TY - JOUR A1 - García-Acosta, B. A1 - Albiach-Martí, X. A1 - García, E. A1 - Gil, R. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Sancenón, F. A1 - Soto, J. T1 - Coordinative and electrostatic forces in action: from the design of differential chromogenic anion sensors to selective carboxylate recognition JF - Chemical communications N2 - A new family of differential chromogenic anion chemosensors is described based on anilinopyridine–metal cation coordinative signalling ensembles KW - Differentielle Sensoren KW - Anionen KW - Carboxylat KW - Chromogene Sensoren KW - Koordinative Bindungen KW - Elektrostatische Wechselwirkungen PY - 2004 DO - https://doi.org/10.1039/b314997h SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x IS - 7 SP - 774 EP - 775 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-3438 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 JF - Journal of the American chemical society 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 - 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 JF - Chemical communications 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+ JF - Angewandte Chemie 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 - 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 JF - Journal of the American chemical society 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 - 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 JF - Journal of materials chemistry 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) JF - Chemical communications 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 - 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 JF - Inorganic Chemistry 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 - 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 JF - European journal of organic chemistry 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 - 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 JF - Chemistry - A European journal 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 -