL - 103 IS - 48 SP - 9626 EP - 9635 PB - Soc. CY - Washington, DC AN - OPUS4-2093 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Rettig, W. A1 - Resch-Genger, Ute T1 - Unusually high cation-induced fluorescence enhancement of a structurally simple intrinsic fluoroionophore with a donor-acceptor-donor constitution N2 - Upon cation complexation, donor–acceptor–donor–substituted intrinsic fluoroionophore 3 shows red-shifted emission spectra accompanied by an extraordinarily high fluorescence enhancement. KW - Fluoreszenz KW - Ionophor KW - Ladungstransfer PY - 2000 DO - https://doi.org/10.1039/a909899b SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x VL - 2000 IS - 5 SP - 407 EP - 408 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-2091 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Rettig, W. T1 - Global analysis of time-resolved emission-a powerful tool for the analytical discrimination of chemically similar ZnII and CdII complexes N2 - The simultaneous analytical discrimination of spectrally very similar components with time- and wavelength-resolved fluorescence spectroscopy is demonstrated for the fluorescent probe BP(OH)2 and its complexes with the d10 metal ions CdII and ZnII in water. Whereas the absorption and emission spectra of the three components largely overlap the fluorescence lifetimes differ significantly. As a consequence, analyzing steady-state emission spectra of samples containing unknown amounts of both metal ions yields poor results for the analytical validity but the recording of fluorescence decay curves at different emission wavelengths improves the quality of the results drastically. The two techniques are compared in terms of goodness and analytical accuracy of the fit as well as analytical applicability. KW - Time-resolved KW - Fluorescence KW - ZnII KW - CdII KW - 2,2´-Bipyridyl-3,3´-diol PY - 1998 DO - https://doi.org/10.1016/S1010-6030(98)00369-4 SN - 1010-6030 SN - 1873-2666 VL - 118 IS - 3 SP - 143 EP - 149 PB - Elsevier CY - Lausanne AN - OPUS4-2096 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Sczepan, M. A1 - Spieles, Monika A1 - Resch-Genger, Ute A1 - Rettig, W. T1 - Correlations between complex stability and charge distribution in the ground state for CaII and NaI complexes of charge transfer (CT) chromo- and fluoroionophores N2 - Several series of crown fluoro-chromo-ionophores covering a broad spectral range are investigated experimentally and compared to their theoretically studied dimethylamino (DMA) analogues. It is shown that the logarithm of the complex stability constants log KS for NaI and CaII ions do not correlate with the observed complexation-induced shift. Likewise, an unsatisfactory correlation is found between the local charge density on the amino nitrogen of the DMA dyes and log KS. However, using the charge of the whole dimethylamino group instead strongly improves this correlation. This can be understood by considering pyramidalization and hyperconjugation effects on the amino nitrogen. The observed correlation allows a novel approach to the design of fluoroionophores with optimized properties. KW - Ionophor KW - Komplex KW - Ladungsverteilung KW - Calcium KW - Natrium PY - 2000 DO - https://doi.org/10.1016/S0009-2614(00)00203-7 SN - 0009-2614 SN - 1873-4448 VL - 320 IS - 1-2 SP - 87 EP - 94 PB - North-Holland Publ. Co. CY - Amsterdam AN - OPUS4-2090 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Kollmannsberger, M. A1 - Daub, J. A1 - Rettig, W. T1 - Design of an efficient charge-transfer processing molecular system containing a weak electron donor: spectroscopic and redox properties and cation-induced fluorescence enhancement N2 - The acceptor strength of the boron-dipyrromethene chromophore in directly linked donor–acceptor compounds can be tuned by substituents in such a way that a fast excited state charge transfer takes place even for the comparatively weak benzo crown electron donor. This leads to strong fluorescence quenching. Upon binding of cations (Na+ and K+) to the benzo crown receptor, the donor properties of the latter are further reduced, partly suppressing charge transfer. Large fluorescence enhancement factors and cation-selective fluorescence decay times result which are the basis for improved analytical application of these dyes as highly sensitive fluorescent probes. PY - 2000 DO - https://doi.org/10.1016/S0009-2614(00)01058-7 SN - 0009-2614 SN - 1873-4448 VL - 329 IS - 5-6 SP - 363 EP - 369 PB - North-Holland Publ. Co. CY - Amsterdam AN - OPUS4-1049 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Rettig, W. T1 - Fluoreszenzmarker für Schwer- und Übergangsmetallionen - Selektivität durch gezieltes Rezeptordesign und ionenspezifische Fluoreszenzverstärkung T2 - Tagung "Tag der Chemie 2000" CY - Potsdam, Deutschland DA - 2000-11-08 KW - Fluoreszenzmarker KW - Schwermetalle KW - Rezeptoren PY - 2000 SP - 87 AN - OPUS4-1016 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -