TY - RPRT A1 - Rurack, Knut T1 - Steady-State and Time-Resolved Spectroscopy of Ion-Sensitive Fluorescent Probes N2 - Im Mittelpunkt der vorliegenden Arbeit stehen Untersuchungen des spektroskopischen und komplexometrischen Verhaltens verschiedener Ionen-sensitiver Fluoreszenzsonden. Drei der vier Sondentypen folgen dabei einem herkömmlichen Prinzip zur Signalerzeugung und entsprechen in ihrem molekularen Aufbau einem fluoreszierenden Liganden (BP(OH)2 ) bzw. sogenannten intrinsischen Ladungstransfer-(ICT)- Fluoreszenzsonden (Donor-Akzeptor-substituierte Chalkone) und Elektronentransfer-(ET)-Fluoreszenzsonden (substituierte Triaryl-Δ2-pyrazoline). Die beiden letzten Systeme sind modular konzipiert, so dass signalgebender Fluorophor und komplexierender Rezeptor gezielt modellierbar sind. Im Fall der ICT-Sonden sind beide Einheiten elektronisch konjugiert, bei den ET-Sonden sind sie dagegen elektronisch weitgehend entkoppelt und das Signal wird durch Beeinflussung eines weitreichenden Elektronentransferprozesses generiert. Die Sonde vierten Typs, ein Bordipyrromethenderivat (BDP), ist ebenfalls modular aufgebaut. Bei ihr sind Fluorophor und Rezeptor aber nur durch den stark vorverdrillten Aufbau des Moleküls „virtuell“ entkoppelt. Neben diesem Einsatz eines alternativen Mechanismus zur Signalerzeugung standen vor allem die Steuerung der Selektivität durch gezielte Modifikation des Rezeptors sowie mögliche Verbesserungen der fluorometrischen Metallionenanalytik hinsichtlich Nachweisselektivität und -sensitivität durch Aufnahme zeitaufgelöster Fluoreszenzspektren (TRES) im Vordergrund der Untersuchungen. Unter Zuhilfenahme einer Reihe von Modellsubstanzen, NMR spektroskopischer Messmethoden und quantenchemischer Rechnungen wurden ausserdem allgemeine Erkenntnisse über das lichtinduzierte Verhalten der einzelnen Farbstoffklassen gewonnen. Der fluoreszierende Ligand BP(OH)2 zeigt, analog seiner Mutterverbindung 2,2‘-Bipyridyl, komplexierungsinduzierte Änderungen in seinem Absorptions- und Fluoreszenzverhalten bei Anwesenheit von Übergangs- und Schwermetallionen. Während paramagnetische Ionen wie CuII oder NiII (und auch HgII) zur statischen Fluoreszenzlöschung führen, bilden die diamagnetischen Ionen ZnII und CdII stark fluoreszierende Komplexe mit einer ionenspezifischen Fluoreszenzlebensdauer im ns-Zeitbereich. Beide Komplexe sind im angeregten Zustand stabil, was sich u. a. in einer, gegenüber dem freien Liganden stark herabgesetzten Geschwindigkeitskonstante für strahlungslose Desaktivierungsprozesse manifestiert. Die Absorptions- und Emissionsspektren der Komplexe überlappen stark und eine Unterscheidung mittels statischer Spektroskopie ist in beiden Fällen nur sehr begrenzt möglich. Die Trennung beider Komponenten gelingt allerdings unter Einsatz der zeitaufgelösten Fluoreszenzspektroskopie und an mehreren synthetischen ZnII/CdII-haltigen Proben konnte beispielhaft der Gewinn an Selektivität durch Aufnahme der TRES mit anschliessender global- analytischer Auswertung gezeigt werden. Die intrinsischen Fluoreszenzsonden des Chalkontyps tragen den Kationen-selektiven Rezeptor im Donorteil des Moleküls und zeigen bei Komplexierung durch Schwächung des Donors eine starke Abnahme des intramolekularen Ladungstransferprozesses. Im unkomplexierten Zustand erfolgt Fluoreszenz, je nach molekularem Aufbau und Polarität des Lösungsmittels, aus einem polaren direkt angeregten (E*) oder unter Einfachbindungsverdrillung und Reaktion im angeregten Zustand besetzten, hochpolaren Ladungstransferzustand (A*). Als konkurrierende Prozesse spielen dabei mögliche Besetzungen eines nicht fluoreszierenden, polaren (K*) bzw. schwach polaren (P*) Übergangszustandes eine Rolle. Des Weiteren ist in diesem Farbstoffsystem die Möglichkeit der Fluoreszenzlöschung durch benachbarte, tiefliegende nπ* Zustände (in unpolaren Lösungsmitteln) sowie durch verstärkte interne Konversion aufgrund des geringen energetischen Abstandes von Grund und angeregtem Zustand (in hochpolaren Lösungsmitteln) gegeben. Bei Kationenkomplexierung in polaren Lösungsmitteln wird vor allem, wie oben angedeutet, der Donor abgeschwächt, und es kommt zu einer moderaten Fluoreszenzverstärkung. Neben der erhöhten Fluoreszenzquantenausbeute resultiert der Effekt in Ionen-spezifischen Fluoreszenzlebensdauern der Komplexe. Durch den Austausch eines Stickstoff-Sauerstoff- gegen einen Stickstoff-Schwefel-Makrozyklus im Rezeptorteil des Systems konnte die Ionenselektivität von den Alkali- und Erdalkalimetallionen zu den thiophilen Metallionen AgI und HgII umgeleitet werden, wobei insbesondere die Fluoreszenzverstärkung in Gegenwart des herkömmlich als Fluoreszenzlöscher bekannten HgII-Ions analytisch wertvoll ist. Die ET-Sonden des Triaryl-Δ2-pyrazolin-Typs zeigen gegenüber den ICT-Sonden nur geringe spektrale Effekte, die Ioneninduzierte Fluoreszenzverstärkung ist dagegen wesentlich größer. Durch den gezielten Einsatz der unterschiedlichen Rezeptoren lassen sich hier ebenfalls die Selektivitäten steuern. In vergleichenden Untersuchungen konnten für die 5-p-N,NDialkylanilino-3-benzthiazol-1-phenyl-Δ2-pyrazoline die intramolekularen Prozesse charakterisiert werden, die Fluoreszenzlöschung im unkomplexierten und ein „Anschalten“ der Fluoreszenz im gebundenen Zustand bewirken. In diesen Molekülen findet der intramolekulare Ladungstransfer im Hauptchromophor im sub-ps Bereich statt und wird in hochpolaren Lösungsmitteln durch einen Elektronentransferprozess auf der ps-Zeitskala vom weitgehend elektronisch entkoppelten Rezeptor zum Akzeptorteil des Hauptchromophors gelöscht. Die „virtuelle“ Entkopplung von Fluorophor und Rezeptor im BDP-Derivat ermöglicht schließlich die Erzeugung von sehr grossen Fluoreszenzverstärkungssignalen bei Komplexierung. In diesen stark vorverdrillten Donor- Akzeptor-Biarylen geht der direkt angeregte emittierende Zustand (LE) in polaren Lösungsmitteln in einen hochpolaren, verdrillten radikalionischen Ladungstransferzustand (CT) über. Emission aus letzterem ist stark verboten und erfolgt, je nach Lösungsmittelpolarität, (weit) rotverschoben zur Fluoreszenz des LE, so dass schon in mittelpolaren Lösungsmitteln eine weithin getrennte, duale Fluoreszenz zu beobachten ist. In hochpolaren Lösungsmitteln sind beide Fluoreszenzen nahezu vollständig gelöscht. Metallionenkomplexierung führt zur Unterbrechung des CT-Prozesses und somit zu einem „Anschalten“ der LE- Emission mit Fluoreszenzverstärkungsfaktoren > 1000. Dieser Prozess ist dabei so sensitiv, dass für die meisten Kationenkomplexe zwei spektral sehr stark überlappend absorbierende und emittierende Komplexkonformere anhand ihrer Fluoreszenzlebensddauer unterschieden werden können. N2 - The present work is focused on the study of the spectroscopic and complexometric behavior of different ion-sensitive fl uorescent probes. Three of the four types of probes studied follow a conventional principle of signal generation and their molecular constitution corresponds to either a fl uorescent ligand ( BP(OH)2), so-called intrinsic charge transfer (ICT) fl uorescent probes (donor- acceptor-substituted chalcones), or electron transfer (ET) fl uorescent probes (substituted triaryl-Δ2- pyrazolines). The latter two systems are designed in a modular way and thus, both the signal generating fl uorophore and the complexing receptor can be carefully tuned. Whereas in the case of the ICT probes both units are electronically conjugated, these moieties are more or less electronically decoupled in the ET probes and signal generation is based on the modifi cation of a long range electron transfer process. The fourth type of probe investigated, a boron dipyrromethene derivative (BDP), is also designed in a modular way. But here, due to the highly pretwisted constitution of the molecule, fl uorophore and receptor are only “virtually” decoupled. Besides employing this alternative mechanism of signal generation, control of the selectivity by carefully directed receptor design and improvement of the selectivity and sensitivity of fl uorometric metal ion analysis by recording time resolved emission spectra (TRES) were the main aims of these investigations. Furthermore, with the aid of various model compounds, NMR spectroscopy as well as quantum chemical calculations, a fundamental understanding of the photophysical behavior of the different classes of dyes was obtained. In accordance with its parent compound 2,2‘- bipyridyl, the fl uorescent ligand BP(OH)2 shows complexation induced changes of its absorption and emission behavior in the presence of heavy and transition metal ions. Whereas paramagnetic ions such as CuII or NiII (and also HgII) lead to static fl uorescence quenching, the diamagnetic ions ZnII and CdII form strongly fl uorescent complexes with ion specifi c fl uorescence lifetimes in the ns time range. Both complexes are stable in the excited state which is manifested by a strongly reduced rate constant of non radiative deactivation compared to that of the free ligand. Both the absorption and emission spectra of the complexes largely overlap and a discrimination with steady-state fl uorometry is very limited. Nevertheless, with time resolved fl uorometry a separation of both components is possible and for a series of synthetic ZnII/CdII containing samples this gain in selectivity by global analysis of the time resolved emission spectra (TRES) could be demonstrated. The intrinsic fl uorescent probes of chalcone type contain a cation selective receptor in the donor part of the molecule and show a strong decrease of the intramolecular charge transfer process due to complexation induced weakening of the donor. Depending on molecular probe design and solvent polarity, the fl uorescence of the uncomplexed molecule occurs either from a polar directly exicted (E*) or a highly polar charge transfer state (A*) which is populated via an excited state reaction involving single bond twisting. Here, competing processes include population of a non emissive polar (K*) or weakly polar (P*) transient state. Furthermore, the fl uorescence of these dyes can be quenched by energetically close lying nπ* states (in apolar solvents) or by enhanced internal conversion due to the decreasing energy gap between ground and excited state (in highly polar solvents). As mentioned above, the donor strength is reduced upon cation complexation in polar solvents and a moderate fl uorescence enhancement occurs. Besides increased fl uorescence quantum yields, this effect results in ion specifi c fl uorescence lifetimes of the complexes. Upon exchanging the aza oxa for an aza thia macrocycle in the receptor part of the system, the cation selectivity could be tuned from alkali and alkaline earth metal ions to the thiophilic metal ions AgI and HgII. Here, especially the fl uorescence enhancement in the presence of the well-known quencher HgII is analytically valuable. Upon cation binding the ET probes of the triaryl-Δ2-pyrazoline type show very small spectral shifts but much larger fl uorescence enhancement compared to the ICT probes. Again, by problem specifi c use of different receptors, the selectivities can be controlled. Based on a detailed investigation, for the 5-p-N,N-dialkylanilino-3-benzthiazol-1-phenyl-Δ2-pyrazolines, the intramolecular processes which lead to fl uorescence quencing in the unbound state and “switching on” of the fl uorescence in the complexed state could be identifi ed. For these molecules, the intramolecular charge transfer in the basic chromophore occurs in the sub ps time range and is quenched by an electron transfer process from the largely electronically decoupled receptor to the acceptor part of the basic chromophore on the ps time scale in highly polar solvents. “Virtually” decoupling fl uorophore and receptor in the BDP derivative fi nally makes it possible to yield extremely high complexation induced fl uorescence enhancement signals. For these highly pretwisted donor acceptor biaryls, the directly excited emissive state (LE) forms a highly polar, twisted charge separated charge transfer state (CT) in polar solvents. Emission of the latter is strongly forbidden and, depending on solvent polarity, is largely red shifted compared to the LE fl uorescence. Thus, a largely separated dual fl uorescence is already observed in solvents of medium polarity and in highly polar solvents both fl uorescence bands are nearly completely quenched. Metal ion complexation blocks off the CT process and leads to a “switching on” of the LE emission yielding fl uorescence enhancement factors > 1000. This process is so sensitive that for most of the cation complexes studied, two emissive complex conformers with strongly overlapping absorption and emission spectra occur which could be distinguished by their fl uorescence lifetimes. T3 - BAM Forschungsberichtreihe - 235 PY - 2009 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-2150 SN - 978-3-89701-362-2 SN - 0938-5533 VL - 235 SP - 1 EP - 136 PB - Wirtschaftsverlag NW CY - Bremerhaven AN - OPUS4-215 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Rurack, Knut A1 - Resch-Genger, Ute T1 - Design, Synthese und Charakterisierung von Fluoreszenzstandards und Fluoreszenzmarkern für die zeitaufgelöste Fluorometrie N2 - Im Rahmen dieses Projekts wurden Fluoreszenzfarbstoffe und neue intrinsische und konjugierte Fluoreszenzmarker mit Sauerstoff, Schwefel, Stickstoff-Heteromakrozyklen als kationenspezifische Rezeptoren für analytische Applikationen der zeitaufgelösten Fluorometrie von der Kiewer Gruppe synthetisiert. Die in Berlin an diesen Verbindungen durchgeführten fluorometrischen Charakterisierungen und spektroskopischen Untersuchungen zum Kationenkomplexierungsverfahren ermöglichten die Aufstellung von ersten Designprinzipien für Fluoreszenzmarker für Übergangs- und Schwermetallionen. T3 - BAM Forschungsberichtreihe - 223 PY - 1998 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-2273 SN - 978-3-89701-038-0 SN - 0938-5533 VL - 223 SP - 1 EP - 40 PB - Wirtschaftsverlag NW CY - Bremerhaven AN - OPUS4-227 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Radeglia, Reiner T1 - Transition Metal Ion Complexes of 2,2'-Bipyridyl-3,3'-diol and 2,2'-Bipyridyl-3-ol: Spectroscopic Properties and Solvent-Dependent Binding Modes N2 - The complexation behaviour of 2,2-bipyridyl-3,3-diol and 2,2-bipyridyl-3-ol, BP(OH)2 and BPOH, with various heavy and transition metal ions has been investigated in aqueous, alcoholic, and acetonitrile solutions. Whereas the complexes with paramagnetic ions and HgII are non-fluorescent, ZnII and CdII form highly fluorescent complexes, their coordination geometries depending on the solvent proticity and hydrogen-bond donating ability. Through a comparative study with the corresponding chelates of 2,2-bipyridyl (bipy), N,O-coordination in a six-membered ring chelate has been found to be the dominant binding mode in both the ZnII and CdII complexes in the protic solvents water and ethanol. Only for ZnII and BPOH is exclusive N,N-chelation found in acetonitrile. NMR measurements on BP(OH)2, BPOH, and bipy in the presence of ZnII and CdII in acetonitrile confirmed these findings. KW - Chelates KW - Hydroxy bipyridyls KW - Fluorescence KW - Cadmium KW - Zinc KW - N ligands PY - 2000 DO - https://doi.org/10.1002/1099-0682(200010)2000:10<2271::AID-EJIC2271>3.0.CO;2-3 SN - 1434-1948 SN - 1099-0682 VL - 2000 IS - 10 SP - 2271 EP - 2282 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-968 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Maus, M. T1 - Monitoring pH and solvent proticity with donor-acceptor-substituted biphenyls: a new approach towards highly sensitive and powerful fluorescent probes by tuning the molecular structure N2 - The ability and structural requirements of 4-dimethylamino-4-cyano-substituted biphenyls showing photoinduced intramolecular charge transfer (CT) to serve as hydrogen bond- or pH-sensitive fluorescent probes is investigated. The donor–acceptor (D–A) biphenyls I and II being planar in the CT excited state are most suitable as pH-sensitive fluorescent probes. The two compounds show analytically valuable features such as well-separated absorption and emission bands and signal changes spanning four orders of magnitude and can be employed in ratiometric, self-calibrating, and highly sensitive pH fluorosensing in the range 0103. This efficient "switching on" of the fluorescence renders the crowned BDP dye an extremely sensitive fluorescent probe for metal ions. PY - 1998 DO - https://doi.org/10.1021/jp982701c SN - 1089-5639 SN - 1520-5215 VL - 102 IS - 50 SP - 10211 EP - 10220 PB - Soc. CY - Washington, DC AN - OPUS4-2095 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 - GEN A1 - Rurack, Knut A1 - Bricks, J. L. A1 - Slominskii, J. L. A1 - Resch-Genger, Ute ED - Dähne, S. T1 - Long wavelength emitting fluorescence probes for metal ions T2 - NATO Advanced Research Workshop on Syntheses, Optical Properties and Applications of Near-Infrared (NIR) Dyes in High Technology Fields CY - Trest', Czech Republic DA - 1997-09-24 PY - 1998 IS - 52 SP - 191 EP - 200 PB - Kluwer CY - Dordrecht AN - OPUS4-2097 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Bricks, J.L. A1 - Slominskii, J.L. A1 - Resch-Genger, Ute T1 - Cation complexing fluorescence probes containing the benz[c,d]indole fluorophore PY - 1998 SN - 0143-7208 SN - 1873-3743 VL - 36 IS - 2 SP - 121 EP - 138 PB - Elsevier Science CY - Kidlington AN - OPUS4-2098 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Resch-Genger, Ute A1 - Rurack, Knut ED - Lieberman, R. T1 - Steady-state and time-resolved fluorometry of fluorescent pollutants and heavy metal complexes N2 - Time-resolved laser-induced fluorescence spectroscopy is one of the most sensitive optical methods which is well suited for on-line in situ analysis. Here, three examples for the steady- state and time-resolved fluorescence analysis of environmentally important analytes, the fluorescent monoaromatic hydrocarbons benzene, toluene, and xylene as well as non fluorescent heavy metal ions forming a fluorescent complex with a cation coordinating fluorescence probe, are presented and the potential of both methods is discussed. For BTX, various mixtures of the spectrally similar compounds B, T, and X showing different fluorescence lifetimes were studied with both methods. As an example for fluorometric metal ion analysis, the fluorescence probe BP(OH)2 (2,2'-bipyridyl- 3,3'-diol) was employed for the determination of d10 metal ions in water and the newly developed fluorescence probe APTA for the detection of Cu(II). Cation complexation of BP(OH2 yields spectrally very similar complexes which differ in their fluorescence lifetimes. Complexation of APTA to Cu(II) leads to small spectral changes and a strong increase in fluorescence quantum yield and lifetime. For the analytes studied, a comparison of the detection limits, standard deviations, and linear dynamic range of both methods clearly demonstrates the analytical potential of time-resolved fluorometry. T2 - Conference CY - Munich, Germany DA - 1997-06-16 KW - Fluorescence KW - Time-resolved KW - Probe KW - Heavy metal ion KW - Cation complex PY - 1997 SN - 0-8194-2526-5 DO - https://doi.org/10.1117/12.276139 SN - 1605-7422 N1 - Serientitel: SPIE proceedings series – Series title: SPIE proceedings series IS - 3105 SP - 96 EP - 103 PB - SPIE CY - Bellingham, Wash. AN - OPUS4-2099 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute A1 - Rurack, Knut A1 - Bricks, J.L. A1 - Slominskii, J.L. T1 - New fluorophore receptor systems for heavy metal ions: a spectroscopic study KW - Fluorescence KW - Probe KW - Cation complex KW - Ion responsive KW - Chelation enhanced PY - 1997 SN - 1053-0509 SN - 1573-4994 VL - 7 IS - 1 SP - 231S EP - 233S PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-2100 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Bricks, J.L. A1 - Kachkovski, A. A1 - Resch-Genger, Ute T1 - Complexing fluorescence probes consisting of various fluorophores linked to 1-aza-15-Crown-5 KW - Fluoroinophore KW - Calcium KW - Sodium KW - Ion sensor KW - Photoinduced electron transfer PY - 1997 SN - 1053-0509 SN - 1573-4994 VL - 7 IS - 1 SP - 63S EP - 66S PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-2101 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 - Rurack, Knut A1 - Senoner, Mathias A1 - Resch-Genger, Ute A1 - Dähne, Siegfried T1 - Heavy metal complexes of 2,2'-bipyridyl-3,3'-diol PY - 1994 SN - 0323-598x VL - 21 SP - 683 EP - 684 PB - Akad. Verl. CY - Berlin AN - OPUS4-2103 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute A1 - Rurack, Knut A1 - Senoner, Mathias T1 - Zeitaufgelöste Fluorometrie in der Wasseranalytik PY - 1994 SN - 0341-5163 SN - 1521-3854 VL - 42 IS - 5 SP - 504 EP - 506 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-2104 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Senoner, Mathias A1 - Dähne, Siegfried T1 - A new fluorescence probe for trace metal ions: cation dependent spectroscopic properties KW - 2,2´-Bipyridyl-3,3´-diol KW - Metal ions KW - Cation dependence KW - Fluorescence probe PY - 1993 SN - 1053-0509 SN - 1573-4994 VL - 3 IS - 3 SP - 141 EP - 143 PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-2105 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Bricks, J. L. A1 - Reck, Günter A1 - Schulz, Burkhard A1 - Spieles, Monika T1 - Cation coordination of bisamidopyridine-derived receptors as investigated in the solid-state and in solution N2 - A bisamidopyridine-type receptor, N,N'-bis(6-methyl-2-pyridyl)pyridine-2,6-dicarboxamide (1), and its CoIII complex were prepared and their X-ray structures were compared to those of N,N'-diphenylpyridine-2,6-dicarboxamide (2) and CoIII(2)2. Introduction of the two additional coordinative groups resulted in second-order interactions between the central ion and the nitrogen atoms of the terminal pyridine moieties in the crystalline state. Solution studies in acetonitrile revealed the importance of these interactions for the ligand's metal ion recognition ability. Whereas 2 only binds to PbII and CuII, 1 yields complexes with a majority of the heavy and transition metal ions studied, CoII, NiII, CuII, ZnII, FeIII, FeII, HgII, and PbII, respectively. The cation binding properties in solution were investigated by absorption spectroscopy and in the case of 1-MII/III, the formation of two spectroscopically distinguishable types of complexes was found. Protonation experiments and theoretical considerations helped to gain further insight into possible modes of coordination in solution. KW - Pyridine carboxamides KW - Ion recognition KW - Crystal structure KW - N-coordination PY - 2003 DO - https://doi.org/10.1080/1061027031000078239 SN - 1061-0278 SN - 1029-0478 VL - 15 IS - 3 SP - 189 EP - 197 PB - Gordon and Breach Science Publ. CY - New York, NY AN - OPUS4-2106 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - JOUR A1 - Fery-Forgues, S. A1 - Rurack, Knut A1 - Delavaux-Nicot, B. A1 - Lavabre, D. T1 - 1,3-Diphenyl-1H-pyrazolo[3,4-b]-quinoline (DPPQ)-a versatile fluorophore for the design of brightly emissive molecular sensors PY - 2002 SN - 1010-6030 SN - 1873-2666 PB - Elsevier CY - Lausanne AN - OPUS4-2108 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Kollmannsberger, M. A1 - Daub, J. T1 - A highly efficient sensor molecule emitting in the near infrared (NIR): 3,5-distyryl-8-(p-dimethylaminophenyl)-difluoroboradiaza-s-indacene N2 - The spectroscopic properties and the photophysical behaviour of difluoroboradiaza-s-indacene 1, especially designed for the near infrared (NIR) spectral region and equipped with a p-dimethylaminophenyl group at the meso-position, were studied by steady-state and time-resolved optical spectroscopy. Solvent-dependent measurements revealed that for 1, excited state deactivation is governed by population of a non-emissive charge transfer excited state (1CT) as the solvent polarity increases, whereas reference compound 2 shows strong fluorescence from a locally excited state (1LE) in all the solvents employed. Accordingly, protonation of 1 completely suppresses the quenching excited state charge transfer process and leads to strong enhancement of fluorescence in the NIR, distinguishing 1 as a very sensitive fluorescent sensor molecule for pH or solvent acidity in this favourable wavelength region. PY - 2001 DO - https://doi.org/10.1039/b007379m SN - 0398-9836 VL - 25 SP - 289 EP - 292 PB - Le Centre National de la Recherche Scientifique CY - Paris AN - OPUS4-1085 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Kollmannsberger, M. A1 - Daub, J. T1 - Molekulares Schalten im nahen Infrarot (NIR) mit einem funktionalisierten Bordipyrromethen-Farbstoff KW - Molekularer Schalter KW - Solvatochromie KW - Donor-Akzeptor-System KW - Elektrochromie PY - 2001 DO - https://doi.org/10.1002/1521-3757(20010119)113:2<396::AID-ANGE396>3.0.CO;2-W SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 113 IS - 2 SP - 396 EP - 399 PB - Wiley-VCH CY - Weinheim AN - OPUS4-1077 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Kollmannsberger, M. A1 - Daub, J. T1 - Molecular Switching in the Near Infrared (NIR) with a Functionalized Boron-Dipyrromethene Dye PY - 2001 DO - https://doi.org/10.1002/1521-3773(20010119)40:2<385::AID-ANIE385>3.0.CO;2-F SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 40 IS - 2 SP - 385 EP - 387 PB - Wiley-VCH CY - Weinheim AN - OPUS4-1078 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Unger, Brita A1 - Rurack, Knut A1 - Müller, Ralf A1 - Resch-Genger, Ute A1 - Buttke, K. T1 - Effects of the Sol-Gel Processing on the Fluorescence Properties of Laser Dyes in Tetraethoxysilane Derived Matrices N2 - Two fluorescent dyes were incorporated into sol-gel derived SiO2 matrices. The dye was added to SiO2 precursors of different degrees of pre-condensation and the spectroscopic properties of the immobilized dye were measured at various aging and drying stages of the resulting gels. The significant influence of the processing parameters on the spectroscopic properties is manifested in the relative intensity of a second red shifted emission band (550–560 nm), which was observed besides the typical coumarin emission band (495 nm). The appearance of this long wavelength emission might be attributed to dye aggregation or to other reactions with the ambient matrix forced by micro porosity phenomena. KW - Sol-gel KW - Precursor chemistry KW - Fluorescence properties KW - Optical solids PY - 2000 DO - https://doi.org/10.1023/A:1008768318418 SN - 0928-0707 SN - 1573-4846 VL - 19 SP - 799 EP - 802 PB - Kluwer Academic Publ. CY - Dordrecht AN - OPUS4-1080 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo, Ana B. A1 - Martínez-Mánez, Ramon A1 - Radeglia, Reiner A1 - Rurack, Knut A1 - Soto, J. T1 - Coupling Selectivity with Sensitivity in an Integrated Chemosensor Framework: Design of a Hg2+-Responsive Probe, Operating above 500 nm N2 - For the highly selective and sensitive sensing of Hg2+ in water, a new design concept was realized where the selectivity of the probe's binding site is amplified by electronic properties of the chromophore. The molecular architecture of this phenoxazinone-type sensor molecule combines two potential coordination sites via an amino-keto conjugative backbone. These structural prerequisites allow only the most preferred mercuric ion to bind to the dithia dioxa monoaza crown unit, while other heavy, transition, and main group metal ions as well as protons are trapped at the keto group, inducing opposite spectral effects due to interaction with either the donor (Hg2+) or the acceptor group (other cations) of the probe. Besides these advantageous features, the probe operates well within the visible range of the spectrum and displays rather intense molar absorptivities as well as fluorescence quantum yields. PY - 2003 DO - https://doi.org/10.1021/ja0290779 SN - 0002-7863 SN - 1520-5126 VL - 125 IS - 12 SP - 3418 EP - 3419 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2377 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Descalzo, Ana B. A1 - Weißhoff, Hardy A1 - Martínez-Mánez, Ramon A1 - Marcos, M. Dolores A1 - Amorós, P. A1 - Hoffmann, Katrin A1 - Soto, J. T1 - A Chromo- and Fluorogenic Hybrid Chemosensor Material for the Detection of Long-chain Carboxylates T2 - ANAKON 2005 CY - Regensburg, Germany DA - 2005-03-15 PY - 2005 AN - OPUS4-7427 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Descalzo, Ana B. A1 - Weißhoff, Hardy A1 - Martínez-Mánez, Ramon A1 - Marcos, M. Dolores A1 - Hoffmann, Katrin A1 - Soto, J. T1 - A hybrid chemosensor material for the colorimetric and fluorometric detection of long-chain carboxylates T2 - 9th Conference on Methods and Applications of Fluorescence: Spectroscopy, Imaging and Probes CY - Lisbon, Portugal DA - 2005-09-04 PY - 2005 AN - OPUS4-7428 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Unger, Brita A1 - Rurack, Knut A1 - Müller, Ralf A1 - Jancke, Harald A1 - Resch-Genger, Ute T1 - Microscopic vs. macroscopic structural evolution of SiO2 sols and gels employing a tailor-made fluorescent reporter dye N2 - The short- and long-term structural evolution and aging of sol–gel materials prepared under mild conditions are studied by fluorometry, dynamic light scattering (DLS), 29Si NMR and gravimetry. In combination with the first, a newly developed donor–acceptor-substituted fluorescent probe with two acidophilic sites of different strength and topology is introduced. Its performance in detecting changes in parameters such as polarity, proticity, and pore volume on the microscopic scale is compared to two other dyes and to the macroscopic changes revealed by DLS, NMR and gravimetry. At early stages of the sol–gel process, fluorometry, DLS and NMR reveal similar changes which are typical of the structural evolution of SiO2 sols having different synthesis parameters. During later times of sol aging, DLS and NMR reflect the growth of the network and indicate that all sols approach similar structural equilibria. Fluorometry supports these findings by signalling a gradual decrease in mobile species with high proton activity. The formation of the spanning cluster upon gelation is strongly evident only from DLS results while the local environment of the fluorophore remains largely unchanged. However, the fluorescent dye is able to report microscopic changes even during long-term aging. Drying of the gels with a pronounced contraction of solvated pores is readily observable by fluorometry and gravimetry. During the late reaction stages, the fluorescence properties of the tailor-made dye are still sensitive toward the environment. PY - 2005 DO - https://doi.org/10.1039/b501622c SN - 0959-9428 SN - 1364-5501 VL - 15 IS - 30 SP - 3069 EP - 3083 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-10378 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Marcos, M. Dolores A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Soto, J. T1 - Ein regeneratives Chemodosimeter für die hoch selektive und empfindliche optische Bestimmung von Hg2+, basierend auf der metallinduzierten Bildung eines Farbstoffes KW - Fluorometrischer Nachweis KW - Chromogener Nachweis KW - Quecksilber KW - Chemodosimeter PY - 2005 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 117 IS - 28 SP - 4479 EP - 4482 PB - Wiley-VCH CY - Weinheim AN - OPUS4-10379 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute A1 - Pfeifer, Dietmar A1 - Monte, Christian A1 - Pilz, Walter A1 - Hoffmann, Angelika A1 - Spieles, Monika A1 - Rurack, Knut A1 - Hollandt, J. A1 - Taubert, D. A1 - Schönenberger, B. A1 - Nording, P. T1 - Traceability in Fluorometry: Part II. Spectral Fluorescence Standards N2 - The need for the traceable characterization of fluorescence instruments is emphasized from a chemist’s point of view, focusing on spectral fluorescence standards for the determination of the wavelength- and polarization-dependent relative spectral responsivity and relative spectral irradiance of fluorescence measuring systems, respectively. In a first step, major sources of error of fluorescence measurements and instrument calibration are revealed to underline the importance of this issue and to illustrate advantages and disadvantages of physical and chemical transfer standards for generation of spectral correction curves. Secondly, examples for sets of traceable chemical emission and excitation standards are shown that cover a broad spectral region and simple procedures for the determination of corrected emission spectra with acceptable uncertainties are presented. With proper consideration of the respective measurement principle and geometry, these dye-based characterization procedures can be not only applied to spectrofluorometers but also to other types of fluorescence measuring systems and even to Raman spectrometers. KW - Fluorescence KW - Standard KW - Spectral correction KW - Emission KW - Excitation KW - Traceability PY - 2005 DO - https://doi.org/10.1007/s10895-005-2629-9 SN - 1053-0509 SN - 1573-4994 VL - 15 IS - 3 SP - 315 EP - 336 PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-10824 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yu, Y.-H. A1 - Descalzo López, Ana Belén A1 - Sgen, Z. A1 - Röhr, Holger A1 - Liu, Q. A1 - Wang, Y.-W. A1 - Spieles, Monika A1 - Li, Y.-Z. A1 - Rurack, Knut A1 - You, X.-Z. T1 - Mono- and Di(dimethylamino)styryl-Substituted Borondipyrromethene and Borondiindomethene Dyes with Intense Near-Infrared Fluorescence N2 - Four novel borondipyrromethene (BDP) and -diindomethene (BDI) dyes with one or two (dimethylamino)styryl extensions at the chromophore were synthesized and spectroscopically investigated. An X-ray crystal structure shows that the extended auxochrome is virtually planar. All dyes thus display intense red/near infrared (NIR) absorption and emission. The (dimethylamino)styryl group induces a charge-transfer character that entails bright solvatochromic fluorescence, which is only quenched with increasing solvent polarity according to the energy-gap law. The dye with an additional dimethylanilino group at the meso position of BDP shows a remarkable switching of lipophilicity by protonation. Two dyes with an 8-hydroxyquinoline ligand at the meso position display quenched emission in the presence of Hg2+ or Al3+ owing to electron transfer from the excited BDP to the complexed receptor. The BDI dye presents a pH indicator with bright fluorescence and extremely low fluorescence anisotropy. KW - Borondipyrromethene KW - Dyes KW - Fluorescence KW - Indicators KW - Protonation PY - 2006 DO - https://doi.org/10.1002/asia.200600042 SN - 1861-4728 SN - 1861-471X VL - 1 IS - 1-2 SP - 176 EP - 187 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-12561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - García-Acosta, B. A1 - Comes, M. A1 - Bricks, J.L. A1 - Kudinova, M.A. A1 - Kurdyukov, V.V. A1 - Tolmachev, A.I. A1 - Descalzo López, Ana Belén A1 - Marcos, M. Dolores A1 - Martínez-Mánez, Ramon A1 - Moreno, A. A1 - Sancenón, F. A1 - Soto, J. A1 - Villaescusa, L.A. A1 - Rurack, Knut A1 - Barat, J. M. A1 - Escriche, I. A1 - Amorós, P. T1 - Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines KW - Biogene Amine KW - Histamin KW - Farbreaktion KW - Pyralium-Farbstoffe KW - Fluoreszenz KW - Hybrid-Materialien PY - 2006 SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x IS - 21 SP - 2239 EP - 2241 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-12563 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Soto, J. T1 - A regenerative chemodosimeter based on metal-induced dye formation for the highly selective and sensitive optical detection of Hg2+ KW - Fluormetrischer Nachweis KW - Chromogener Nachweis KW - Quecksilber KW - Chemodosimeter PY - 2005 DO - https://doi.org/10.1002/ange.200500583 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 117 SP - 4479 EP - 4482 PB - Wiley-VCH CY - Weinheim AN - OPUS4-7282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Descalzo, Ana B. A1 - Martínez-Mánez, Ramon A1 - Radeglia, Reiner A1 - Soto, J. T1 - Novel Modular Sensors: Design of Efficient Probes for Various Analytes Utilizing the Phenoxazinone Chromophore T2 - Tag der Chemie CY - Potsdam, Germany DA - 2004-07-07 PY - 2004 AN - OPUS4-5353 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Rurack, Knut A1 - Weißhoff, Hardy A1 - Martínez-Mánez, Ramon A1 - Marcos, M. Dolores A1 - Amorós, P. A1 - Hoffmann, Katrin A1 - Soto, J. T1 - Rational Design of a Chromo- and Fluorogenic Hybrid Chemosensor Material for the Detection of Long-Chain Carboxylates N2 - A strategy for the rational design of a new optical sensor material for the selective recognition of long-chain carboxylates in water is presented. The approach relies on the combination of structure-property relationships to single out the optimal molecular sensor unit and the tuning of the sensing characteristics of an inorganic support material. A spacer-substituted 7-urea-phenoxazin-3-one was employed as the signaling moiety and a mesoporous trimethylsilylated UVM-7 (MCM-41 type) material served as the solid support. The sensor material shows the advantageous features of both modules that is absorption and emission in the visible spectral range, a fluorescence red-shift and enhancement upon analyte coordination, and the amplification of noncovalent (binding) and hydrogen-bonding (recognition) interactions in the detection event. Besides these basic results that are related to the design and performance of the sensor material, the paper discusses general aspects of amido-substituted phenoxazinone photophysics and addresses some general features of molecular anion recognition chemistry in aqueous vs nonaqueous media, utilizing steady-state and time-resolved optical as well as NMR spectroscopies. Detailed studies on potentially competing biochemical species and a first access to the schematic model of the response of the sensor material as obtained by a combination of fluorescence lifetime distribution analysis and Langmuir-type fitting of the gross binding constants complement the key issues of the paper. KW - Chemosensor KW - Carboxylate KW - Rationales Design KW - Hybridmaterialien KW - Fluoreszenz PY - 2005 DO - https://doi.org/10.1021/ja045683n SN - 0002-7863 SN - 1520-5126 VL - 127 SP - 184 EP - 200 PB - American Chemical Society CY - Washington, DC AN - OPUS4-5985 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Soto, J. T1 - A regenerative chemodosimeter based on metal-induced dye formation for the highly selective and sensitive optical detection of Hg2+ KW - Chemodosimeter KW - Chromogener Nachweis KW - Fluormetrischer Nachweis KW - Quecksilber PY - 2005 DO - https://doi.org/10.1002/anie.200500583 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 N1 - Sprachen: Deutsch/Englisch - Languages: German/English VL - 44 SP - 4405 EP - 4407 PB - Wiley-VCH CY - Weinheim AN - OPUS4-11006 LA - mul AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wan, Wei A1 - Biyikal, Mustafa A1 - Wagner, R. A1 - Sellergren, B. A1 - Rurack, Knut T1 - Sensorische Mikropartikel aus einem Silicatkern und einem molekular geprägten Polymer als Schale mit aufleuchtender Fluoreszenz N2 - Und es ward Licht – der Einbau eines auf Harnstoff basierenden Fluoreszenzfarbstoffs in eine mit Anionen geprägte dünne Polymerschale (MIP) auf Silicatmikropartikeln führt zu einem spezifischen und enantioselektiven Aufleuchten der Fluoreszenz in Gegenwart des Zielanalyten. KW - Enantioselektivität KW - Fluoreszenz KW - Kern-Schale-Partikel KW - Molekular geprägte Polymere KW - Sensoren PY - 2013 DO - https://doi.org/10.1002/ange.201300322 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 125 IS - 27 SP - 7161 EP - 7165 PB - Wiley-VCH CY - Weinheim AN - OPUS4-28739 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wan, Wei A1 - Biyikal, Mustafa A1 - Wagner, R. A1 - Sellergren, B. A1 - Rurack, Knut T1 - Fluorescent sensorymicroparticles that 'light-up' consisting of a silica core and a molecularly imprinted polymer (MIP) shell N2 - From darkness came light: Incorporation of urea-based fluorescent dyes in an anion-imprinted thin polymer shell coated onto silica microparticles leads to a unique and highly enantioselective fluorescent 'light-up' response to analytes (see scheme, MIP molecularly imprinted polymer). KW - Core–shell particles KW - Enantioselectivity KW - Fluorescence KW - Molecularly imprinted polymers KW - Sensors PY - 2013 DO - https://doi.org/10.1002/anie.201300322 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 52 IS - 27 SP - 7023 EP - 7027 PB - Wiley-VCH CY - Weinheim AN - OPUS4-28740 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Biyikal, Mustafa A1 - Hecht, Mandy A1 - Rurack, Knut T1 - Mimicking tricks from nature with sensory organic-inorganic hybrid materials N2 - Design strategies for (bio)chemical systems that are inspired by nature's accomplishments in system design and operation on various levels of complexity are increasingly gaining in importance. Within the broad field of biomimetic chemistry, this article highlights various attempts toward improved and sophisticated sensory materials that rely on the combination of supramolecular (bio)chemical recognition principles and nanoscopic solid structures. Examples range from more established concepts such as hybrid sensing ensembles with improved sensitivity and selectivity or for target analytes for which selectivity is hard to achieve by conventional methods, which were often inspired by protein binding pockets or ion channels in membranes, to very recent approaches relying on target-gated amplified signalling with functionalised mesoporous inorganic supports and the integration of native biological sensory species such as transmembrane proteins in spherically supported bilayer membranes. Besides obvious mimicry of recognition-based processes, selected approaches toward chemical transduction junctions utilizing artificially organized synapses, hybrid ensembles for improved antibody generation and uniquely colour changing systems are discussed. All of these strategies open up exciting new prospects for the development of sensing concepts and sensory devices at the interface of nanotechnology, smart materials and supramolecular (bio)chemistry. KW - Sensorik KW - Supramolekulare Chemie KW - Biomimetik KW - Nanotechnologie KW - Hybridmaterialien PY - 2011 DO - https://doi.org/10.1039/c1jm11210d SN - 0959-9428 SN - 1364-5501 VL - 21 IS - 34 SP - 12588 EP - 12604 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-24352 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Calero, P. A1 - Hecht, Mandy A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Vivancos, J.L. A1 - Rurack, Knut T1 - Silica nanoparticles functionalised with cation coordination sites and fluorophores for the differential sensing of anions in a quencher displacement assay (QDA) N2 - In conjunction with quenching metal ions, silica nanoparticles carrying terpyridine coordination sites and sulforhodamine B signalling units were employed for the differential fluorometric recognition of anions. KW - Hybridmaterial KW - Silica-Nanopartikel KW - Fluoreszenz KW - Anionen KW - Verdrängungsassay PY - 2011 DO - https://doi.org/10.1039/c1cc13039k SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x VL - 47 IS - 38 SP - 10599 EP - 10601 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-24489 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xu, H.-J. A1 - Mack, J. A1 - Wu, D. A1 - Xue, Z.-L. A1 - Descalzo López, Ana Belén A1 - Rurack, Knut A1 - Kobayashi, N. A1 - Shen, Z. T1 - Synthesis and properties of fused-ring-expanded porphyrins that were core-modified with group 16 heteroatoms N2 - The synthesis of a series of novel core-modified and fused-ring-expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem-crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine-tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso-phenyl rings, is also examined. KW - Density functional calculations KW - Fluorescence KW - MCD spectroscopy KW - Porphyrinoids KW - Ring expansion PY - 2012 DO - https://doi.org/10.1002/chem.201200956 SN - 0947-6539 SN - 1521-3765 VL - 18 IS - 52 SP - 16844 EP - 16867 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-27488 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hecht, Mandy A1 - Kraus, Werner A1 - Rurack, Knut T1 - A highly fluorescent pH sensing membrane for the alkaline pH range incorporating a BODIPY dye N2 - A robust and re-usable dipstick-type fluorescent pH sensor for the alkaline pH range was developed by embedding a brightly fluorescent boron–dipyrromethene (BODIPY) dye bearing an acidic phenol moiety into a polyurethane matrix immobilized on a 3D epoxy-functionalized polymer support. The sensor strip has a dynamic working range of pH 10.0–13.1, i.e., operates in strongly basic media where pH glass electrodes can suffer from alkaline errors, and tolerates a high electrolyte background such as simulated seawater and sewage. This work describes the preparation of the sensing material and provides insight into the features that a hydrogel sensing membrane can bestow on an embedded pH-responsive dye by means of optical spectroscopic investigations. KW - pH-Wert KW - Farbstoffe KW - Fluoreszenz KW - Teststreifen KW - Hydrogel PY - 2013 DO - https://doi.org/10.1039/c2an35860c SN - 0003-2654 SN - 1364-5528 VL - 138 IS - 1 SP - 325 EP - 332 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-27638 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wagner, R. A1 - Wan, Wei A1 - Biyikal, Mustafa A1 - Benito-Pena, E. A1 - Moreno-Bondi, M.C. A1 - Lazraq, I. A1 - Rurack, Knut A1 - Sellergren, B. T1 - Synthesis, spectroscopic, and analyte-responsive behavior of a polymerizable naphthalimide-based carboxylate probe and molecularly imprinted polymers prepared thereof N2 - A naphthalimide-based fluorescent indicator monomer 1 for the integration into chromo- and fluorogenic molecularly imprinted polymers (MIPs) was synthesized and characterized. The monomer was equipped with a urea binding site to respond to carboxylate-containing guests with absorption and fluorescence changes, namely a bathochromic shift in absorption and fluorescence quenching. Detailed spectroscopic analyses of the title compound and various models revealed the signaling mechanism. Titration studies employing benzoate and Z-ʟ-phenylalanine (Z-ʟ-Phe) suggest that indicator monomers such as the title compound undergo a mixture of deprotonation and complex formation in the presence of benzoate but yield hydrogen-bonded complexes, which are desirable for the molecular imprinting process, with weakly basic guests like Z-ʟ-Phe. Compound 1 could be successfully employed in the synthesis of monolithic and thin-film MIPs against Z-ʟ-Phe, Z-L-glutamic acid, and penicillin G. Chromatographic assessment of the selectivity features of the monoliths revealed enantioselective discrimination and clear imprinting effects. Immobilized on glass coverslips, the thin-film MIPs of 1 displayed a clear signaling behavior with a pronounced enantioselective fluorescence quenching dependence and a promising discrimination against cross-analytes. KW - Aminosäuren KW - Enantioselektivität KW - Fluoreszenz KW - Molekular geprägte polymere KW - Sensorfilme PY - 2013 DO - https://doi.org/10.1021/jo3019522 SN - 0022-3263 SN - 1520-6904 VL - 78 IS - 4 SP - 1377 EP - 1389 PB - American Chemical Society CY - Washington, DC AN - OPUS4-27741 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ast, S. A1 - Fischer, Tobias A1 - Müller, H. A1 - Mickler, W. A1 - Schwichtenberg, M. A1 - Rurack, Knut A1 - Holdt, H.-J. T1 - Integration of the 1,2,3-triazole 'click' motif as a potent signalling element in metal ion responsive fluorescent probes N2 - In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D-A) substituted 1,2,3-triazoles as conjugative π-linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 3–5, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores. KW - Charge transfer KW - Click chemistry KW - Electron transfer KW - Fluorescent probes KW - Metal ions PY - 2013 DO - https://doi.org/10.1002/chem.201201575 SN - 0947-6539 SN - 1521-3765 VL - 19 IS - 9 SP - 2990 EP - 3005 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-27742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hecht, Mandy A1 - Fischer, Tobias A1 - Dietrich, Paul A1 - Kraus, Werner A1 - Descalzo López, Ana Belén A1 - Unger, Wolfgang A1 - Rurack, Knut T1 - Fluorinated Boron-Dipyrromethene (BODIPY) dyes: bright and versatile probes for surface analysis N2 - A family of bright boron-dipyrromethene-type fluorophores with a high number of fluorine atoms (F-BODIPYs) has been developed and characterized by X-ray crystallography and optical spectroscopy. The introduction of 3,5-bis(trifluoromethyl)phenyl and pentafluorophenyl moieties significantly enhances the photostability of such dyes, yielding for instance photostable near-infrared (NIR) fluorophores that show emission maxima>750 nm, when the BODIPY's π system is extended with two (dimethylamino)styryl and (dimethylamino)naphthastyryl moieties, or green-emitting BODIPYs with fluorescence quantum yields of unity. When equipped with a suitable group that selectively reacts for instance with amines, F-BODIPYs can be used as potent dual labels for the quantification of primary amino groups on surfaces by X-ray photoelectron spectroscopy (XPS) and fluorescence, two powerful yet complementary tools for the analysis of organic surface functional groups. The advantage of reactive F-BODIPYs is that they allow a fast and non-destructive mapping of the labelled supports with conventional fluorescence scanners and a subsequent quantification of selected areas of the same sample by the potentially traceable XPS technique. The performance is exemplarily shown here for the assessment of the amino group density on SiO2 supports, one of the most common reactive silica supports, in particular, for standard microarray applications. KW - Amino groups KW - Dyes KW - Fluorescence KW - Surface analysis KW - X-ray photoelectron spectroscopy KW - Amino-Gruppen KW - Farbstoffe KW - Fluoreszenz KW - Oberflächenanalytik KW - Röntgen-Photoelektronen-Spektroskopie PY - 2013 DO - https://doi.org/10.1002/open.201200039 SN - 2191-1363 VL - 2 IS - 1 SP - 25 EP - 38 PB - Wiley-VCH-Verl. CY - Weinheim AN - OPUS4-27783 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martínez, R. A1 - Sancenón, F. A1 - Hoffmann, Katrin A1 - Rurack, Knut A1 - Descalzo López, Ana Belén T1 - Materiales híbridos en química analítica N2 - El desarrollo de receptores sintéticos complejos basados en conceptos de la química supramolecular no garantiza en ocasiones un reconocimiento molecular selectivo. Una alternativa en ciertos aspectos más simple y prometedora es el empleo de materiales híbridos orgánico-inorgánicos preparados mediante la funcionalización de sólidos inorgánicos porosos con receptores sintéticos adecuados. El anclaje de estos sistemas coordinantes a un soporte sólido da lugar a ciertos efectos sinérgicos que no están presentes ni en el material inicial ni en el receptor por separado y que sugieren que estos nuevos materiales híbridos pueden ser empleados en el desarrollo de nuevos sensores y nuevos protocolos de reconocimiento molecular y/o iónico. The development of synthetic receptors based in supramolecular chemistry concepts will no allow a selective molecular recognition. A more simple, convenient and innovative approach relies on the use of organic-inorganic hybrid materials. These hybrid materials will be prepared by the grafting of certain synthetic receptors onto porous inorganic solids. The grafting of these coordinating systems onto a solid support leads to synergic effects that are hardly achievable with only the synthetic receptors or the solids alone. The presence of these synergic effects suggests that these organic-inorganic hybrid materials will be used for the development of novel sensory systems and novel molecular and/or ionic recognitionprotocols. KW - Soportes inorgánicos KW - Receptores sintéticos KW - Materiales híbridos KW - Efectos sinérgicos KW - Química analítica KW - Inorganic supports KW - Synthetic receptors KW - Hybrid materials KW - Synergic effects KW - Analytical chemistry PY - 2007 SN - 1575-3417 VL - 103 IS - 4 SP - 22 EP - 27 PB - Springer AN - OPUS4-17512 LA - spa AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - García-Acosta, B. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Rurack, Knut A1 - Spieles, Monika A1 - García-Breijo, E. A1 - Gil, L. T1 - Ditopic N-Crowned 4-(p-Aminophenyl)-2,6-diphenylpyridines: Implications of Macrocycle Topology on the Spectroscopic Properties, Cation Complexation, and Differential Anion Responses N2 - A family of N-crowned 4-p-(aminophenyl)-2,6-diphenylpyridines DA (1-6) has been synthezised, characterized, and studied as potential hosts for the signaling of cationic and anionic guests. The ditopic probes contain two coordination sites, a monodentate 2,6-diphenylpyridine and an anilino group with macrocycles of different ring size, denticity, and type of secondary heteroatom (O and/or S). X-ray structure analysis of aza-oxa-thia-crowned 5 indicated a largely planar chromophore. Optical spectroscopic and electrochemical studies revealed that the anilino-type donor (D) and the 2,6-diphenylpyridine acceptor (A) are strongly -conjugated, entailing intense intramolecular charge-transfer absorption bands at 340 nm. Binding studies with protons and metal ions (M = Cu2+, Zn2+, Hg2+, Fe3+, Pb2+, Ni2+, Cd2+) showed shifts of the band to the visible (440 nm) when coordination at the pyridine group occurs, strengthening its acceptor character. In contrast, no band in the visible is formed if binding takes place at the anilino group. Three different responses were found for various pairs of DA and M: selective metal coordination to D or A as well as coordination at both sites. A selective response was found for 5 and Hg2+. Because of the multitude of coordination-induced effects, the DA-M ensembles were further employed for differential anion sensing. In this protocol, the addition of an anion X to a certain, weakly coordinated DA-M can (i) lead to the formation of a ternary ion pair complex (DA-M-X), (ii) change the preference for A or D coordination, (iii) induce dissociation of the complex, or (iv) can have no effect. Various patterns of absorption changes were obtained as a result of different responses (i)-(iv) of the DA-M's in the presence of various X's. Data analysis yielded recognition patterns for acetate, F- and CN-, demonstrating the potential of simple chromogenic host-guest pairs for differential anion signaling. KW - Fluoreszenz KW - Absorption KW - Molekular Logik KW - Farbstoffe PY - 2007 DO - https://doi.org/10.1021/ic062069z SN - 0020-1669 SN - 1520-510X VL - 46 IS - 8 SP - 3123 EP - 3135 PB - American Chemical Society CY - Washington, DC AN - OPUS4-16084 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Trieflinger, C. A1 - Kovalchuck, Anton V. A1 - Daub, J. T1 - An ionically driven molecular IMPLICATION gate operating in fluorescence Mode N2 - An asymmetrically core-extended boron-dipyrromethene (BDP) dye was equipped with two electron-donating macrocyclic binding units with different metal ion preferences to operate as an ionically driven molecular IMPLICATION gate. A Na+-responsive tetraoxa-aza crown ether (R2) was integrated into the extended π system of the BDP chromophore to trigger strong intramolecular charge transfer (ICT2) fluorescence and guarantee cation-induced spectral shifts in absorption. A dithia-oxa-aza crown (R1) that responds to Ag+ was attached to the meso position of BDP in an electronically decoupled fashion to independently control a second ICT1 process of a quenching nature. The bifunctional molecule is designed in such a way that in the absence of both inputs, ICT1 does not compete with ICT2 and a high fluorescence output is obtained (InA=InB=0→Out=1). Accordingly, binding of only Ag+ at R1 (InA=1, InB=0) as well as complexation of both receptors (InA=InB=1) also yields Out=1. Only for the case in which Na+ is bound at R2 and R1 is in its free state does quenching occur, which is the distinguishing characteristic for the InA=0 and InB=1→Out=0 state that is required for a logic IMPLICATION gate and Boolean operations such as IF-THEN or NOT. KW - Charge transfer KW - Dyes/pigments KW - Fluorescence KW - Logic gates KW - Molecular devices PY - 2007 DO - https://doi.org/10.1002/chem.200700858 SN - 0947-6539 SN - 1521-3765 VL - 13 IS - 32 SP - 8998 EP - 9003 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-16085 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Hoffmann, Katrin A1 - Rurack, Knut A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. T1 - Hybridmaterialien in der analytischen Chemie KW - Analytische Chemie KW - Hybridmaterialien KW - Sensorik KW - Fluoreszenz KW - Absorption KW - Mesoporöse Silicate KW - Goldnanopartikel KW - Quantenpunkte PY - 2007 SN - 1439-9598 SN - 1521-3854 VL - 55 IS - 02 SP - 124 EP - 129 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-16080 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Rurack, Knut A1 - Weißhoff, Hardy T1 - Signalling Mechanisms in Anion-Responsive Push-Pull Chromophores: The Hydrogen-Bonding, Deprotonation and Anion-Exchange Chemistry of Functionalized Azo Dyes N2 - A family of azo dyes containing amide (1), urea (2), thiourea (3), carbamate (4) or amino (5) hydrogen-bond donating groups were synthesized and their response toward anions was studied. Acetonitrile solutions of 1-5 show bright yellow colours, due to charge-transfer bands in the 375-400 nm region, slightly modulated by the electron donor strength of the group attached to the 4 end of the 4-nitroazobenzene scaffold. Anions of different shape and size (i.e., spherical F-,Cl-, Br- and I-, planar and tetrahedral oxoanions such as NO3-, H2PO4- and HSO4-, carboxylates such as acetate and benzoate and the linear anions cyanide and thiocyanate) were employed in the recognition studies. Two different effects were distinguished: (i) bathochromic shifts of <40 nm to pale orange, due to anion coordination, and (ii) strong red shifts of ca. 200 nm with a concomitant colour change to blue, due to deprotonation. This behaviour was explained as a balance between the deprotonation tendency of the binding sites in the different receptors and the proton affinities of the anions. Semiempirical calculations were carried out to evaluate the hydrogen bond-donating abilities of the anions and the dyes and a good correlation with the experimentally found values was observed. Stability constants for the receptor-anion complexes were determined spectrophotometrically and the different responses toward fluoride and acetate were assessed by NMR titration experiments. Finally, as a special case, we also report the use of this family of compounds as colorimetric carbon dioxide sensors through reaction with the unprotonated forms of the azo dyes. KW - Chromophores KW - Dyes/Pigments KW - Chemosensors KW - Gas sensors KW - Carbon dioxide PY - 2007 DO - https://doi.org/10.1002/ejoc.200601111 SN - 1434-193X SN - 1099-0690 VL - 2007 IS - 15 SP - 2449 EP - 2458 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-16081 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Köster, D. A1 - Mayer-Enthart, Elke A1 - Sialelli, J. A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Seitz, H. T1 - Hula Hoop für DNA - Eine hoch sensitive Detektionsmethode für DNA Microarrays N2 - DNA Microarrays, auch als „DNA-Chips“ bekannt, werden verwendet, um das Vorkommen von Genen bzw. Gentranskripten zu analysieren. Sie finden breite Anwendung in der Diagnostik, der Genomanalyse und bei der Erstellung von Genexpressionsprofilen. Vor der Analyse muß auf Grund der oftmals geringen Menge an Probenmaterial eine Vervielfältigung der Probe durchgeführt werden, die jedoch leicht zu Fehlern führt. Im Rahmen dieses Projektes werden zwei experimentelle Ansätze verfolgt, durch die ohne einen Verlust an Sensitivität eine Vervielfältigung der Probe vermieden werden kann, 1) das Etablieren eines RCA-basierten Microarray Assays und 2) die Optimierung des Assays für die Detektion der Fluoreszenzsignale. KW - Newsletter von GABI KW - NGFN KW - GenoMik und FUGATO mit Informationen aus der deutschen Genomforschung PY - 2008 SN - 1617-562X VL - 1 SP - 23 EP - 25 PB - DHGP CY - Berlin AN - OPUS4-17393 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Xu, H.-J. A1 - Shen, Z. A1 - Rurack, Knut T1 - Red/Near-infrared Boron-Dipyrromethene Dyes as Strongly Emitting Fluorophores KW - BODIPY dyes KW - Near-infrared fluorophores KW - Fluorescent indicators KW - Charge transfer KW - Ring-fusion PY - 2008 DO - https://doi.org/10.1196/annals.1430.016 SN - 0077-8923 SN - 1749-6632 SN - 0094-8500 VL - 1130 SP - 164 EP - 171 PB - New York Academy of Sciences CY - New York, NY AN - OPUS4-17632 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Casasús, R. A1 - Comes, M. A1 - Coll, C. A1 - Marcos, M. Dolores A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Amorós, P. A1 - El Haskouri, J. A1 - Garró, N. A1 - Rurack, Knut T1 - A mesoporous 3D hybrid material with dual functionality for Hg2+ detection and adsorption KW - Dyes/pigments KW - Environmental chemistry KW - Mercury KW - Mesoporous materials KW - Sensors PY - 2008 DO - https://doi.org/10.1002/chem.200800632 SN - 0947-6539 SN - 1521-3765 VL - 14 SP - 8267 EP - 8278 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-18443 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Spieles, Monika A1 - Rurack, Knut T1 - Aquaraines as reporter units: insights into their photophysics, protonation, and metal-ion coordination behaviour KW - Dyes/pigments KW - Fluorescence KW - Metal ions KW - Protonation KW - Squaraines KW - Farbstoffe KW - Fluoreszenz KW - Metallionen KW - Protonierung PY - 2008 DO - https://doi.org/10.1002/chem.200800300 SN - 0947-6539 SN - 1521-3765 VL - 14 SP - 10101 EP - 10114 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-18444 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Rurack, Knut ED - Resch-Genger, Ute ED - O.S. Wolfbeis, T1 - Fluorescence Quantum Yields:Methods of Determination and Standards N2 - The fluorescence quantum yield Φ f is a key property that characterizes the ability of a fluorophore to convert absorbed photons into emitted photons under various environmental conditions. Knowledge of it is important for the successful development of fluorometric indication and visualization methods and for the understanding of light-driven processes in the natural sciences. Φ f is a molecule- or material-related parameter and can thus significantly differ from the fraction of absorbed photons that are actually measured as the fluorescence signal of a certain sample, e.g., when the signal is modulated by reabsorption, self-quenching or polarization effects. The determination of Φ f can be performed in absolute measurements or relative to a fluorescent standard material with a known Φ f by optical or calorimetric methods. Here the different procedures and techniques are described and compared, and the suitability of a representative number of dyes that have been proposed as fluorescence reference materials in the past 25 years is discussed. Besides addressing specific issues such as low-temperature measurements and the appropriate choice of standards and measurement conditions, we conclude with recommendations for better standardization and quality management in this area. PY - 2008 SN - 978-3-540-75206-6 DO - https://doi.org/10.1007/4243_2008_019 SN - 1617-1306 N1 - Serientitel: Springer Series on Fluorescence – Series title: Springer Series on Fluorescence VL - 5 IS - Part B SP - 101 EP - 145 PB - Springer AN - OPUS4-18445 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Marcos, M. Dolores A1 - Monte, Christian A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut T1 - Mesoporous silica materials with covalently anchored phenoxazinone dyes as fluorescent hybrid materials for vapour sensing KW - Anorganisch-organische Hybridmaterialien KW - Sensorik KW - Fluoreszenz KW - Flüchtige organische Verbindungen PY - 2007 DO - https://doi.org/10.1039/b707473e SN - 0959-9428 SN - 1364-5501 VL - 17 SP - 4716 EP - 4723 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-16139 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wu, D. A1 - Descalzo López, Ana Belén A1 - Weik, F. A1 - Emmerling, Franziska A1 - Shen, Z. A1 - You, X.-Z. A1 - Rurack, Knut T1 - Ein kernmodifiziertes Rubyrin mit meso-Aryl-Subsituenten und Phenanthren-anellierten Pyrrolringen als hoch konjugierter NIR-Farbstoff und Hg2+-Sonde KW - Fluoreszenz KW - NIR-Farbstoffe KW - Porphyrinoide KW - Quecksilber KW - Sensoren PY - 2008 DO - https://doi.org/10.1002/ange.200702854 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 120 IS - 1 SP - 199 EP - 203 PB - Wiley-VCH CY - Weinheim AN - OPUS4-16447 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wu, D. A1 - Descalzo López, Ana Belén A1 - Weik, F. A1 - Emmerling, Franziska A1 - Shen, Z. A1 - You, X.-Z. A1 - Rurack, Knut T1 - A core-modified Rubyrin with meso-aryl substituents and phenanthrene-fused pyrrole rings: a highly conjugated near-infrared dye and Hg2+ probe KW - Fluorescence KW - Mercury KW - NIR dyes KW - Porphyrinoids KW - Sensors PY - 2008 DO - https://doi.org/10.1002/Anie.200702854 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 47 IS - 1 SP - 193 EP - 197 PB - Wiley-VCH CY - Weinheim AN - OPUS4-16448 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mayer-Enthart, Elke A1 - Sialelli, Julien A1 - Rurack, Knut A1 - Resch-Genger, Ute A1 - Köster, D. A1 - Seitz, H. T1 - Toward Improved Biochips Based on Rolling Circle Amplification - Influences of the Microenvironment on the Fluorescence Properties of Labeled DNA Oligonucleotides KW - Rolling circle amplification KW - Fluorescence KW - Biochips KW - Microarrays KW - Signal amplification KW - Cy3-labeled oligonucleotides KW - DNA technology PY - 2008 DO - https://doi.org/10.1196/annals.1430.022 SN - 0077-8923 SN - 1749-6632 SN - 0094-8500 VL - 1130 SP - 287 EP - 292 PB - New York Academy of Sciences CY - New York, NY AN - OPUS4-17633 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Bricks, J.L. A1 - Descalzo, Ana B. A1 - Garcia, B. A1 - Kovalchuck, Anton V. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. T1 - Macrocycles in a Different Light: The Influence of the Nature and Substitution Pattern of Heteroatoms on the Photophysics of Chromophore-Appended Crown Ethers T2 - 28th International Symposium on Macrocyclic Chemistry CY - Gdansk, Poland DA - 2003-07-13 PY - 2003 AN - OPUS4-4889 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Büschel, M. A1 - Daub, J. T1 - Intramolecular Charge-Transfer Characteristics of Fluorescent Donor-[Ethynyl-Donor]n (n=1,2) Dyads and Triads T2 - 8th Conference on Methods and Applications of Fluorescence: Spectroscopy, Imaging and Probes CY - Prague, Czech Republic DA - 2003-08-24 PY - 2003 AN - OPUS4-4894 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hennrich, G. A1 - Rurack, Knut A1 - Spieles, Monika T1 - Reconfiguration of the Symmetry and Charge-Transfer Characteristics of a Triply Crowned 1,3,5-Tris(arylalkynyl)mesitylene by Successive Metal Ion Complexation N2 - A triply benzocrown-ether-functionalized trialkynylmesitylene derivative with C3 symmetry as well as its linear analogue have been synthesized and their optical properties have been studied by UV/Vis absorption, steady-state and time-resolved fluorescencece spectroscopy. The spectroscopic investigation of the uncomplexed compounds revealed the nature of the electronic and excitonic communication pathway in the ground and excited states of the all-meta-substituted chromophore system. Upon cation complexation, the octopolar character of the free trialkynyl compound becomes dipolar and finally returns to octopolar in the fully complexed species. KW - Acetylenic scaffolding KW - Donor-acceptor systems KW - Fluorescence spectroscopy KW - UV/Vis spectroscopy KW - Supramolecular chemistry PY - 2006 DO - https://doi.org/10.1002/ejoc.200500595 SN - 1434-193X SN - 1099-0690 VL - 2006 IS - 2 SP - 516 EP - 521 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-12171 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Trieflinger, C. A1 - Röhr, Holger A1 - Rurack, Knut A1 - Daub, J. T1 - Multiples Schalten und photogesteuerte Elektrochemilumineszenz einer Dihydroazulen-Bordipyrromethen-Dyade KW - Bordipyrromethen KW - Elektrochemilumineszenz KW - Fluoreszenz KW - Molekulare Schalter KW - Photochromie PY - 2005 DO - https://doi.org/10.1002/ange.200501573 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 117 IS - 42 SP - 7104 EP - 7107 PB - Wiley-VCH CY - Weinheim AN - OPUS4-12172 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Röhr, Holger A1 - Trieflinger, C. A1 - Rurack, Knut A1 - Daub, J. T1 - Proton- and Redox-Controlled Switching of Photo- and Electrochemiluminescence in Thiophenyl-Substituted Boron-Dipyrromethene Dyes N2 - A luminescent molecular switch in which the active thiol/disulfide switching element is attached to a meso-phenyl-substituted boron-dipyrromethene (BDP) chromophore as the signalling unit is presented. The combination of these two functional units offers great versatility for multimodal switching of luminescence: 1) deprotonation/protonation of the thiol/thiolate moiety allows the highly fluorescent meso-p-thiophenol-BDP and its nonfluorescent thiolate analogue to be chemically and reversibly interconverted, 2) electrochemical oxidation of the monomeric dyes yields the fluorescent disulfide-bridged bichromophoric dimer, also in a fully reversible process, and 3) besides conventional photoexcitation, the well separated redox potentials of the BDP also allow the excited BDP state to be generated electrochemically (i.e., processes 1) and 2) can be employed to control both photo- and electrochemiluminescence (ECL) of the BDP). The paper introduces and characterizes the various states of the switch and discusses the underlying mechanisms. Investigation of the ortho analogue of the dimer provided insight into potential chromophore-chromophore interactions in such bichromophoric architectures in both the ground and the excited state. Comparison of the optical and redox properties of the two disulfide dimers further revealed structural requirements both for redox switches and for ECL-active molecular ensembles. By employing thiol/disulfide switching chemistry and BDP luminescence features, it was possible to create a prototype molecular ensemble that shows both fully reversible proton- and redox-gated electrochemiluminescence. KW - Boron-dipyrromethene KW - Electrochemiluminescence KW - Fluorescence KW - Molecular switches KW - Redox chemistry KW - Thiol/disulfide chemistry KW - Fluoreszenz KW - Elektrochemilumineszenz KW - Redox-Kontrolle KW - Molekulare Sensoren PY - 2006 DO - https://doi.org/10.1002/chem.200500729 SN - 0947-6539 SN - 1521-3765 VL - 12 IS - 3 SP - 689 EP - 700 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-12175 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Monte, Christian T1 - Metallionen auf der Spur KW - Fluoreszenzsonden KW - Schwermetalle KW - Übergangsmetalle KW - Faseroptik PY - 2006 SN - 0344-1733 SN - 1610-8256 IS - 1/2 SP - 20 EP - 22 PB - Vogel CY - Würzburg AN - OPUS4-12179 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bricks, J.L. A1 - Kovalchuck, Anton V. A1 - Trieflinger, C. A1 - Nofz, Marianne A1 - Büschel, M. A1 - Tolmachev, A.I. A1 - Daub, J. A1 - Rurack, Knut T1 - On the Development of Sensor Molecules that Display FeIII-amplified Fluorescence N2 - Incorporation of a tailor-made size-restricted dithia-aza-oxa macrocycle, 1-oxa-4,10-dithia-7-aza-cyclododecane, via a phenyl linker into two fluorescent sensor molecules with electronically decoupled, rigidly fixed, and sterically preoriented architectures, a 1,3,5-triaryl-2-pyrazoline and a meso-substituted boron-dipyrromethene (BDP), yields amplified fluorescence in the red-visible spectral range upon binding of FeIII ions. The response to FeIII and potentially interfering metal ions is studied in highly polar aprotic and protic solvents for both probes as well as in neat and buffered aqueous solution for one of the sensor molecules, the BDP derivative. In organic solvents, the fluorescence of both indicators is quenched by an intramolecular charge or electron transfer in the excited state and coordination of FeIII leads to a revival of their fluorescence without pronounced spectral shifts. Most remarkably, the unbound BDP derivative shows dual emission in water and can be employed for the selective ratiometric signaling of FeIII in buffered aqueous solutions. KW - Fluoreszenz KW - Eisen KW - Fluoreszenzmarker PY - 2005 DO - https://doi.org/10.1021/ja050652t SN - 0002-7863 SN - 1520-5126 VL - 127 SP - 13522 EP - 13529 PB - American Chemical Society CY - Washington, DC AN - OPUS4-12180 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Hoffmann, Katrin A1 - Rurack, Knut T1 - Die supramolekulare Chemie organisch-anorganischer Hybrid-Nanomaterialien N2 - Die Entwicklung von Hybridmaterialien mit stark verbesserten Funktionen gelingt durch die Kombination geeigneter Nanomaterialien als Träger mit Motiven aus der supramolekularen Chemie. Diese hetero-supramolekularen Konzepte bieten vielfältige Möglichkeiten, die Lücken zwischen der Molekülchemie, Materialwissenschaften und Nanotechnologie zu schließen. Im Hinblick auf funktionelle Aspekte wurden in jüngster Zeit wichtige Fortschritte erzielt, z. B. verbesserte Erkennungs- und Sensoreigenschaften durch die Anordnung von Molekülen auf vororganisierten Oberflächen, der reversible Aufbau von nanometergroßen Netzwerken und dreidimensionalen Strukturen oder biomimetische und gesteuerte chemische Prozesse in Hybrid-Nanomaterialien, die als Grundlage für hoch spezialisierte Protokolle in dreidimensionalen Gerüststrukturen dienen können. Diese Ansätze ermöglichen eine Feinabstimmung der Eigenschaften von Nanomaterialien und eröffnen neue Perspektiven für die Anwendung supramolekularer Konzepte. KW - Supramolekulare Chemie KW - Anorganisch-organische Hybridmaterialien KW - Sensorik KW - Molekulare Maschinen KW - Aggregation KW - Mesoporöse Materialien KW - Molekulare Erkennung KW - Nanopartikel KW - Sensoren PY - 2006 DO - https://doi.org/10.1002/ange.200600734 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 118 IS - 36 SP - 6068 EP - 6093 PB - Wiley-VCH CY - Weinheim AN - OPUS4-12821 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -