788 research outputs found

    Synthesis and evaluation of a novel pyrenyl-appended triazole-based thiacalix[4]arene as a fluorescent sensor for Ag+ ion

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    New fluorescent chemosensors 1,3-alternate-1 and 2 with pyrenyl-appended triazole-based on thiacalix[4]arene were synthesized. The fluorescence spectra changes suggested that chemosensors 1 and 2 are highly selective for Ag+ over other metal ions by enhancing the monomer emission of pyrene in neutral solution. However, other heavy metal ions, such as Cu2+, and Hg2+ quench both the monomer and excimer emission of pyrene acutely. The 1H NMR results indicated that Ag+ can be selectively recognized by the triazole moieties on the receptors 1 and 2 together with the ionophoricity cavity formed by the two inverted benzene rings and sulfur atoms of the thiacalix[4]arene

    Mimicking tricks from nature with sensory organic-inorganic hybrid materials

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    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. © 2011 The Royal Society of Chemistry.Martínez Mañez, R.; Sancenón Galarza, F.; Biyikal, M.; Hecht, M.; Rurack, K. (2011). Mimicking tricks from nature with sensory organic-inorganic hybrid materials. Journal of Materials Chemistry. 21(34):12588-12604. doi:10.1039/c1jm11210dS12588126042134Ma, M. (2007). Encoding Olfactory Signals via Multiple Chemosensory Systems. Critical Reviews in Biochemistry and Molecular Biology, 42(6), 463-480. doi:10.1080/10409230701693359Leinders-Zufall, T., Lane, A. P., Puche, A. C., Ma, W., Novotny, M. V., Shipley, M. T., & Zufall, F. (2000). Ultrasensitive pheromone detection by mammalian vomeronasal neurons. Nature, 405(6788), 792-796. doi:10.1038/35015572Serezani, C. H., Ballinger, M. N., Aronoff, D. M., & Peters-Golden, M. (2008). Cyclic AMP. 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Optical Sensor Based on Nanomaterial for the Selective Detection of Toxic Metal Ions. Advanced Functional Materials, 17(17), 3441-3446. doi:10.1002/adfm.200601202Palomares, E., Vilar, R., & Durrant, J. R. (2004). Heterogeneous colorimetric sensor for mercuric saltsElectronic supplementary information (ESI) available: Materials and methods. See http://www.rsc.org/suppdata/cc/b3/b314138a/. Chemical Communications, (4), 362. doi:10.1039/b314138aWang, Y., Li, B., Zhang, L., Liu, L., Zuo, Q., & Li, P. (2010). A highly selective regenerable optical sensor for detection of mercury(ii) ion in water using organic–inorganic hybrid nanomaterials containing pyrene. New Journal of Chemistry, 34(9), 1946. doi:10.1039/c0nj00039fLi, L.-L., Sun, H., Fang, C.-J., Xu, J., Jin, J.-Y., & Yan, C.-H. (2007). Optical sensors based on functionalized mesoporous silica SBA-15 for the detection of multianalytes (H+ and Cu2+) in water. Journal of Materials Chemistry, 17(42), 4492. doi:10.1039/b708857dZhang, H., Zhang, P., Ye, K., Sun, Y., Jiang, S., Wang, Y., & Pang, W. (2006). Mesoporous material grafted with luminescent molecules for the design of selective metal ion chemosensor. Journal of Luminescence, 117(1), 68-74. doi:10.1016/j.jlumin.2005.04.009Gao, L., Wang, J. Q., Huang, L., Fan, X. X., Zhu, J. H., Wang, Y., & Zou, Z. G. (2007). Novel Inorganic−Organic Hybrid Fluorescence Chemosensor Derived from SBA-15 for Copper Cation. Inorganic Chemistry, 46(24), 10287-10293. doi:10.1021/ic7008732Wang, J.-Q., Huang, L., Xue, M., Wang, Y., Gao, L., Zhu, J. H., & Zou, Z. (2008). Architecture of a Hybrid Mesoporous Chemosensor for Fe3+ by Covalent Coupling Bis-Schiff Base PMBA onto the CPTES-Functionalized SBA-15. The Journal of Physical Chemistry C, 112(13), 5014-5022. doi:10.1021/jp7099948Gao, L., Wang, Y., Wang, J., Huang, L., Shi, L., Fan, X., … Li, Z. (2006). A Novel ZnII-Sensitive Fluorescent Chemosensor Assembled within Aminopropyl-Functionalized Mesoporous SBA-15. Inorganic Chemistry, 45(17), 6844-6850. doi:10.1021/ic0516562Balaji, T., Sasidharan, M., & Matsunaga, H. (2005). Naked eye detection of cadmium using inorganic–organic hybrid mesoporous material. Analytical and Bioanalytical Chemistry, 384(2), 488-494. doi:10.1007/s00216-005-0187-2Balaji, T., El-Safty, S. A., Matsunaga, H., Hanaoka, T., & Mizukami, F. (2006). Optical Sensors Based on Nanostructured Cage Materials for the Detection of Toxic Metal Ions. Angewandte Chemie International Edition, 45(43), 7202-7208. doi:10.1002/anie.200602453El-Safty, S. A., Ismail, A. A., Matsunaga, H., & Mizukami, F. (2007). Optical Nanosensor Design with Uniform Pore Geometry and Large Particle Morphology. Chemistry - A European Journal, 13(33), 9245-9255. doi:10.1002/chem.200700499El-Safty, S. A., Ismail, A. A., Matsunaga, H., Hanaoka, T., & Mizukami, F. (2008). Optical Nanoscale Pool-on-Surface Design for Control Sensing Recognition of Multiple Cations. Advanced Functional Materials, 18(10), 1485-1500. doi:10.1002/adfm.200701059Ros-Lis, J. V., Casasús, R., Comes, M., Coll, C., Marcos, M. D., Martínez-Máñez, R., … Rurack, K. (2008). A Mesoporous 3D Hybrid Material with Dual Functionality for Hg2+Detection and Adsorption. Chemistry - A European Journal, 14(27), 8267-8278. doi:10.1002/chem.200800632Lee, S. J., Bae, D. R., Han, W. S., Lee, S. S., & Jung, J. H. (2008). Different Morphological Organic–Inorganic Hybrid Nanomaterials as Fluorescent Chemosensors and Adsorbents for CuII Ions. European Journal of Inorganic Chemistry, 2008(10), 1559-1564. doi:10.1002/ejic.200701073Lee, H. Y., Bae, D. R., Park, J. C., Song, H., Han, W. S., & Jung, J. H. (2009). A Selective Fluoroionophore Based on BODIPY-functionalized Magnetic Silica Nanoparticles: Removal of Pb2+ from Human Blood. 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    Multiplexed Detection of Analytes on Single Test Strips with Antibody-Gated Indicator-Releasing Mesoporous Nanoparticles

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    This is the peer reviewed version of the following article: Climent, E., Biyikal, M., Gröninger, D., Weller, M. G., Martínez¿Máñez, R., & Rurack, K. (2020). Multiplexed Detection of Analytes on Single Test Strips with Antibody-Gated Indicator-Releasing Mesoporous Nanoparticles. Angewandte Chemie International Edition, 59(52), 23862-23869, which has been published in final form at https://doi.org/10.1002/anie.202009000. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] Rapid testing methods for the use directly at a point of need are expected to unfold their true potential especially when offering adequate capabilities for the simultaneous measurement of multiple analytes of interest. Considering the unique modularity, high sensitivity, and selectivity of antibody-gated indicator delivery (gAID) systems, a multiplexed assay for three small-molecule explosives (TATP, TNT, PETN) was thus developed, allowing to detect the analytes simultaneously with a single test strip at lower ppb concentrations in the liquid phase in 2 adsorption/desorption measurements, Y. Salinas and L. E. Santos for support on the materials screening, A. Walter, S. Ramin and A. Hesse for obtaining the sera and R. Gotor and J. Bell for their help in the fabrication of the home-made smartphone periphery. Open access funding enabled and organized by Projekt DEAL.Climent Terol, E.; Biyikal, M.; Gröninger, D.; Weller, MG.; Martínez-Máñez, R.; Rurack, K. (2020). Multiplexed Detection of Analytes on Single Test Strips with Antibody-Gated Indicator-Releasing Mesoporous Nanoparticles. Angewandte Chemie International Edition. 59(52):23862-23869. https://doi.org/10.1002/anie.2020090002386223869595

    Anilinopyridine metal complexes for the selective chromogenic sensing of cyanide anion

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    [EN] Probe 1, which contains an anilinopyridine chromophore and an aza-oxa macrocyclic subunit, presented an absorption band centered at 340 nm in acetonitrile. Addition of Fe(III), Cr(III) and Hg(II) induced the growth of a new absorption band at 430 nm (with color change from colorless to yellow), whereas in the presence of Cu(II), Zn(II) and Pb(II), less marked changes were observed. The color changes observed upon addition of Fe(III), Cr(III) and Hg(II) were ascribed to the formation of 1:1 stoichiometry complexes with probe 1. Coordination of Fe(III), Cr(III) and Hg(II) with the pyridine fragment of 1 induced an enhancement of the charge transfer character accompanied with a marked bathochromic shift that was reflected in a color change from colorless to yellow. The strength of the interaction between probe 1 and Fe(III) cation was modulated upon interaction with anions. Of all the anions tested, only cyanide was able to induce the bleaching of the yellow 1Fe(III) complex solution. This bleaching was ascribed to the formation of 1Fe(III)-CN complex that restored, to some extent, the optical features of the free probe allowing the chromogenic sensing of cyanide. Besides, 1Fe(III) complex was used to detect cyanide in acetonitrile-water 90:10 v/v mixtures with good recoveries.This work was supported by the Generalitat Valenciana [grant number PROMETEOII/2014/047]; Ministerio de Economia y Competitividad [grant number MAT2015-64139-C4-1-R], [grant number AGL2015-70235-C2-2-R (MINECO/FEDER)].Lozano-Torres, B.; Marcos Martínez, MD.; Pardo Vicente, MT.; Sancenón Galarza, F.; Martínez-Máñez, R.; Rurack, K. (2018). Anilinopyridine metal complexes for the selective chromogenic sensing of cyanide anion. Journal of Coordination Chemistry. 71(6):786-796. https://doi.org/10.1080/00958972.2018.1434719S786796716Boening, D. W., & Chew, C. M. (1999). Water, Air, and Soil Pollution, 109(1/4), 67-79. doi:10.1023/a:1005005117439Tylleskar, T., Howlett, W. P., Rwiza, H. T., Aquilonius, S. M., Stalberg, E., Linden, B., … Rosling, H. (1993). Konzo: a distinct disease entity with selective upper motor neuron damage. Journal of Neurology, Neurosurgery & Psychiatry, 56(6), 638-643. doi:10.1136/jnnp.56.6.638(a) WHO. Guidelines for Drinking-Water Quality, p. 342, World Health Organisation, Geneva, Switzerland (2011)Safavi, A., Maleki, N., & Shahbaazi, H. . (2004). Indirect determination of cyanide ion and hydrogen cyanide by adsorptive stripping voltammetry at a mercury electrode. Analytica Chimica Acta, 503(2), 213-221. doi:10.1016/j.aca.2003.10.032Batista, R. M. F., Oliveira, E., Costa, S. P. G., Lodeiro, C., & Raposo, M. M. M. (2013). Cyanide and fluoride colorimetric sensing by novel imidazo-anthraquinones functionalised with indole and carbazole. Supramolecular Chemistry, 26(2), 71-80. doi:10.1080/10610278.2013.824082Santos-Figueroa, L. E., Moragues, M. E., Climent, E., Agostini, A., Martínez-Máñez, R., & Sancenón, F. (2013). Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the years 2010–2011. Chemical Society Reviews, 42(8), 3489. doi:10.1039/c3cs35429fWiskur, S. L., Ait-Haddou, H., Lavigne, J. J., & Anslyn, E. V. (2001). Teaching Old Indicators New Tricks. Accounts of Chemical Research, 34(12), 963-972. doi:10.1021/ar9600796Kaur, K., Saini, R., Kumar, A., Luxami, V., Kaur, N., Singh, P., & Kumar, S. (2012). Chemodosimeters: An approach for detection and estimation of biologically and medically relevant metal ions, anions and thiols. Coordination Chemistry Reviews, 256(17-18), 1992-2028. doi:10.1016/j.ccr.2012.04.013García-Acosta, B., Albiach-Martí, X., García, E., Gil, L., Martínez-Máñez, R., Rurack, K., … Soto, J. (2004). Coordinative and electrostatic forces in action: from the design of differential chromogenic anion sensors to selective carboxylate recognition. Chem. Commun., (7), 774-775. doi:10.1039/b314997hGarcía-Acosta, B., Martínez-Máñez, R., Sancenón, F., Soto, J., Rurack, K., Spieles, M., … Gil, L. (2007). Ditopic N-Crowned 4-(p-Aminophenyl)-2,6-diphenylpyridines:  Implications of Macrocycle Topology on the Spectroscopic Properties, Cation Complexation, and Differential Anion Responses. Inorganic Chemistry, 46(8), 3123-3135. doi:10.1021/ic062069zVerhoeven, J. W. (s. f.). Sigma-coupled Charge-transfer Probes of the Fluoroprobe and Fluorotrope Type. Topics in Fluorescence Spectroscopy, 249-284. doi:10.1007/0-387-23335-0_7Kurihara, M., Kawashima, T., & Ozutsumi, K. (2000). Complexation of Cobalt(II), Nickel(II), and Copper(II) Ions with Pyridine, 2-Methylpyridine, 3-Methylpyridine, and 4-Methylpyridine in Acetonitrile. Zeitschrift für Naturforschung B, 55(3-4), 277-284. doi:10.1515/znb-2000-3-409Xu, Z., Chen, X., Kim, H. N., & Yoon, J. (2010). Sensors for the optical detection ofcyanide ion. Chem. Soc. Rev., 39(1), 127-137. doi:10.1039/b907368

    Luminescence Lifetime-Based Sensing Platform Based on Cyclometalated Iridium(III) Complexes for the Detection of Perfluorooctanoic Acid in Aqueous Samples

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    Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a "forever chemical". In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations &gt;100 μg/L (240 nM).</p

    Dyes That Bear Thiazolylazo Groups as Chromogenic Chemosensors for Metal Cations

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    A family of dyes (L 1-L 6) that contain a thiazolylazo group as signalling subunit and several macrocyclic cavities with different ring sizes and type and number of heteroatoms as binding sites has been synthesized and characterized. Solutions of L 1-L 6 in acetonitrile show broad and structureless absorption bands in the 554-577 nm range with typicalmolar absorption coefficients that range from 20000 to 32000 M -1 cm -1. A detailed protonation study was carried out with solutions of L 1, L 2 and L 5 in acetonitrile. Addition of one equivalent of protons to L 1 and L 2 resulted in the development of a new band at 425 and 370 nm, respectively, which was ascribed to protonation in the aniline nitrogen. In contrast, protonation of L 5 resulted in a bathochromic shift of 25 nm of the absorption band that was conceivable with protonation of one of the nitrogen atoms of the azo moiety. These results were in agreement with 1H NMR spectroscopic data. Theoretical studies on the model ligand L 1 and on different possible protonation species were also performed by using density functional theory (DFT) quantum mechanical calculations. Colour modulations in solutions of L 1-L 6 in acetonitrile in the presence of the metal cations Fe 3+, Ni 2+, Zn 2+, Cd 2+, Pb 2+ and Hg 2+ have been studied. A selective chromogenic response of L 4 in the presence of Pb 2+ and L 5 in the presence of Hg 2+ was observed. To get a better insight into the chromophoric nature in the presence of metal cations, the interaction of Hg 2+ with the model compound L 1 in two different coordination modes was studied theoretically by using density functional theory (DFT) quantum mechanical calculations.Financial support by the Spanish Ministerio de Ciencia e Innovacion (MICINN) through projects MAT2009-14564-C04-01, CTQ2010-15364, Molecular Nanoscience (Consolider Ingenio CSD2007-00010) and Generalitat Valenciana (PROMETEO/2009/016 and PROMETEO/2009/108) is gratefully acknowledged.Abalos Aguado, T.; Moragues Pons, ME.; Royo Calvo, S.; Jiménez, D.; Martínez Mañez, R.; Soto Camino, J.; Sancenón Galarza, F.... (2012). Dyes That Bear Thiazolylazo Groups as Chromogenic Chemosensors for Metal Cations. European Journal of Inorganic Chemistry. (1):76-84. doi:10.1002/ejic.201100834S76841Fabbrizzi, L., & Poggi, A. (1995). Sensors and switches from supramolecular chemistry. Chemical Society Reviews, 24(3), 197. doi:10.1039/cs9952400197Bissell, R. A., de Silva, A. P., Gunaratne, H. Q. N., Lynch, P. L. M., Maguire, G. E. M., & Sandanayake, K. R. A. S. (1992). Molecular fluorescent signalling with ‘fluor–spacer–receptor’ systems: approaches to sensing and switching devices via supramolecular photophysics. Chem. Soc. Rev., 21(3), 187-195. doi:10.1039/cs9922100187Dix, J. P., & Vögtle, F. (1978). Ionenselektive Kronenether-Farbstoffe. Angewandte Chemie, 90(11), 893-894. doi:10.1002/ange.19780901109Martínez-Máñez, R., & Sancenón, F. (2003). Fluorogenic and Chromogenic Chemosensors and Reagents for Anions. Chemical Reviews, 103(11), 4419-4476. doi:10.1021/cr010421eBeer, P. D., & Gale, P. A. (2001). Erkennung und Nachweis von Anionen: gegenwärtiger Stand und Perspektiven. Angewandte Chemie, 113(3), 502-532. doi:10.1002/1521-3757(20010202)113:33.0.co;2-aValeur, B. (2000). Design principles of fluorescent molecular sensors for cation recognition. Coordination Chemistry Reviews, 205(1), 3-40. doi:10.1016/s0010-8545(00)00246-0Czarnik, A. W. (1994). Chemical Communication in Water Using Fluorescent Chemosensors. Accounts of Chemical Research, 27(10), 302-308. doi:10.1021/ar00046a003Rurack, K., & Resch-Genger, U. (2002). Rigidization, preorientation and electronic decoupling—the ‘magic triangle’ for the design of highly efficient fluorescent sensors and switches. Chemical Society Reviews, 31(2), 116-127. doi:10.1039/b100604pDe Silva, A. P., Gunaratne, H. Q. N., Gunnlaugsson, T., Huxley, A. J. M., McCoy, C. P., Rademacher, J. T., & Rice, T. E. (1997). Signaling Recognition Events with Fluorescent Sensors and Switches. Chemical Reviews, 97(5), 1515-1566. doi:10.1021/cr960386pRurack, K. (2001). Flipping the light switch ‘ON’ – the design of sensor molecules that show cation-induced fluorescence enhancement with heavy and transition metal ions. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 57(11), 2161-2195. doi:10.1016/s1386-1425(01)00492-9Loehr, H. G., & Voegtle, F. (1985). Chromo- and fluoroionophores. A new class of dye reagents. Accounts of Chemical Research, 18(3), 65-72. doi:10.1021/ar00111a001Takagi, M., & Ueno, K. (1984). Crown compounds as alkali and alkaline earth metal ion selective chromogenic reagents. Host Guest Complex Chemistry III, 39-65. doi:10.1007/3-540-12821-2_2Ros-Lis, J. V., Martínez-Máñez, R., Sancenón, F., Soto, J., Rurack, K., & Weißhoff, H. (2007). Signalling Mechanisms in Anion-Responsive Push-Pull Chromophores: The Hydrogen-Bonding, Deprotonation and Anion-Exchange Chemistry of Functionalized Azo Dyes. European Journal of Organic Chemistry, 2007(15), 2449-2458. doi:10.1002/ejoc.200601111Chen, Y.-J., & Chung, W.-S. (2009). Tetrazoles and para-Substituted Phenylazo-Coupled Calix[4]arenes as Highly Sensitive Chromogenic Sensors for Ca2+. European Journal of Organic Chemistry, 2009(28), 4770-4776. doi:10.1002/ejoc.200900603Lee, H. G., Lee, J.-E., & Choi, K. S. (2006). Chromoionophoric N2S2 macrocycles exhibiting mercury(II) selectivity. Inorganic Chemistry Communications, 9(6), 582-585. doi:10.1016/j.inoche.2006.03.005Mahato, P., Ghosh, A., Saha, S., Mishra, S., Mishra, S. K., & Das, A. (2010). Recognition of Hg2+Using Diametrically Disubstituted Cyclam Unit. Inorganic Chemistry, 49(24), 11485-11492. doi:10.1021/ic1014797Hovind, H. R. (1975). Thiazolylazo dyes and their applications in analytical chemistry. A review. The Analyst, 100(1196), 769. doi:10.1039/an9750000769Lemos, V. A., Santos, E. S., Santos, M. S., & Yamaki, R. T. (2007). Thiazolylazo dyes and their application in analytical methods. Microchimica Acta, 158(3-4), 189-204. doi:10.1007/s00604-006-0704-9Saeed, M. M., Bajwa, S. Z., Ansari, M. S., & Ahmed, R. (2005). Solid phase sorption of microamount of Hg(II) onto 1-(2-thiazolylazo)-2-naphthol (TAN) loaded polyurethane foam. Radiochimica Acta, 93(3). doi:10.1524/ract.93.3.177.61610Starvin, A. M., & Rao, T. P. (2004). Removal and recovery of mercury(II) from hazardous wastes using 1-(2-thiazolylazo)-2-naphthol functionalized activated carbon as solid phase extractant. Journal of Hazardous Materials, 113(1-3), 75-79. doi:10.1016/j.jhazmat.2004.04.021Wang, M., Lin, J.-M., Qu, F., Shan, X., & Chen, Z. (2004). On-capillary complexation of metal ions with 4-(2-thiazolylazo)resorcinol in capillary electrophoresis. Journal of Chromatography A, 1029(1-2), 249-254. doi:10.1016/j.chroma.2003.12.011Takase, I. (2003). The use of 2-2-thiazolylazo-p-cresol to minimize the interference of Ni and Cu for the bismuth determination in alloys by hydride generation atomic absorption spectrometry. Talanta, 61(5), 597-602. doi:10.1016/s0039-9140(03)00365-5Amin, A. S. (2001). SPECTROPHOTOMETRIC DETERMINATION OF CADMIUM USING THIAZOLYLAZO CHROMOGENIC REAGENTS IN THE PRESENCE OF TRITON X-100: APPLICATION IN ENVIRONMENTAL SAMPLES. Analytical Letters, 34(1), 163-176. doi:10.1081/al-100002714Moragues, M. E., Martínez-Máñez, R., & Sancenón, F. (2011). Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the year 2009. Chemical Society Reviews, 40(5), 2593. doi:10.1039/c0cs00015aMartínez-Máñez, R., Sancenón, F., Hecht, M., Biyikal, M., & Rurack, K. (2010). Nanoscopic optical sensors based on functional supramolecular hybrid materials. Analytical and Bioanalytical Chemistry, 399(1), 55-74. doi:10.1007/s00216-010-4198-2Richman, J. E., & Atkins, T. J. (1974). Nitrogen analogs of crown ethers. Journal of the American Chemical Society, 96(7), 2268-2270. doi:10.1021/ja00814a056MACROCYCLIC POLYAMINES: 1,4,7,10,13,16-HEXA&#196;ZACYCLO&#214;CTADECANE. (1978). Organic Syntheses, 58, 86. doi:10.15227/orgsyn.058.0086Krakowiak, K. E., Bradshaw, J. S., & Zamecka-Krakowiak, D. J. (1989). Synthesis of aza-crown ethers. Chemical Reviews, 89(4), 929-972. doi:10.1021/cr00094a008Higashino, K., Nakaya, T., & Ishiguro, E. (1994). Photovoltaic properties of azo compounds containing the thiazole group. Journal of Photochemistry and Photobiology A: Chemistry, 79(1-2), 81-88. doi:10.1016/1010-6030(94)87017-9Mustroph, H., & Epperlein, J. (2010). Quantitative Beschreibung der Absorptionsmaxima von substituierten 2-Thiazol-azofarbstoffen. Zeitschrift für Chemie, 23(8), 298-299. doi:10.1002/zfch.19830230810Ros-Lis, J. V., Martínez-Máñez, R., Sancenón, F., Soto, J., Spieles, M., & Rurack, K. (2008). Squaraines as Reporter Units: Insights into their Photophysics, Protonation, and Metal-Ion Coordination Behaviour. Chemistry - A European Journal, 14(32), 10101-10114. doi:10.1002/chem.200800300Forlani, L., De Maria, P., & Fini, A. (1980). Electrical effects in substituted thiazoles. pK a Values of some 5-substituted 2-aminothiazoles and 5-substituted 2-NN-dimethylaminothiazoles. Journal of the Chemical Society, Perkin Transactions 2, (8), 1156. doi:10.1039/p29800001156Haake, P., & Bausher, L. P. (1968). Thiazolium ions and related heteroaromatic systems. II. The acidity constants of thiazolium, oxazolium, and imidazolium ions. The Journal of Physical Chemistry, 72(6), 2213-2217. doi:10.1021/j100852a057SAWICKI, E. (1957). Physical Properties of the Aminoazobenzene Dyes. IV. The Position of Proton Addition1. The Journal of Organic Chemistry, 22(4), 365-367. doi:10.1021/jo01355a004Siiman, O., & Lepp, A. (1984). Protonation of the methyl orange derivative of aspartate adsorbed on colloidal silver: a surface-enhanced resonance Raman scattering and fluorescence emission study. The Journal of Physical Chemistry, 88(12), 2641-2650. doi:10.1021/j150656a043WADA, H., NAKAZAWA, O., & NAKAGAWA, G. (1974). Evaluation of 1-(2-thiazolylazo)-2-hydroxy-3-naphthoic acid as a metallochromic indicator. Talanta, 21(1), 97-102. doi:10.1016/0039-9140(74)80068-8Critical Stability Cosntants R. M. Smith A. E. Martell New York Vol. 2 1974García-Acosta, B., Martínez-Máñez, R., Sancenón, F., Soto, J., Rurack, K., Spieles, M., … Gil, L. (2007). Ditopic N-Crowned 4-(p-Aminophenyl)-2,6-diphenylpyridines:  Implications of Macrocycle Topology on the Spectroscopic Properties, Cation Complexation, and Differential Anion Responses. Inorganic Chemistry, 46(8), 3123-3135. doi:10.1021/ic062069zHyperChem. 6.03 Molecular Modeling System 2000(s. f.). doi:10.1021/ol062351Kim, H. J., Kim, S. H., Kim, J. H., Anh, L. N., Lee, J. H., Lee, C.-H., & Kim, J. S. (2009). ICT-based Cu(II)-sensing 9,10-anthraquinonecalix[4]crown. Tetrahedron Letters, 50(23), 2782-2786. doi:10.1016/j.tetlet.2009.03.149Ábalos, T., Jiménez, D., Moragues, M., Royo, S., Martínez-Máñez, R., Sancenón, F., … Gil, S. (2010). Multi-channel receptors based on thiopyrylium functionalised with macrocyclic receptors for the recognition of transition metal cations and anions. Dalton Transactions, 39(14), 3449. doi:10.1039/b921486kSchmittel, M., & Lin, H.-W. (2007). Quadruple-Channel Sensing: A Molecular Sensor with a Single Type of Receptor Site for Selective and Quantitative Multi-Ion Analysis. Angewandte Chemie, 119(6), 911-914. doi:10.1002/ange.200603362Nolan, E. M., & Lippard, S. J. (2008). Tools and Tactics for the Optical Detection of Mercuric Ion. Chemical Reviews, 108(9), 3443-3480. doi:10.1021/cr068000qZhang, X., & Huang, J. (2010). Functional surface modification of natural cellulose substances for colorimetric detection and adsorption of Hg2+ in aqueous media. Chemical Communications, 46(33), 6042. doi:10.1039/c0cc01072cZhao, Q., Liu, S., Li, F., Yi, T., & Huang, C. (2008). Multisignaling detection of Hg2+ based on a phosphorescent iridium(iii) complex. Dalton Transactions, (29), 3836. doi:10.1039/b804858dTatay, S., Gaviña, P., Coronado, E., & Palomares, E. (2006). Optical Mercury Sensing Using a Benzothiazolium Hemicyanine Dye. Organic Letters, 8(17), 3857-3860. doi:10.1021/ol0615580Lee, H., & Lee, S. S. (2009). Thiaoxaaza-Macrocyclic Chromoionophores as Mercury(II) Sensors: Synthesis and Color Modulation. Organic Letters, 11(6), 1393-1396. doi:10.1021/ol900241pYoon, S., Miller, E. W., He, Q., Do, P. H., & Chang, C. J. (2007). A Bright and Specific Fluorescent Sensor for Mercury in Water, Cells, and Tissue. Angewandte Chemie, 119(35), 6778-6781. doi:10.1002/ange.200701785Rurack, K., Resch-Genger, U., Spieles, M., & Bricks, J. L. (2000). Cation-triggered ‘switching on’ of the red/near infra-red (NIR) fluorescence of rigid fluorophore–spacer–receptor ionophores. Chemical Communications, (21), 2103-2104. doi:10.1039/b006430kSu Lim, C., Won Kang, D., Shun Tian, Y., Hee Han, J., Lim Hwang, H., & Rae Cho, B. (2010). Detection of mercury in fish organs with a two-photon fluorescent probe. Chemical Communications, 46(14), 2388. doi:10.1039/b922305cRos-Lis, J. V., Martínez-Máñez, R., Rurack, K., Sancenón, F., Soto, J., & Spieles, M. (2004). Highly Selective Chromogenic Signaling of Hg2+in Aqueous Media at Nanomolar Levels Employing a Squaraine-Based Reporter. Inorganic Chemistry, 43(17), 5183-5185. doi:10.1021/ic049422qDescalzo, A. B., Martínez-Máñez, R., Radeglia, R., Rurack, K., & Soto, J. (2003). Coupling Selectivity with Sensitivity in an Integrated Chemosensor Framework:  Design of a Hg2+-Responsive Probe, Operating above 500 nm. Journal of the American Chemical Society, 125(12), 3418-3419. doi:10.1021/ja0290779Yuan, M., Li, Y., Li, J., Li, C., Liu, X., Lv, J., … Zhu, D. (2007). A Colorimetric and Fluorometric Dual-Modal Assay for Mercury Ion by a Molecule. Organic Letters, 9(12), 2313-2316. doi:10.1021/ol0706399Zhu, M., Yuan, M., Liu, X., Xu, J., Lv, J., Huang, C., … Zhu, D. (2008). Visible Near-Infrared Chemosensor for Mercury Ion. Organic Letters, 10(7), 1481-1484. doi:10.1021/ol800197tTian, M., & Ihmels, H. (2009). Selective ratiometric detection of mercury(ii) ions in water with an acridizinium-based fluorescent probe. Chemical Communications, (22), 3175. doi:10.1039/b821830gTian, M., Ihmels, H., & Benner, K. (2010). Selective detection of Hg2+ in the microenvironment of double-stranded DNA with an intercalator crown-ether conjugate. Chemical Communications, 46(31), 5719. doi:10.1039/c002727hWang, H.-H., Xue, L., Qian, Y.-Y., & Jiang, H. (2010). Novel Ratiometric Fluorescent Sensor for Silver Ions. Organic Letters, 12(2), 292-295. doi:10.1021/ol902624hAtilgan, S., Kutuk, I., & Ozdemir, T. (2010). A near IR di-styryl BODIPY-based ratiometric fluorescent chemosensor for Hg(II). Tetrahedron Letters, 51(6), 892-894. doi:10.1016/j.tetlet.2009.12.025Jiménez, D., Martínez-Máñez, R., Sancenón, F., Ros-Lis, J. V., Soto, J., Benito, Á., & García-Breijo, E. (2005). 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    Surface Photochemistry: 3,3′-Dialkylthia and Selenocarbocyanine Dyes Adsorbed onto Microcrystalline Cellulose

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    In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission ΦF and τF, on powdered solid samples a decrease of ΦF and τF was observed. The use of an integrating sphere enabled us to obtain absolute ΦF’s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the ΦF values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples

    Oligonucleotide-capped mesoporous silica nanoparticles as DNA-responsive dye delivery systems for genomic DNA detection

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    [EN] New hybrid oligonucleotide-capped mesoporous silica nanoparticles able to detect genomic DNA were designed.Financial support from the Spanish Government (Project MAT2012-38429-C04) and the Generalitat Valencia (Project PROMETEOII/2014/047) is gratefully acknowledged. Ll. P. is grateful to the Universidad Politecnica de Valencia for his grant.Pascual Vidal, L.; Baroja, I.; Aznar Gimeno, E.; Sancenón Galarza, F.; Marcos Martínez, MD.; Murguía Ibáñez, JR.; Amoros Del Toro, PJ.... (2015). Oligonucleotide-capped mesoporous silica nanoparticles as DNA-responsive dye delivery systems for genomic DNA detection. Chemical Communications. 51(8):1414-1416. https://doi.org/10.1039/C4CC08306GS14141416518Agostini, A., Mondragón, L., Bernardos, A., Martínez-Máñez, R., Marcos, M. D., Sancenón, F., … Murguía, J. R. (2012). Targeted Cargo Delivery in Senescent Cells Using Capped Mesoporous Silica Nanoparticles. Angewandte Chemie International Edition, 51(42), 10556-10560. doi:10.1002/anie.201204663Zhang, Q., Wang, X., Li, P.-Z., Nguyen, K. T., Wang, X.-J., Luo, Z., … Zhao, Y. (2013). Biocompatible, Uniform, and Redispersible Mesoporous Silica Nanoparticles for Cancer-Targeted Drug Delivery In Vivo. Advanced Functional Materials, 24(17), 2450-2461. doi:10.1002/adfm.201302988Chen, C., Geng, J., Pu, F., Yang, X., Ren, J., & Qu, X. (2010). Polyvalent Nucleic Acid/Mesoporous Silica Nanoparticle Conjugates: Dual Stimuli-Responsive Vehicles for Intracellular Drug Delivery. Angewandte Chemie International Edition, 50(4), 882-886. doi:10.1002/anie.201005471Zhou, L., Chen, Z., Dong, K., Yin, M., Ren, J., & Qu, X. (2013). DNA-mediated Construction of Hollow Upconversion Nanoparticles for Protein Harvesting and Near-Infrared Light Triggered Release. Advanced Materials, 26(15), 2424-2430. doi:10.1002/adma.201304437Agostini, A., Mondragón, L., Pascual, L., Aznar, E., Coll, C., Martínez-Máñez, R., … Gil, S. (2012). Design of Enzyme-Mediated Controlled Release Systems Based on Silica Mesoporous Supports Capped with Ester-Glycol Groups. Langmuir, 28(41), 14766-14776. doi:10.1021/la303161eColl, C., Bernardos, A., Martínez-Máñez, R., & Sancenón, F. (2012). Gated Silica Mesoporous Supports for Controlled Release and Signaling Applications. Accounts of Chemical Research, 46(2), 339-349. doi:10.1021/ar3001469Climent, E., Martínez-Máñez, R., Maquieira, Á., Sancenón, F., Marcos, M. D., Brun, E. M., … Amorós, P. (2012). Antibody-Capped Mesoporous Nanoscopic Materials: Design of a Probe for the Selective Chromo-Fluorogenic Detection of Finasteride. ChemistryOpen, 1(6), 251-259. doi:10.1002/open.201100008Oroval, M., Climent, E., Coll, C., Eritja, R., Aviñó, A., Marcos, M. D., … Amorós, P. (2013). An aptamer-gated silica mesoporous material for thrombin detection. Chemical Communications, 49(48), 5480. doi:10.1039/c3cc42157kChen, M., Huang, C., He, C., Zhu, W., Xu, Y., & Lu, Y. (2012). A glucose-responsive controlled release system using glucose oxidase-gated mesoporous silica nanocontainers. Chemical Communications, 48(76), 9522. doi:10.1039/c2cc34290aCliment, E., Martínez-Máñez, R., Sancenón, F., Marcos, M. D., Soto, J., Maquieira, A., & Amorós, P. (2010). Controlled Delivery Using Oligonucleotide-Capped Mesoporous Silica Nanoparticles. Angewandte Chemie International Edition, 49(40), 7281-7283. doi:10.1002/anie.201001847Climent, E., Mondragón, L., Martínez-Máñez, R., Sancenón, F., Marcos, M. D., Murguía, J. R., … Pérez-Payá, E. (2013). Selective, Highly Sensitive, and Rapid Detection of Genomic DNA by Using Gated Materials:MycoplasmaDetection. Angewandte Chemie International Edition, 52(34), 8938-8942. doi:10.1002/anie.201302954Zhang, Z., Balogh, D., Wang, F., Sung, S. Y., Nechushtai, R., & Willner, I. (2013). Biocatalytic Release of an Anticancer Drug from Nucleic-Acids-Capped Mesoporous SiO2 Using DNA or Molecular Biomarkers as Triggering Stimuli. ACS Nano, 7(10), 8455-8468. doi:10.1021/nn403772jWu, L., Ren, J., & Qu, X. (2014). Target-responsive DNA-capped nanocontainer used for fabricating universal detector and performing logic operations. Nucleic Acids Research, 42(21), e160-e160. doi:10.1093/nar/gku858Drexler, H. G., & Uphoff, C. C. (2002). Cytotechnology, 39(2), 75-90. doi:10.1023/a:1022913015916Matas Andreu, L., Molinos Abós, S., Fernández Rivas, G., González Soler, V., & Ausina Ruiz, V. (2006). Diagnóstico serológico de las infecciones por Mycoplasma pneumoniae. Enfermedades Infecciosas y Microbiología Clínica, 24, 19-23. doi:10.1157/13094274V. Ausina , Infecciones causadas por micoplasmas, Medicina Interna, Elsevier España, 2004, 15th edn, pp. 2363–236

    A New bis(rhodamine)-Based Fluorescent Chemosensor for Fe3+

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    A new bis(rhodamine)-based fluorescent probe 4 was synthesized, and it exhibited high selectivity for Fe3+ over other commonly coexistent metal ions in both 50% ethanol and Tris–HCl buffer. Upon the addition of Fe3+, the spirocyclic ring of 4 was opened and a significant enhancement of visible color and fluorescence in the range of 500–600 nm was observed
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