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 U6 - 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 U6 - 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 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Hecht, Mandy A1 - Biyikal, Mustafa A1 - Rurack, Knut T1 - Nanoscopic optical sensors based on functional supramolecular hybrid materials N2 - This review highlights how the combination of supramolecular principles and nanoscopic solid structures enables the design of new hybrid sensing ensembles with improved sensitivity and/or selectivity and for the targeting of analytes for which selectivity is hard to achieve by conventional methods. Such ideas are bridging the gap between molecules, materials sciences and nanotechnology. Relevant examples will be detailed, taking into account functional aspects such as (1) enhanced coordination of functionalized solids, (2) enhanced signalling through preorganization, (3) signalling by assembly–disassembly of nanoscopic objects, (4) biomimetic probes utilizing discrimination by polarity and size and (5) distinct switching and gating protocols. These strategies are opening new prospects for sensor research and signalling paradigms at the frontier between nanotechnology, smart materials and supramolecular chemistry. KW - Supramolecular chemistry KW - Optical probes KW - Nanotechnology KW - Hybrid organic-inorganic materials PY - 2011 U6 - https://doi.org/10.1007/s00216-010-4198-2 SN - 1618-2642 SN - 1618-2650 VL - 399 IS - 1 SP - 55 EP - 74 PB - Springer CY - Berlin AN - OPUS4-22908 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xu, H.-J. A1 - Mack, J. A1 - Descalzo López, Ana Belén A1 - Shen, Z. A1 - Kobayashi, N. A1 - You, X.-Z. A1 - Rurack, Knut T1 - meso-Aryl phenanthroporphyrins: Synthesis and spectroscopic properties N2 - The successful synthesis of tetraphenyltetraphenanthroporphyrin (TPTPhenP; 5a) in 2006 under modified Rothemund–Lindsey conditions yielded a tetraphenyl porphyrinoid with a B band redshifted to an unprecedented 576 nm. Radially symmetric fused-ring expansion of tetraphenylporphyrin with phenanthrene moieties results in very deep saddling due to steric crowding and very marked redshifts of the Q and B (or Soret) porphyrinoid absorption bands. The extent to which the TPTPhenP structure can be further modified is explored, and the optical properties of TPTPhenPs are analyzed based on a perimeter model approach that makes use of time-dependent DFT calculations and magnetic circular dichroism spectroscopy and also based on a detailed analysis of the fluorescence emission. Attempts to introduce substituents at the ortho and meta positions of the meso-phenyl groups and to insert a central metal proved unsuccessful. The synthesis of a series of TPTPhenPs with strong electron-withdrawing (—CN, —NO2) and -donating (—CH3, —N(CH3)2) substituents at the para positions of the meso-phenyl rings is reported. Marked redshifts of the main spectral bands were consistently observed. The most pronounced spectral changes were observed with —N(CH3)2 groups (5i) due to a marked destabilization of the HOMO, which has large MO coefficients on the meso-carbon atoms. Protonation of 5i at both the ligand core and at the —N(CH3)2 groups resulted in unprecedented Q00 band absorption at wavelengths greater than 1200 nm. KW - Charge transfer KW - Circular dichroism KW - Dyes/pigments KW - Porphyrinoids KW - Protonation PY - 2011 U6 - https://doi.org/10.1002/chem.201002596 SN - 0947-6539 SN - 1521-3765 VL - 17 IS - 32 SP - 8965 EP - 8983 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-24208 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Wagner, R. A1 - Wan, Wei A1 - Lazrag, I. A1 - Sellergren, B. A1 - Fernandez Sanchez, J. F. A1 - Urraca-Ruiz, J. A1 - Moreno-Bondi, C. A1 - Orellana, G. T1 - Molecularly Imprinted Polymer Films as Sensory Materials for the Selective Detection of Carboxylates via Flourescence T2 - European Polymer Congress 2011(EPF) CY - Granada, Spain DA - 2011-06-26 PY - 2011 AN - OPUS4-23931 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Climent Terol, Estela A1 - Martínez-Mánez, Ramon T1 - Implementing Signal Amplification Features with Gated Mesoporous Sensory Hybrids for Methymercury Determination T2 - Hybrid Materials 2011 CY - Strasbourg, France DA - 2011-03-03 PY - 2011 AN - OPUS4-23935 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rurack, Knut A1 - Martínez-Mánez, Ramon T1 - Organically functionalized mesopporous silica particles as a versatile platform for Hg2+ determination, sequestration and CH3Hg+ speciation witz simple analytical protocols T2 - ANAKON 2011 CY - Zurich, Switzerland DA - 2011-03-22 PY - 2011 AN - OPUS4-23936 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nöll, G. A1 - Daub, J. A1 - Lutz, M. A1 - Rurack, Knut T1 - Synthesis, spectroscopic properties, and electropolymerization of azulene dyads N2 - Four azulene dyads have been synthesized and studied by spectroscopic and electrochemical methods. A triarylamine, a boron-dipyrromethene (BDP or BODIPY), a porphyrin, and an isoalloxazine moiety have been linked to an extended π electron system at the 2-position of azulene, leading to the dyads 1–4, respectively. For the synthesis of 1–4, first 2-(4-ethynyl-phenyl)azulene (EPA) was prepared, which was further reacted with the halogenated chromophores by Pd-catalyzed cross-coupling reactions. The dyads 1–4 exhibit strong absorption bands in the visible range, which are dominated by the absorption spectra of the individual subchromophores. Fluorometric studies of 2–4 revealed that after excitation of the subchromophoric unit attached to the parent azulene moiety, quenching mainly through energy transfer to azulene is effective, whereas possible charge-transfer interactions play only a minor role. Potentiodynamic oxidation of the dyads 1–4 leads to the formation of polymer films, which are deposited at the electrode. The polymer film derived from 1 was further characterized by spectroelectrochemistry. During positive doping of poly-1, a strong absorption band appears at 13,200 cm–1, which is typical for triarylamine radical cations. This band is overlapping with a broad absorption band in the low-energy region that might be caused by charge-transfer interactions within the polymer. KW - Azulen KW - Elektropolymerisation KW - Energietransfer KW - Farbstoffe KW - Fluoreszenz PY - 2011 U6 - https://doi.org/10.1021/jo200080v SN - 0022-3263 SN - 1520-6904 VL - 76 IS - 12 SP - 4859 EP - 4873 PB - American Chemical Society CY - Washington, DC AN - OPUS4-23987 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Soto, J. A1 - Villaescusa, L.A. A1 - Rurack, Knut T1 - Squaraine 'ships' in the Y zeolite 'bottle': a chromogenic sensing material for the detection of volatile amines and thiols N2 - The inclusion of squaraine (SQ) dye I into the supercages of zeolite Y (structure code FAU) with a SiO2/Al2O3 ratio of 30 (Z30) through a two-step ship-in-the-bottle approach is reported, resulting in the squaraine-containing hybrid material Z30-SQ. Attempts to use the same synthetic procedure on sodium and ammonium Y zeolites were unsuccessful, stressing the importance of the presence of Brønsted acid centres in the Z30 zeolite. The reflectance spectra of Z30-SQ show a maximum in the typical squaraine monomer region at 618 nm and a shoulder at 570 nm. Spectral analyses revealed that the major species are SQ dimers and (tightly adsorbed) SQ monomers and SQ aggregates are only formed to a minor degree. The emission spectrum of Z30-SQ shows a single band at 669 nm. The sensory performance of this material was tested in the presence of volatile propylamine and propylthiol and other volatile organic compounds (acetone, ethanol, dichloromethane, hexane, acetonitrile, ethyl acetate, ethyl ether and acetic acid). The blue Z30-SQ material reacts with the thiol and amine derivatives, resulting in the bleaching of the solid and disappearance of the absorption band in the visible region, but does not undergo spectroscopic changes in the presence of other volatile organic compounds (VOCs). Whereas the reaction with propylamine is irreversible, a partial reversibility was found in the presence of the thiol. Theoretical investigations of the reactivity of I with several VOC molecules at the semi-empirical level reproduced well the experimentally observed reactivity. KW - Fluoreszenz KW - Gassensorik KW - Squarain-Farbstoffe KW - Zeolite PY - 2011 U6 - https://doi.org/10.1039/c0jm03780j SN - 0959-9428 SN - 1364-5501 VL - 21 IS - 13 SP - 5004 EP - 5010 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-23480 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Spieles, Monika T1 - Fluorescence quantum yields of a series of red and near-infrared dyes emitting at 600-1000 nm N2 - The determination of the fluorescence quantum yields (QY, Φf) of a series of fluorescent dyes that span the absorption/excitation and emission ranges of 520-900 and 600-1000 nm is reported. The dyes encompass commercially available rhodamine 101 (Rh-101, Φf = 0.913), cresyl violet (0.578), oxazine 170 (0.579), oxazine 1 (0.141), cryptocyanine (0.012), HITCI (0.283), IR-125 (0.132), IR-140 (0.167), and four noncommercial cyanine dyes with specific spectroscopic features, all of them in dilute ethanol solution. The QYs have been measured relative to the National Institute of Standards and Technology's standard reference material (SRM) 936a (quinine sulfate, QS) on a traceably characterized fluorometer, employing a chain of transfer standard dyes that include coumarin 102 (Φf = 0.764), coumarin 153 (0.544), and DCM (0.435) as links between QS and Rh-101. The QY of Rh-101 has also been verified in direct measurements against QS using two approaches that rely only on instrument correction. In addition, the effects of temperature and the presence of oxygen on the fluorescence quantum yield of Rh-101 have been assessed. KW - Farbstoffe KW - Fluoreszenz KW - Nahes Infrarot KW - Quantenausbeute PY - 2011 U6 - https://doi.org/10.1021/ac101329h SN - 0003-2700 SN - 1520-6882 VL - 83 IS - 4 SP - 1232 EP - 1242 PB - American Chemical Society CY - Washington, DC AN - OPUS4-23481 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -