Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the year 2009

This critical review is focused on examples reported in the year 2009 dealing with the design of chromogenic and fluorogenic chemosensors or reagents for anions (264 references). © 2011 The Royal Society of Chemistry.Moragues Pons, ME.; Martínez Mañez, R.; Sancenón Galarza, F. (2011). Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the year 2009. Chemical Society Reviews. 40(5):2593-2643. doi:10.1039/c0cs00015a25932643405Schmidtchen, F. P., Gleich, A., & Schummer, A. (1989). Selective molecular hosts for anions. Pure and Applied Chemistry, 61(9), 1535-1546. doi:10.1351/pac198961091535Dietrich, B. (1993). Design of anion receptors: Applications. Pure and Applied Chemistry, 65(7), 1457-1464. doi:10.1351/pac199365071457Atwood, J. L., Holman, K. T., & Steed, J. W. (1996). Laying traps for elusive prey: recent advances in the non-covalent binding of anions. Chemical Communications, (12), 1401. doi:10.1039/cc9960001401Schmidtchen, F. 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A., García-Garrido, S. E., & Garric, J. (2008). Anion receptors based on organic frameworks: highlights from 2005 and 2006. Chem. Soc. Rev., 37(1), 151-190. doi:10.1039/b715825dCaltagirone, C., & Gale, P. A. (2009). Anion receptor chemistry: highlights from 2007. Chem. Soc. Rev., 38(2), 520-563. doi:10.1039/b806422aKubik, S. (2009). Amino acid containing anion receptors. Chem. Soc. Rev., 38(2), 585-605. doi:10.1039/b810531fSchmidtchen, F. P. (2005). Artificial Host Molecules for the Sensing of Anions. Anion Sensing, 1-29. doi:10.1007/b101160Schmidtchen, F. P. (2006). Reflections on the construction of anion receptors. Coordination Chemistry Reviews, 250(23-24), 2918-2928. doi:10.1016/j.ccr.2006.07.009Gale, P. A. (2006). Structural and Molecular Recognition Studies with Acyclic Anion Receptors†. Accounts of Chemical Research, 39(7), 465-475. doi:10.1021/ar040237qSessler, J. L., Camiolo, S., & Gale, P. A. (2003). Pyrrolic and polypyrrolic anion binding agents. Coordination Chemistry Reviews, 240(1-2), 17-55. doi:10.1016/s0010-8545(03)00023-7Bondy, C. R., & Loeb, S. J. (2003). Amide based receptors for anions. Coordination Chemistry Reviews, 240(1-2), 77-99. doi:10.1016/s0010-8545(02)00304-1Choi, K., & Hamilton, A. D. (2003). Macrocyclic anion receptors based on directed hydrogen bonding interactions. Coordination Chemistry Reviews, 240(1-2), 101-110. doi:10.1016/s0010-8545(02)00305-3Davis, A. P. (2006). Anion binding and transport by steroid-based receptors. Coordination Chemistry Reviews, 250(23-24), 2939-2951. doi:10.1016/j.ccr.2006.05.008Best, M. D., Tobey, S. L., & Anslyn, E. V. (2003). Abiotic guanidinium containing receptors for anionic species. Coordination Chemistry Reviews, 240(1-2), 3-15. doi:10.1016/s0010-8545(02)00256-4Llinares, J. M., Powell, D., & Bowman-James, K. (2003). Ammonium based anion receptors. Coordination Chemistry Reviews, 240(1-2), 57-75. doi:10.1016/s0010-8545(03)00019-5Schug, K. A., & Lindner, W. (2005). Noncovalent Binding between Guanidinium and Anionic Groups:  Focus on Biological- and Synthetic-Based Arginine/Guanidinium Interactions with Phosph[on]ate and Sulf[on]ate Residues. Chemical Reviews, 105(1), 67-114. doi:10.1021/cr040603jYoon, J., Kim, S. K., Singh, N. J., & Kim, K. S. (2006). Imidazolium receptors for the recognition of anions. Chemical Society Reviews, 35(4), 355. doi:10.1039/b513733kBlondeau, P., Segura, M., Pérez-Fernández, R., & de Mendoza, J. (2007). Molecular recognition of oxoanions based on guanidinium receptors. Chem. Soc. Rev., 36(2), 198-210. doi:10.1039/b603089kXu, Z., Kim, S. K., & Yoon, J. (2010). Revisit to imidazolium receptors for the recognition of anions: highlighted research during 2006–2009. Chemical Society Reviews, 39(5), 1457. doi:10.1039/b918937hGarcía-España, E., Díaz, P., Llinares, J. M., & Bianchi, A. (2006). Anion coordination chemistry in aqueous solution of polyammonium receptors. Coordination Chemistry Reviews, 250(23-24), 2952-2986. doi:10.1016/j.ccr.2006.05.018Schmuck, C. (2006). How to improve guanidinium cations for oxoanion binding in aqueous solution? Coordination Chemistry Reviews, 250(23-24), 3053-3067. doi:10.1016/j.ccr.2006.04.001Amendola, V. (2001). Anion recognition by dimetallic cryptates. Coordination Chemistry Reviews, 219-221, 821-837. doi:10.1016/s0010-8545(01)00368-xBeer, P. D., & Hayes, E. J. (2003). Transition metal and organometallic anion complexation agents. Coordination Chemistry Reviews, 240(1-2), 167-189. doi:10.1016/s0010-8545(02)00303-xSteed, J. W. (2009). Coordination and organometallic compounds as anion receptors and sensors. Chem. Soc. Rev., 38(2), 506-519. doi:10.1039/b810364jO’Neil, E. J., & Smith, B. D. (2006). Anion recognition using dimetallic coordination complexes. Coordination Chemistry Reviews, 250(23-24), 3068-3080. doi:10.1016/j.ccr.2006.04.006Rice, C. R. (2006). Metal-assembled anion receptors. Coordination Chemistry Reviews, 250(23-24), 3190-3199. doi:10.1016/j.ccr.2006.05.017Amendola, V., & Fabbrizzi, L. (2009). Anion receptors that contain metals as structural units. Chem. Commun., (5), 513-531. doi:10.1039/b808264mMartínez-Máñez, R., & Sancenón, F. (2003). Fluorogenic and Chromogenic Chemosensors and Reagents for Anions. Chemical Reviews, 103(11), 4419-4476. doi:10.1021/cr010421eKatayev, E. A., Ustynyuk, Y. A., & Sessler, J. L. (2006). Receptors for tetrahedral oxyanions. Coordination Chemistry Reviews, 250(23-24), 3004-3037. doi:10.1016/j.ccr.2006.04.013Suksai, C., & Tuntulani, T. (2003). Chromogenic anion sensors. Chemical Society Reviews, 32(4), 192. doi:10.1039/b209598jKim, S. K., Lee, D. H., Hong, J.-I., & Yoon, J. (2009). Chemosensors for Pyrophosphate. Accounts of Chemical Research, 42(1), 23-31. doi:10.1021/ar800003fBeer, P. (2000). Electrochemical and optical sensing of anions by transition metal based receptors. Coordination Chemistry Reviews, 205(1), 131-155. doi:10.1016/s0010-8545(00)00237-xBeer, P. D. (1996). Anion selective recognition and optical/electrochemical sensing by novel transition-metal receptor systems. Chemical Communications, (6), 689. doi:10.1039/cc9960000689De 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/cr960386pGunnlaugsson, T., Glynn, M., Tocci (née Hussey), G. M., Kruger, P. E., & Pfeffer, F. M. (2006). Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors. Coordination Chemistry Reviews, 250(23-24), 3094-3117. doi:10.1016/j.ccr.2006.08.017Amendola, V., Esteban-Gómez, D., Fabbrizzi, L., & Licchelli, M. (2006). What Anions Do to N−H-Containing Receptors. Accounts of Chemical Research, 39(5), 343-353. doi:10.1021/ar050195lGunnlaugsson, T., Ali, H. D. P., Glynn, M., Kruger, P. E., Hussey, G. M., Pfeffer, F. M., … Tierney, J. (2005). Fluorescent Photoinduced Electron Transfer (PET) Sensors for Anions; From Design to Potential Application. Journal of Fluorescence, 15(3), 287-299. doi:10.1007/s10895-005-2627-yWiskur, 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/ar9600796Nguyen, B. T., & Anslyn, E. V. (2006). Indicator–displacement assays. Coordination Chemistry Reviews, 250(23-24), 3118-3127. doi:10.1016/j.ccr.2006.04.009Xu, 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/b907368jMartínez-Máñez, R., & Sancenón, F. (2005). New Advances in Fluorogenic Anion Chemosensors. Journal of Fluorescence, 15(3), 267-285. doi:10.1007/s10895-005-2626-zHijji, Y. M., Barare, B., Kennedy, A. P., & Butcher, R. (2009). Synthesis and photophysical characterization of a Schiff base as anion sensor. Sensors and Actuators B: Chemical, 136(2), 297-302. doi:10.1016/j.snb.2008.11.045Zhang, Y.-M., Lin, Q., Wei, T.-B., Wang, D.-D., Yao, H., & Wang, Y.-L. (2009). Simple colorimetric sensors with high selectivity for acetate and chloride in aqueous solution. Sensors and Actuators B: Chemical, 137(2), 447-455. doi:10.1016/j.snb.2009.01.015Anzenbacher, P., Nishiyabu, R., & Palacios, M. A. (2006). N-confused calix[4]pyrroles. Coordination Chemistry Reviews, 250(23-24), 2929-2938. doi:10.1016/j.ccr.2006.09.001Anzenbacher,, P., Try, A. C., Miyaji, H., Jursíková, K., Lynch, V. M., Marquez, M., & Sessler, J. L. (2000). Fluorinated Calix[4]pyrrole and Dipyrrolylquinoxaline:  Neutral Anion Receptors with Augmented Affinities and Enhanced Selectivities. Journal of the American Chemical Society, 122(42), 10268-10272. doi:10.1021/ja002112wBlack, C. B., Andrioletti, B., Try, A. C., Ruiperez, C., & Sessler, J. L. (1999). Dipyrrolylquinoxalines:  Efficient Sensors for Fluoride Anion in Organic Solution. Journal of the American Chemical Society, 121(44), 10438-10439. doi:10.1021/ja992579aMizuno, T., Wei, W.-H., Eller, L. R., & Sessler, J. L. (2002). Phenanthroline Complexes Bearing Fused Dipyrrolylquinoxaline Anion Recognition Sites:  Efficient Fluoride Anion Receptors. Journal of the American Chemical Society, 124(7), 1134-1135. doi:10.1021/ja017298tMaeda, H., & Kusunose, Y. (2005). Dipyrrolyldiketone Difluoroboron Complexes: Novel Anion Sensors With C-H⋅⋅⋅X− Interactions. Chemistry - A European Journal, 11(19), 5661-5666. doi:10.1002/chem.200500627Ghosh, T., Maiya, B. G., & Samanta, A. (2006). A colorimetric chemosensor for both fluoride and transition metal ions based on dipyrrolyl derivative. Dalton Transactions, (6), 795. doi:10.1039/b510469fAldakov, D., & Anzenbacher, P. (2004). Sensing of Aqueous Phosphates by Polymers with Dual Modes of Signal Transduction. Journal of the American Chemical Society, 126(15), 4752-4753. doi:10.1021/ja039934oSessler, J. L., Cho, D.-G., & Lynch, V. (2006). Diindolylquinoxalines:  Effective Indole-Based Receptors for Phosphate Anion. Journal of the American Chemical Society, 128(51), 16518-16519. doi:10.1021/ja067720bChauhan, S. M. S., Bisht, T., & Garg, B. (2009). 1-Arylazo-5,5-dimethyl dipyrromethanes: Versatile chromogenic probes for anions. Sensors and Actuators B: Chemical, 141(1), 116-123. doi:10.1016/j.snb.2009.06.013Liu, W.-X., Yang, R., Li, A.-F., Li, Z., Gao, Y.-F., Luo, X.-X., … Jiang, Y.-B. (2009). N-(Acetamido)thiourea based simple neutral hydrogen-bonding receptors for anions. Organic & Biomolecular Chemistry, 7(19), 4021. doi:10.1039/b910255hBabu, J. N., Bhalla, V., Kumar, M., Puri, R. K., & Mahajan, R. K. (2009). Chloride ion recognition using thiourea/urea based receptors incorporated into 1,3-disubstituted calix[4]arenes. New Journal of Chemistry, 33(3), 675. doi:10.1039/b816610bBoiocchi, M., Fabbrizzi, L., Garolfi, M., Licchelli, M., Mosca, L., & Zanini, C. (2009). Templated Synthesis of Copper(II) Azacyclam Complexes Using Urea as a Locking Fragment and Their Metal-Enhanced Binding Tendencies towards Anions. Chemistry - A European Journal, 15(42), 11288-11297. doi:10.1002/chem.200901364Lin, Y.-S., Tu, G.-M., Lin, C.-Y., Chang, Y.-T., & Yen, Y.-P. (2009). Colorimetric anion chemosensors based on anthraquinone: naked-eye detection of isomeric dicarboxylate and tricarboxylate anions. New Journal of Chemistry, 33(4), 860. doi:10.1039/b811172cQing, G.-Y., Sun, T.-L., Wang, F., He, Y.-B., & Yang, X. (2009). Chromogenic Chemosensors forN-Acetylaspartate Based on Chiral Ferrocene-Bearing Thiourea Derivatives. European Journal of Organic Chemistry, 2009(6), 841-849. doi:10.1002/ejoc.200800961Lu, Q.-S., Dong, L., Zhang, J., Li, J., Jiang, L., Huang, Y., … Yu, X.-Q. (2009). Imidazolium-Functionalized BINOL as a Multifunctional Receptor for Chromogenic and Chiral Anion Recognition. Organic Letters, 11(3), 669-672. doi:10.1021/ol8027303Bao, X., Yu, J., & Zhou, Y. (2009). Selective colorimetric sensing for F− by a cleft-shaped anion receptor containing amide and hydroxyl as recognition units. Sensors and Actuators B: Chemical, 140(2), 467-472. doi:10.1016/j.snb.2009.04.056Bhardwaj, V. K., Hundal, M. S., & Hundal, G. (2009). A tripodal receptor bearing catechol groups for the chromogenic sensing of F− ions via frozen proton transfer. Tetrahedron, 65(41), 8556-8562. doi:10.1016/j.tet.2009.08.023Caltagirone, C., Mulas, A., Isaia, F., Lippolis, V., Gale, P. A., & Light, M. E. (2009). Metal-induced pre-organisation for anion recognition in a neutral platinum-containing receptor. Chemical Communications, (41), 6279. doi:10.1039/b912942aShiraishi, Y., Maehara, H., Sugii, T., Wang, D., & Hirai, T. (2009). A BODIPY–indole conjugate as a colorimetric and fluorometric probe for selective fluoride anion detection. Tetrahedron Letters, 50(29), 4293-4296. doi:10.1016/j.tetlet.2009.05.018Shiraishi, Y., Maehara, H., & Hirai, T. (2009). Indole-azadiene conjugate as a colorimetric and fluorometric probe for selective fluoride ion sensing. Organic & Biomolecular Chemistry, 7(10), 2072. doi:10.1039/b821466bBhosale, S. V., Bhosale, S. V., Kalyankar, M. B., & Langford, S. J. (2009). A Core-Substituted Naphthalene Diimide Fluoride Sensor. Organic Letters, 11(23), 5418-5421. doi:10.1021/ol9022722Lin, Z., Chen, H. C., Sun, S.-S., Hsu, C.-P., & Chow, T. J. (2009). Bifunctional maleimide dyes as selective anion sensors. Tetrahedron, 65(27), 5216-5221. doi:10.1016/j.tet.2009.04.090Yoo, J., Kim, M.-S., Hong, S.-J., Sessler, J. L., & Lee, C.-H. (2009). Selective Sensing of Anions with Calix[4]pyrroles Strapped with Chromogenic Dipyrrolylquinoxalines. The Journal of Organic Chemistry, 74(3), 1065-1069. doi:10.1021/jo802059cShang, X.-F., Li, J., Lin, H., Jiang, P., Cai, Z.-S., & Lin, H.-K. (2009). Anion recognition and sensing of ruthenium(ii) and cobalt(ii) sulfonamido complexes. Dalton Transactions, (12), 2096. doi:10.1039/b804445gDydio, P., Zieliński, T., & Jurczak, J. (2009). Bishydrazide Derivatives of Isoindoline as Simple Anion Receptors. The Journal of Organic Chemistry, 74(4), 1525-1530. doi:10.1021/jo802288uZimmermann-Dimer, L. M., Reis, D. C., Machado, C., & Machado, V. G. (2009). Chromogenic anionic chemosensors based on protonated merocyanine solvatochromic dyes in trichloromethane and in trichloromethane–water biphasic system. Tetrahedron, 65(21), 4239-4248. doi:10.1016/j.tet.2009.03.049Goswami, S., Hazra, A., Chakrabarty, R., & Fun, H.-K. (2009). Recognition of Carboxylate Anions and Carboxylic Acids by Selenium-Based New Chromogenic Fluorescent Sensor: A Remarkable Fluorescence Enhancement of Hindered Carboxylates. Organic Letters, 11(19), 4350-4353. doi:10.1021/ol901737sBarnard, A., Dickson, S. J., Paterson, M. J., Todd, A. M., & Steed, J. W. (2009). Enantioselective lactate binding by chiral tripodal anion hosts derived from amino acids. Organic & Biomolecular Chemistry, 7(8), 1554. doi:10.1039/b817889eHung, C.-Y., Singh, A. S., Chen, C.-W., Wen, Y.-S., & Sun, S.-S. (2009). Colorimetric and luminescent sensing of F− anion through strong anion–π interaction inside the π-acidic cavity of a pyridyl-triazine bridged trinuclear Re(i)–tricarbonyl diimine complex. Chemical Communications, (12), 1511. doi:10.1039/b820234fMetzger, A., & Anslyn, E. V. (1998). A Chemosensor for Citrate in Beverages. Angewandte Chemie International Edition, 37(5), 649-652. doi:10.1002/(sici)1521-3773(19980316)37:53.0.co;2-hNiikura, K., Metzger, A., & Anslyn, E. V. (1998). Chemosensor Ensemble with Selectivity for Inositol-Trisphosphate. Journal of the American Chemical Society, 120(33), 8533-8534. doi:10.1021/ja980990cAït-Haddou, H., Wiskur, S. L., Lynch, V. M., & Anslyn, E. V. (2001). Achieving Large Color Changes in Response to the Presence of Amino Acids:  A Molecular Sensing Ensemble with Selectivity for Aspartate. Journal of the American Chemical Society, 123(45), 11296-11297. doi:10.1021/ja011905vWiskur, S. L., & Anslyn, E. V. (2001). Using a Synthetic Receptor to Create an Optical-Sensing Ensemble for a Class of Analytes:  A Colorimetric Assay for the Aging of Scotch. Journal of the American Chemical Society, 123(41), 10109-10110. doi:10.1021/ja011800sZhong, Z., & Anslyn, E. V. (2002). A Colorimetric Sensing Ensemble for Heparin. 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(2006). Differential receptor arrays and assays for solution-based molecular recognition. Chem. Soc. Rev., 35(1), 14-28. doi:10.1039/b505518kKitamura, M., Shabbir, S. H., & Anslyn, E. V. (2009). Guidelines for Pattern Recognition Using Differential Receptors and Indicator Displacement Assays. The Journal of Organic Chemistry, 74(12), 4479-4489. doi:10.1021/jo900433jZhang, T., Edwards, N. Y., Bonizzoni, M., & Anslyn, E. V. (2009). The Use of Differential Receptors to Pattern Peptide Phosphorylation. Journal of the American Chemical Society, 131(33), 11976-11984. doi:10.1021/ja9041675Zhang, D. (2009). Highly selective colorimetric detection of cysteine and homocysteine in water through a direct displacement approach. Inorganic Chemistry Communications, 12(12), 1255-1258. doi:10.1016/j.inoche.2009.09.035Li, S., Zhou, Y., Yu, C., Chen, F., & Xu, J. (2009). Switching the ligand-exchange reactivities of chloro-bridged cyclopalladated azobenzenes for the colorimetric sensing of thiocyanate. 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Opening Up the World of Chemistry

¿knowing that numerous European Chemical Societies support the development of ChemistryOpen, it became apparent that this would be a distinctive project and an exciting opportunity. We expect ChemistryOpen will soon reach the very high-standards of other general chemistry journals published by Wiley- VCH¿Martínez Mañez, R.; Wirth, T. (2012). Opening Up the World of Chemistry. ChemistryOpen. 1(4):4-4. doi:10.1002/open.201100009S441

The implementation of the new technologies for advanced graphic expression in studies conducted using structural graphical statics and its comparison with architectural treatises of the time

Congreso celebrado en la Escuela de Arquitectura de la Universidad de Sevilla desde el 24 hasta el 26 de junio de 2015.Technological evolution has brought us new methods of analysing and studying historical architectural buildings by means of advanced graphic documentation and the use of high definition resources such as the laser scanner and the architectural photogrammetry. The application of these systems and equipment has made it possible to graphically document a number of buildings with a certain degree of thoroughness and precision, while optimising the available resources and the time required for data collection. At the same time, the need for auxiliary devices has been reduced and reliable results have been obtained at a lower cost. Once the necessary graphic documentation has been obtained, it can been used to construct a reverse architectural model, and digital methods will then be implemented in order to apply the structural criteria of the era in which the building was constructed. This entire process will be carried out by means of graphic methods, or what is known as graphical statics, and the results will be compared. The results thus obtained can then be compared with a series of architectural treatises of the time. In this particular case, the studies involved several examples of religious architecture constructed in the early 17th century, in the province of Castellon, Spain, and their stability and approximation have been tested by graphical statics methods applied to advanced graphical documentation by comparing them with the treatises of the time (Rodrigo Gil de Hontañón by Simon Garcia, Hernan Ruiz the younger and Blondel) and the stability of the temple itself (Kooharian - Heyman)

Antibody-Capped Mesoporous Nanoscopic Materials:Design of a Probe for the Selective Chromo-FluorogenicDetection of Finasteride

[EN] The synthesis of capped mesoporous silica nanoparticles (MSN) conjugated with an antibody (AB) as a gatekeeper has been carried out in order to obtain a delivery system able to release an entrapped cargo (dye) in the presence of a target molecule (antigen) to which the conjugated antibody binds selectively. In particular, MSN loaded with rhodamine B and functionalized on the external surface with a suitable derivative of N-(t-butyl)- 3-oxo-(5a,17b)-4-aza-androst-1-ene-17-carboxamide (finasteride) have been prepared (S1). The addition of polyclonal antibodies against finasteride induced capping of the pores due to the interaction with the anchored hapten-like finasteride derivative to give a MSN¿hapten¿AB nanoparticle S1-AB. It was found that the addition of capped material S1-AB to water solutions containing finasteride resulted in displacement of the antibody, pore uncapping and entrapped-dye release. The response of the gated material is highly selective, and only finasteride, among other steroids, was able to induce a significant uncapping process. Compared with finasteride, the finasteride metabolite was able to release 17% of the dye, whereas the exogen steroids testosterone, metenolone and 16-b-hydroxystanozolol only induced very little release of rhodamine B (lower than 10%) from aqueous suspensions containing sensing solid S1-AB. A detection limit as low as 20 ppb was found for the fluorimetric detection of finasteride. In order to evaluate a possible application of the material for label-free detection of finasteride, the capped material was isolated and stored to give final sensing solid S1-AB-i. It was found to display a similar behavior towards finasteride as to that shown by freshly prepared S1-AB; even after a period of two months, no significant loss of selectivity or sensitivity was noted. Moreover, to study the application for the detection of finasteride in biological samples, this ¿aged¿ material, S1-AB-i, was tested using commercially available blank urine as matrix. Samples containing 70 and 90% blank urine were spiked with a defined amount of finasteride, and the concentration was determined using capped S1-AB-i. Recovery ranges from 94% to 118% were reached.Financial support from the Spanish Government (project MAT2009-14564-C04-01) and the Generalitat Valenciana (Spain) (projects PROMETEO/2009/016 and PROMETEO/2010/008) is gratefully acknowledged. E. C. thanks the Minesterio de Ciencia e Innovacion (MICINN, Spain) for her fellowship.Climent Terol, E.; Martínez Mañez, R.; Maquieira Catala, Á.; Sancenón Galarza, F.; Marcos Martínez, MD.; Brun Sánchez, EM.; Soto Camino, J.... (2012). Antibody-Capped Mesoporous Nanoscopic Materials:Design of a Probe for the Selective Chromo-FluorogenicDetection of Finasteride. ChemistryOpen. 1:251-259. https://doi.org/10.1002/open.201100008S251259

Mimicking tricks from nature with sensory organic-inorganic hybrid materials

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. 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Journal of Materials Chemistry, 15(27-28), 2965. doi:10.1039/b501897hLee, S. J., Lee, J.-E., Seo, J., Jeong, I. Y., Lee, S. S., & Jung, J. H. (2007). 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). 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C., van Veggel, F. C. J. M., & Reinhoudt, D. N. (2000). Cation sensing by patterned self-assembled monolayers on gold. Journal of the Chemical Society, Perkin Transactions 2, (10), 2141-2146. doi:10.1039/b002606iAOKI, H., UMEZAWA, Y., VERTOVA, A., & RONDININI, S. (2006). Ion-channel Sensors Based on ETH 1001 Ionophore Embedded in Charged-alkanethiol Self-assembled Monolayers on Gold Electrode Surfaces. Analytical Sciences, 22(12), 1581-1584. doi:10.2116/analsci.22.1581Aoki, H., Hasegawa, K., Tohda, K., & Umezawa, Y. (2003). Voltammetric detection of inorganic phosphate using ion-channel sensing with self-assembled monolayers of a hydrogen bond-forming receptor. Biosensors and Bioelectronics, 18(2-3), 261-267. doi:10.1016/s0956-5663(02)00177-xAoki, H., & Umezawa, Y. (2003). Trace analysis of an oligonucleotide with a specific sequence using PNA-based ion-channel sensors. The Analyst, 128(6), 681. doi:10.1039/b300465aKatayama, Y., Ohuchi, Y., Higashi, H., Kudo, Y., & Maeda, M. (2000). The Design of Cyclic AMP−Recognizing Oligopeptides and Evaluation of Its Capability for Cyclic AMP Recognition Using an Electrochemical System. Analytical Chemistry, 72(19), 4671-4674. doi:10.1021/ac990847hCliment, E., Casasús, R., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., & Soto, J. (2008). Chromo-fluorogenic sensing of pyrophosphate in aqueous media using silica functionalised with binding and reactive units. Chemical Communications, (48), 6531. doi:10.1039/b813199fCliment, E., Calero, P., Marcos, M. D., Martínez-Máñez, R.

A robust multimedia traffic SDN-Based management system using patterns and models of QoE estimation with BRNN

[EN] Nowadays, network infrastructures such as Software Defined Networks (SDN) achieve a huge computational power. This allows to add a high processing on the network nodes. In this paper, a multimedia traffic management system is presented. This system is based on estimation models of Quality of Experience (QoE) and also on the traffic patterns classification. In order to achieve this, a QoE estimation method has been modeled. This method allows for classifying the multimedia traffic from multimedia transmission patterns. In order to do this, the SDN controller gathers statistics from the network. The patterns used have been defined from a lineal combination of objective QoE measurements. The model has been defined by Bayesian regularized neural networks (BRNN). From this model, the system is able to classify several kind of traffic according to the quality perceived by the users. Then, a model has been developed to determine which video characteristics need to be changed to provide the user with the best possible quality in the critical moments of the transmission. The choice of these characteristics is based on the quality of service (QoS) parameters, such as delay, jitter, loss rate and bandwidth. Moreover, it is also based on subpatterns defined by clusters from the dataset and which represents network and video characteristics. When a critical network situation is given, the model selects, by using network parameters as entries, the subpattern with the most similar network condition. The minimum Euclidean distance between these entries and the network parameters of the subpatters is calculated to perform this selection. Both models work together to build a reliable multimedia traffic management system perfectly integrated into current network infrastructures, which is able to classify the traffic and solve critical situations changing the video characteristics, by using the SDN architecture.This work has been partially supported by the "Ministerio de Educacion, Cultura y Deporte", through the "Ayudas para contratos predoctorales de Formation del Profesorado Universitario FPU (Convocatoria 2015)", grant number FPU15/06837 and by the "Ministerio de Economia y Competitividad" in the "Programa Estatal de Fomento de la Investigation Cientffica y Tecnica de Excelencia, Subprograma Estatal de Generacion de Conocimiento" within the project under Grant TIN2017-84802-C2-1-P.Canovas Solbes, A.; Rego Mañez, A.; Romero Martínez, JO.; Lloret, J. (2020). A robust multimedia traffic SDN-Based management system using patterns and models of QoE estimation with BRNN. Journal of Network and Computer Applications. 150:1-14. https://doi.org/10.1016/j.jnca.2019.102498S114150Cánovas, A., Taha, M., Lloret, J., & Tomás, J. (2018). Smart resource allocation for improving QoE in IP Multimedia Subsystems. Journal of Network and Computer Applications, 104, 107-116. doi:10.1016/j.jnca.2017.12.020Canovas, A., Jimenez, J. M., Romero, O., & Lloret, J. (2018). Multimedia Data Flow Traffic Classification Using Intelligent Models Based on Traffic Patterns. IEEE Network, 32(6), 100-107. doi:10.1109/mnet.2018.1800121Burden, F., & Winkler, D. (2008). Bayesian Regularization of Neural Networks. Artificial Neural Networks, 23-42. doi:10.1007/978-1-60327-101-1_3Goodman, S. N. (2005). Introduction to Bayesian methods I: measuring the strength of evidence. Clinical Trials, 2(4), 282-290. doi:10.1191/1740774505cn098oaHirschen, K., & Schäfer, M. (2006). Bayesian regularization neural networks for optimizing fluid flow processes. Computer Methods in Applied Mechanics and Engineering, 195(7-8), 481-500. doi:10.1016/j.cma.2005.01.015Huang, X., Yuan, T., Qiao, G., & Ren, Y. (2018). Deep Reinforcement Learning for Multimedia Traffic Control in Software Defined Networking. IEEE Network, 32(6), 35-41. doi:10.1109/mnet.2018.1800097Lin, Y. (2002). Data Mining and Knowledge Discovery, 6(3), 259-275. doi:10.1023/a:1015469627679Lopez-Martin, M., Carro, B., Lloret, J., Egea, S., & Sanchez-Esguevillas, A. (2018). Deep Learning Model for Multimedia Quality of Experience Prediction Based on Network Flow Packets. IEEE Communications Magazine, 56(9), 110-117. doi:10.1109/mcom.2018.1701156Hagan, M. T., & Menhaj, M. B. (1994). Training feedforward networks with the Marquardt algorithm. IEEE Transactions on Neural Networks, 5(6), 989-993. doi:10.1109/72.329697Nguyen, T. T. T., & Armitage, G. (2008). A survey of techniques for internet traffic classification using machine learning. IEEE Communications Surveys & Tutorials, 10(4), 56-76. doi:10.1109/surv.2008.080406Queiroz, W., Capretz, M. A. M., & Dantas, M. (2019). An approach for SDN traffic monitoring based on big data techniques. Journal of Network and Computer Applications, 131, 28-39. doi:10.1016/j.jnca.2019.01.016Rego, A., Canovas, A., Jimenez, J. M., & Lloret, J. (2018). An Intelligent System for Video Surveillance in IoT Environments. IEEE Access, 6, 31580-31598. doi:10.1109/access.2018.2842034Seshadrinathan, K., Soundararajan, R., Bovik, A. C., & Cormack, L. K. (2010). Study of Subjective and Objective Quality Assessment of Video. IEEE Transactions on Image Processing, 19(6), 1427-1441. doi:10.1109/tip.2010.2042111Soysal, M., & Schmidt, E. G. (2010). Machine learning algorithms for accurate flow-based network traffic classification: Evaluation and comparison. Performance Evaluation, 67(6), 451-467. doi:10.1016/j.peva.2010.01.001Tan, X., Xie, Y., Ma, H., Yu, S., & Hu, J. (2019). Recognizing the content types of network traffic based on a hybrid DNN-HMM model. Journal of Network and Computer Applications, 142, 51-62. doi:10.1016/j.jnca.2019.06.004Tongaonkar, A., Torres, R., Iliofotou, M., Keralapura, R., & Nucci, A. (2015). Towards self adaptive network traffic classification. Computer Communications, 56, 35-46. doi:10.1016/j.comcom.2014.03.02

Synthesis of a new tripodal chemosensor based on 2,4,6-triethyl-1,3,5-trimethylbencene scaffolding bearing thiourea and fluorescein for the chromo-fluorogenic detection of anions

A tripodal receptor containing thiourea as binding site and fluorescein as signalling subunit has been designed, synthesized and used for the colorimetric detection of basic anions in DMSO solutions. (C) 2012 Elsevier Ltd. All rights reserved.Moragues Pons, ME.; Santos Figueroa, LE.; Abalos Aguado, T.; Sancenón Galarza, F.; Martínez Mañez, R. (2012). Synthesis of a new tripodal chemosensor based on 2,4,6-triethyl-1,3,5-trimethylbencene scaffolding bearing thiourea and fluorescein for the chromo-fluorogenic detection of anions. Tetrahedron Letters. 53(38):5110-5113. doi:10.1016/j.tetlet.2012.07.039S51105113533

Triggered release in lipid bilayer-capped mesoporous silica nanoparticles containing SPION using an alternating magnetic field

[EN] We report here the on-command cargo controlled delivery using an alternating magnetic field (AMF) from magnetic silica mesoporous supports capped with a lipid bilayer. © 2012 The Royal Society of Chemistry.Financial support from the Spanish Government (projects MAT2009-14564-C04-01 and CTQ2008-00690) and the Generalitat Valenciana (project PROMETEO/2009/016) is gratefully acknowledged. E. B. thanks the Spanish Ministry of Education (MEC) for his Jose Castillejo fellowship (JC2010-0090).Bringas, E.; Köysüren, Ö.; Quach, DV.; Mahmoudi, M.; Aznar Gimeno, E.; Roehling, JD.; Marcos Martínez, MD.... (2012). Triggered release in lipid bilayer-capped mesoporous silica nanoparticles containing SPION using an alternating magnetic field. Chemical Communications. 48:5647-5649. https://doi.org/10.1039/C2CC31563GS5647564948Aznar, E., Martínez-Máñez, R., & Sancenón, F. (2009). Controlled release using mesoporous materials containing gate-like scaffoldings. Expert Opinion on Drug Delivery, 6(6), 643-655. doi:10.1517/17425240902895980Cotí, K. K., Belowich, M. E., Liong, M., Ambrogio, M. W., Lau, Y. A., Khatib, H. A., … Stoddart, J. F. (2009). Mechanised nanoparticles for drug delivery. Nanoscale, 1(1), 16. doi:10.1039/b9nr00162jLai, C.-Y., Trewyn, B. G., Jeftinija, D. M., Jeftinija, K., Xu, S., Jeftinija, S., & Lin, V. S.-Y. (2003). A Mesoporous Silica Nanosphere-Based Carrier System with Chemically Removable CdS Nanoparticle Caps for Stimuli-Responsive Controlled Release of Neurotransmitters and Drug Molecules. Journal of the American Chemical Society, 125(15), 4451-4459. doi:10.1021/ja028650lPark, C., Oh, K., Lee, S. C., & Kim, C. (2007). Controlled Release of Guest Molecules from Mesoporous Silica Particles Based on a pH-Responsive Polypseudorotaxane Motif. Angewandte Chemie International Edition, 46(9), 1455-1457. doi:10.1002/anie.200603404Casasús, R., Climent, E., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., … Ruiz, E. (2008). Dual Aperture Control on pH- and Anion-Driven Supramolecular Nanoscopic Hybrid Gate-like Ensembles. Journal of the American Chemical Society, 130(6), 1903-1917. doi:10.1021/ja0756772Liu, R., Liao, P., Liu, J., & Feng, P. (2011). Responsive Polymer-Coated Mesoporous Silica as a pH-Sensitive Nanocarrier for Controlled Release. Langmuir, 27(6), 3095-3099. doi:10.1021/la104973jCliment, 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.201001847Mal, N. K., Fujiwara, M., & Tanaka, Y. (2003). Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica. Nature, 421(6921), 350-353. doi:10.1038/nature01362Aznar, E., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., Amorós, P., & Guillem, C. (2009). pH- and Photo-Switched Release of Guest Molecules from Mesoporous Silica Supports. Journal of the American Chemical Society, 131(19), 6833-6843. doi:10.1021/ja810011pFu, Q., Rao, G. V. R., Ista, L. K., Wu, Y., Andrzejewski, B. P., Sklar, L. A., … López, G. P. (2003). Control of Molecular Transport Through Stimuli-Responsive Ordered Mesoporous Materials. Advanced Materials, 15(15), 1262-1266. doi:10.1002/adma.200305165Thomas, C. R., Ferris, D. P., Lee, J.-H., Choi, E., Cho, M. H., Kim, E. S., … Zink, J. I. (2010). Noninvasive Remote-Controlled Release of Drug Molecules in Vitro Using Magnetic Actuation of Mechanized Nanoparticles. Journal of the American Chemical Society, 132(31), 10623-10625. doi:10.1021/ja1022267Ruiz-Hernández, E., Baeza, A., & Vallet-Regí, M. (2011). Smart Drug Delivery through DNA/Magnetic Nanoparticle Gates. ACS Nano, 5(2), 1259-1266. doi:10.1021/nn1029229Aznar, E., Mondragón, L., Ros-Lis, J. V., Sancenón, F., Marcos, M. D., Martínez-Máñez, R., … Amorós, P. (2011). Finely Tuned Temperature-Controlled Cargo Release Using Paraffin-Capped Mesoporous Silica Nanoparticles. Angewandte Chemie International Edition, 50(47), 11172-11175. doi:10.1002/anie.201102756Bruce, I. J., Taylor, J., Todd, M., Davies, M. J., Borioni, E., Sangregorio, C., & Sen, T. (2004). Synthesis, characterisation and application of silica-magnetite nanocomposites. Journal of Magnetism and Magnetic Materials, 284, 145-160. doi:10.1016/j.jmmm.2004.06.032Sen, T., Magdassi, S., Nizri, G., & Bruce, I. J. (2006). Dispersion of magnetic nanoparticles in suspension. Micro & Nano Letters, 1(1), 39. doi:10.1049/mnl:20065033Zhang, L., Longo, M. L., & Stroeve, P. (2000). Mobile Phospholipid Bilayers Supported on a Polyion/Alkylthiol Layer Pair. Langmuir, 16(11), 5093-5099. doi:10.1021/la9913405Liu, J., Stace-Naughton, A., Jiang, X., & Brinker, C. J. (2009). Porous Nanoparticle Supported Lipid Bilayers (Protocells) as Delivery Vehicles. Journal of the American Chemical Society, 131(4), 1354-1355. doi:10.1021/ja808018yLiu, J., Jiang, X., Ashley, C., & Brinker, C. J. (2009). Electrostatically Mediated Liposome Fusion and Lipid Exchange with a Nanoparticle-Supported Bilayer for Control of Surface Charge, Drug Containment, and Delivery. Journal of the American Chemical Society, 131(22), 7567-7569. doi:10.1021/ja902039yAshley, C. E., Carnes, E. C., Phillips, G. K., Padilla, D., Durfee, P. N., Brown, P. A., … Brinker, C. J. (2011). The targeted delivery of multicomponent cargos to cancer cells by nanoporous particle-supported lipid bilayers. Nature Materials, 10(5), 389-397. doi:10.1038/nmat2992Hoare, T., Timko, B. P., Santamaria, J., Goya, G. F., Irusta, S., Lau, S., … Kohane, D. S. (2011). Magnetically Triggered Nanocomposite Membranes: A Versatile Platform for Triggered Drug Release. Nano Letters, 11(3), 1395-1400. doi:10.1021/nl200494tNappini, S., Bonini, M., Bombelli, F. B., Pineider, F., Sangregorio, C., Baglioni, P., & Nordèn, B. (2011). Controlled drug release under a low frequency magnetic field: effect of the citrate coating on magnetoliposomes stability. Soft Matter, 7(3), 1025-1037. doi:10.1039/c0sm00789gMalam, Y., Loizidou, M., & Seifalian, A. M. (2009). Liposomes and nanoparticles: nanosized vehicles for drug delivery in cancer. Trends in Pharmacological Sciences, 30(11), 592-599. doi:10.1016/j.tips.2009.08.004Mahmoudi, M., Laurent, S., Shokrgozar, M. A., & Hosseinkhani, M. (2011). Toxicity Evaluations of Superparamagnetic Iron Oxide Nanoparticles: Cell «Vision» versus Physicochemical Properties of Nanoparticles. ACS Nano, 5(9), 7263-7276. doi:10.1021/nn2021088Mahmoudi, M., Azadmanesh, K., Shokrgozar, M. A., Journeay, W. S., & Laurent, S. (2011). Effect of Nanoparticles on the Cell Life Cycle. Chemical Reviews, 111(5), 3407-3432. doi:10.1021/cr100316

Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the years 2010-2011

This review focuses on examples reported in the years 2010¿2011 dealing with the design of chromogenic and fluorogenic chemosensors or reagents for anions.Santos Figueroa, LE.; Moragues Pons, ME.; Climent Terol, E.; Agostini, A.; Martínez Mañez, R.; Sancenón Galarza, F. (2013). Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the years 2010-2011. Chemical Society Reviews. 42(8):3489-3613. doi:10.1039/C3CS35429FS34893613428Martínez-Máñez, R., & Sancenón, F. (2003). Fluorogenic and Chromogenic Chemosensors and Reagents for Anions. Chemical Reviews, 103(11), 4419-4476. doi:10.1021/cr010421eKatayev, E. A., Ustynyuk, Y. A., & Sessler, J. L. (2006). Receptors for tetrahedral oxyanions. Coordination Chemistry Reviews, 250(23-24), 3004-3037. doi:10.1016/j.ccr.2006.04.013Suksai, C., & Tuntulani, T. (2003). Chromogenic anion sensors. Chemical Society Reviews, 32(4), 192. doi:10.1039/b209598jKim, S. K., Lee, D. H., Hong, J.-I., & Yoon, J. (2009). Chemosensors for Pyrophosphate. Accounts of Chemical Research, 42(1), 23-31. doi:10.1021/ar800003fBeer, P. (2000). Electrochemical and optical sensing of anions by transition metal based receptors. Coordination Chemistry Reviews, 205(1), 131-155. doi:10.1016/s0010-8545(00)00237-xZhou, Y., Xu, Z., & Yoon, J. (2011). Fluorescent and colorimetric chemosensors for detection of nucleotides, FAD and NADH: highlighted research during 2004–2010. Chemical Society Reviews, 40(5), 2222. doi:10.1039/c0cs00169dGunnlaugsson, T., Glynn, M., Tocci (née Hussey), G. M., Kruger, P. E., & Pfeffer, F. M. (2006). Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors. Coordination Chemistry Reviews, 250(23-24), 3094-3117. doi:10.1016/j.ccr.2006.08.017Amendola, V., Esteban-Gómez, D., Fabbrizzi, L., & Licchelli, M. (2006). What Anions Do to N−H-Containing Receptors. Accounts of Chemical Research, 39(5), 343-353. doi:10.1021/ar050195lGunnlaugsson, T., Ali, H. D. P., Glynn, M., Kruger, P. E., Hussey, G. M., Pfeffer, F. M., … Tierney, J. (2005). Fluorescent Photoinduced Electron Transfer (PET) Sensors for Anions; From Design to Potential Application. Journal of Fluorescence, 15(3), 287-299. doi:10.1007/s10895-005-2627-yWiskur, 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/ar9600796Nguyen, B. T., & Anslyn, E. V. (2006). Indicator–displacement assays. Coordination Chemistry Reviews, 250(23-24), 3118-3127. doi:10.1016/j.ccr.2006.04.009Xu, 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/b907368jKaur, 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.2012.04.013Zhou, Y., & Yoon, J. (2012). Recent progress in fluorescent and colorimetric chemosensors for detection ofamino acids. Chem. Soc. Rev., 41(1), 52-67. doi:10.1039/c1cs15159bMoragues, 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/c0cs00015aAldrey, A., Núñez, C., García, V., Bastida, R., Lodeiro, C., & Macías, A. (2010). Anion sensing properties of new colorimetric chemosensors based on macrocyclic ligands bearing three nitrophenylurea groups. Tetrahedron, 66(47), 9223-9230. doi:10.1016/j.tet.2010.09.054Odago, M. O., Colabello, D. M., & Lees, A. J. (2010). A simple thiourea based colorimetric sensor for cyanide anion. Tetrahedron, 66(38), 7465-7471. doi:10.1016/j.tet.2010.07.006Piątek, P. (2011). A selective chromogenic chemosensor for carboxylate salt recognition. Chemical Communications, 47(16), 4745. doi:10.1039/c0cc05537aHe, X., Herranz, F., Cheng, E. C.-C., Vilar, R., & Yam, V. W.-W. (2010). Design, Synthesis, Photophysics, and Anion-Binding Studies of Bis(dicyclohexylphosphino)methane-Containing Dinuclear Gold(I) Thiolate Complexes with Urea Receptors. Chemistry - A European Journal, 16(30), 9123-9131. doi:10.1002/chem.201000647Lin, W.-C., Tseng, Y.-P., Lin, C.-Y., & Yen, Y.-P. (2011). Synthesis of alanine-based colorimetric sensors and enantioselective recognition of aspartate and malate anions. Organic & Biomolecular Chemistry, 9(15), 5547. doi:10.1039/c1ob05135kRegueiro-Figueroa, M., Djanashvili, K., Esteban-Gómez, D., de Blas, A., Platas-Iglesias, C., & Rodríguez-Blas, T. (2010). Towards Selective Recognition of Sialic Acid Through Simultaneous Binding to Its cis-Diol and Carboxylate Functions. European Journal of Organic Chemistry, 2010(17), 3237-3248. doi:10.1002/ejoc.201000186Carasel, I. A., Yamnitz, C. R., Winter, R. K., & Gokel, G. W. (2010). Halide Ions Complex and Deprotonate Dipicolinamides and Isophthalamides: Assessment by Mass Spectrometry and UV−Visible Spectroscopy. The Journal of Organic Chemistry, 75(23), 8112-8116. doi:10.1021/jo101749aRostami, A., Colin, A., Li, X. Y., Chudzinski, M. G., Lough, A. J., & Taylor, M. S. (2010). N,N′-Diarylsquaramides: General, High-Yielding Synthesis and Applications in Colorimetric Anion Sensing. The Journal of Organic Chemistry, 75(12), 3983-3992. doi:10.1021/jo100104gAmendola, V., Bergamaschi, G., Boiocchi, M., Fabbrizzi, L., & Milani, M. (2010). The Squaramide versus Urea Contest for Anion Recognition. Chemistry - A European Journal, 16(14), 4368-4380. doi:10.1002/chem.200903190Sola, A., Orenes, R. A., García, M. A., Claramunt, R. M., Alkorta, I., Elguero, J., … Molina, P. (2011). Unprecedented 1,3-Diaza[3]ferrocenophane Scaffold as Molecular Probe for Anions. Inorganic Chemistry, 50(9), 4212-4220. doi:10.1021/ic102314rLee, D. Y., Singh, N., Satyender, A., & Jang, D. O. (2011). An azo dye-coupled tripodal chromogenic sensor for cyanide. Tetrahedron Letters, 52(51), 6919-6922. doi:10.1016/j.tetlet.2011.10.061Haridas, V., Sahu, S., & Praveen Kumar, P. P. (2011). Triazole-based chromogenic and non-chromogenic receptors for halides. Tetrahedron Letters, 52(51), 6930-6934. doi:10.1016/j.tetlet.2011.10.066Park, J. J., Kim, Y.-H., Rhim, S., & Kang, J. (2012). Anion receptors with viologen molecular scaffold. Tetrahedron Letters, 53(2), 247-252. doi:10.1016/j.tetlet.2011.11.040Amendola, V., Fabbrizzi, L., Mosca, L., & Schmidtchen, F.-P. (2011). Urea-, Squaramide-, and Sulfonamide-Based Anion Receptors: A Thermodynamic Study. Chemistry - A European Journal, 17(21), 5972-5981. doi:10.1002/chem.201003411You, J.-M., Jeong, H., Seo, H., & Jeon, S. (2010). 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Glucose-triggered release using enzyme-gated mesoporous silica nanoparticles

[EN] A new gated nanodevice design able to control cargo delivery using glucose as a trigger and cyclodextrin-modified glucose oxidase as a capping agent is reported.Financial support from the Spanish Government (projects MAT2012-38429-C04-01 and CTQ2011-24355), Generalitat Valenciana (project PROMETEO/2009/016), UPV (project SP20120795) and Ramon y Cajal Programme (to R. V.) is gratefully acknowledged.Aznar Gimeno, E.; Villalonga, R.; Giménez Morales, C.; Sancenón Galarza, F.; Marcos Martínez, MD.; Martínez Mañez, R.; Díez, P.... (2013). Glucose-triggered release using enzyme-gated mesoporous silica nanoparticles. Chemical Communications. 49(57):6391-6393. https://doi.org/10.1039/c3cc42210kS639163934957Coll, 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/ar3001469Aznar, E., Martínez-Máñez, R., & Sancenón, F. (2009). 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Controlled Release of Guest Molecules from Mesoporous Silica Particles Based on a pH-Responsive Polypseudorotaxane Motif. Angewandte Chemie International Edition, 46(9), 1455-1457. doi:10.1002/anie.200603404Casasús, R., Climent, E., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., … Ruiz, E. (2008). Dual Aperture Control on pH- and Anion-Driven Supramolecular Nanoscopic Hybrid Gate-like Ensembles. Journal of the American Chemical Society, 130(6), 1903-1917. doi:10.1021/ja0756772Liu, R., Liao, P., Liu, J., & Feng, P. (2011). Responsive Polymer-Coated Mesoporous Silica as a pH-Sensitive Nanocarrier for Controlled Release. Langmuir, 27(6), 3095-3099. doi:10.1021/la104973jCliment, 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.201001847Mal, N. K., Fujiwara, M., & Tanaka, Y. (2003). Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica. Nature, 421(6921), 350-353. doi:10.1038/nature01362Fu, Q., Rao, G. V. R., Ista, L. K., Wu, Y., Andrzejewski, B. P., Sklar, L. A., … López, G. P. (2003). Control of Molecular Transport Through Stimuli-Responsive Ordered Mesoporous Materials. Advanced Materials, 15(15), 1262-1266. doi:10.1002/adma.200305165Aznar, E., Mondragón, L., Ros-Lis, J. V., Sancenón, F., Marcos, M. D., Martínez-Máñez, R., … Amorós, P. (2011). Finely Tuned Temperature-Controlled Cargo Release Using Paraffin-Capped Mesoporous Silica Nanoparticles. Angewandte Chemie International Edition, 50(47), 11172-11175. doi:10.1002/anie.201102756Bringas, E., Köysüren, Ö., Quach, D. V., Mahmoudi, M., Aznar, E., Roehling, J. D., … Stroeve, P. (2012). Triggered release in lipid bilayer-capped mesoporous silica nanoparticles containing SPION using an alternating magnetic field. 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