Overview of the Evolution of Silica-Based Chromo-Fluorogenic Nanosensors

[EN] This review includes examples of silica-based, chromo-fluorogenic nanosensors with the aim of illustrating the evolution of the discipline in recent decades through relevant research developed in our group. Examples have been grouped according to the sensing strategies. A clear evolution from simply functionalized materials to new protocols involving molecular gates and the use of highly selective biomolecules such as antibodies and oligonucleotides is reported. Some final examples related to the evolution of chromogenic arrays and the possible use of nanoparticles to communicate with other nanoparticles or cells are also included. A total of 64 articles have been summarized, highlighting different sensing mechanisms.This research was funded by the Spanish Government (projects RTI2018-100910-B-C41, RTI2018-100910-B-C44, and AGL2015-70235-C2-2-R) and the Generalitat Valenciana (project PROMETEO/2018/024) for support. B.L.-T. is grateful to the Spanish MEC for her FPU grant. Additionally, L.P. thanks the Spanish MEC for his FPI fellowship.Pla, L.; Lozano-Torres, B.; Martínez-Máñez, R.; Sancenón Galarza, F.; Ros-Lis, JV. (2019). Overview of the Evolution of Silica-Based Chromo-Fluorogenic Nanosensors. Sensors. 19(23):1-23. https://doi.org/10.3390/s19235138S1231923Martínez-Máñez, R., & Sancenón, F. (2006). Chemodosimeters and 3D inorganic functionalised hosts for the fluoro-chromogenic sensing of anions. Coordination Chemistry Reviews, 250(23-24), 3081-3093. doi:10.1016/j.ccr.2006.04.016Dutta, S. (2019). Point of care sensing and biosensing using ambient light sensor of smartphone: Critical review. TrAC Trends in Analytical Chemistry, 110, 393-400. doi:10.1016/j.trac.2018.11.014Huang, X., Xu, D., Chen, J., Liu, J., Li, Y., Song, J., … Guo, J. (2018). Smartphone-based analytical biosensors. The Analyst, 143(22), 5339-5351. doi:10.1039/c8an01269eYu, L., Qiao, Y., Miao, L., He, Y., & Zhou, Y. (2018). Recent progress in fluorescent and colorimetric sensors for the detection of ions and biomolecules. Chinese Chemical Letters, 29(11), 1545-1559. doi:10.1016/j.cclet.2018.09.005Martínez-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/s00216-010-4198-2Sancenón, F., Pascual, L., Oroval, M., Aznar, E., & Martínez-Máñez, R. (2015). Gated Silica Mesoporous Materials in Sensing Applications. ChemistryOpen, 4(4), 418-437. doi:10.1002/open.201500053Han, W. S., Lee, H. Y., Jung, S. H., Lee, S. J., & Jung, J. H. (2009). Silica-based chromogenic and fluorogenic hybrid chemosensor materials. Chemical Society Reviews, 38(7), 1904. doi:10.1039/b818893aDescalzo, A. B., Jiménez, D., Haskouri, J. E., Beltrán, D., Amorós, P., Marcos, M. D., … Soto, J. (2002). A new method for fluoride determination by using fluorophores and dyes anchored onto MCM-41Electronic supplementary information (ESI) available: IR spectra, SEM images, X-ray diffraction patterns and TG/TD analysis. See http://www.rsc.org/suppdata/cc/b1/b111128k/. Chemical Communications, (6), 562-563. doi:10.1039/b111128kComes, M., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., Villaescusa, L. A., … Beltrán, D. (2004). Chromogenic Discrimination of Primary Aliphatic Amines in Water with Functionalized Mesoporous Silica. Advanced Materials, 16(20), 1783-1786. doi:10.1002/adma.200400143García-Acosta, B., Comes, M., Bricks, J. L., Kudinova, M. A., Kurdyukov, V. V., Tolmachev, A. I., … Amorós, P. (2006). Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines. Chem. Commun., (21), 2239-2241. doi:10.1039/b602497aDescalzo, A. B., Rurack, K., Weisshoff, H., Martínez-Máñez, R., Marcos, M. D., Amorós, P., … Soto, J. (2005). Rational Design of a Chromo- and Fluorogenic Hybrid Chemosensor Material for the Detection of Long-Chain Carboxylates. Journal of the American Chemical Society, 127(1), 184-200. doi:10.1021/ja045683nRos-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.200800632Climent, E., Biyikal, M., Gawlitza, K., Dropa, T., Urban, M., Costero, A. M., … Rurack, K. (2016). A Rapid and Sensitive Strip-Based Quick Test for Nerve Agents Tabun, Sarin, and Soman Using BODIPY-Modified Silica Materials. Chemistry - A European Journal, 22(32), 11138-11142. doi:10.1002/chem.201601269Santos-Figueroa, L. E., Giménez, C., Agostini, A., Aznar, E., Marcos, M. D., Sancenón, F., … Amorós, P. (2013). Selective and Sensitive Chromofluorogenic Detection of the Sulfite Anion in Water Using Hydrophobic Hybrid Organic-Inorganic Silica Nanoparticles. Angewandte Chemie International Edition, 52(51), 13712-13716. doi:10.1002/anie.201306688Climent, 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., Agostini, A., Moragues, M. E., Martínez‐Máñez, R., Sancenón, F., Pardo, T., & Marcos, M. D. (2013). A Simple Probe for the Colorimetric Detection of Carbon Dioxide. Chemistry – A European Journal, 19(51), 17301-17304. doi:10.1002/chem.201302991El Sayed, S., Pascual, L., Licchelli, M., Martínez-Máñez, R., Gil, S., Costero, A. M., & Sancenón, F. (2016). Chromogenic Detection of Aqueous Formaldehyde Using Functionalized Silica Nanoparticles. ACS Applied Materials & Interfaces, 8(23), 14318-14322. doi:10.1021/acsami.6b03224Climent, E., Calero, P., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., & Soto, J. (2009). Selective Chromofluorogenic Sensing of Heparin by using Functionalised Silica Nanoparticles Containing Binding Sites and a Signalling Reporter. Chemistry - A European Journal, 15(8), 1816-1820. doi:10.1002/chem.200802074Climent, E., Martí, A., Royo, S., Martínez-Máñez, R., Marcos, M. D., Sancenón, F., … Parra, M. (2010). Chromogenic Detection of Nerve Agent Mimics by Mass Transport Control at the Surface of Bifunctionalized Silica Nanoparticles. Angewandte Chemie International Edition, 49(34), 5945-5948. doi:10.1002/anie.201001088Climent, E., Giménez, C., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., & Soto, J. (2011). Selective and sensitive chromo-fluorogenic sensing of anionic surfactants in water using functionalised silica nanoparticles. Chemical Communications, 47(24), 6873. doi:10.1039/c1cc11393cColl, C., Martínez-Máñez, R., Marcos, M. D., Sancenón, F., & Soto, J. (2007). A Simple Approach for the Selective and Sensitive Colorimetric Detection of Anionic Surfactants in Water. Angewandte Chemie International Edition, 46(10), 1675-1678. doi:10.1002/anie.200603800Calero, P., Aznar, E., Lloris, J. M., Marcos, M. D., Martínez-Máñez, R., Ros-Lis, J. V., … Sancenón, F. (2008). Chromogenic silica nanoparticles for the colorimetric sensing of long-chain carboxylates. Chemical Communications, (14), 1668. doi:10.1039/b718690hPallás, I., Marcos, M., Martínez-Máñez, R., & Ros-Lis, J. (2017). Development of a Textile Nanocomposite as Naked Eye Indicator of the Exposition to Strong Acids. Sensors, 17(9), 2134. doi:10.3390/s17092134Comes, M., Rodríguez-López, G., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., … Beltrán, D. (2005). Host Solids Containing Nanoscale Anion-Binding Pockets and Their Use in Selective Sensing Displacement Assays. Angewandte Chemie International Edition, 44(19), 2918-2922. doi:10.1002/anie.200461511Comes, M., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., Villaescusa, L. A., & Amorós, P. (2008). Hybrid materials with nanoscopic anion-binding pockets for the colorimetric sensing of phosphate in water using displacement assays. Chemical Communications, (31), 3639. doi:10.1039/b804396eComes, M., Aznar, E., Moragues, M., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., … Amorós, P. (2009). Mesoporous Hybrid Materials Containing Nanoscopic «Binding Pockets» for Colorimetric Anion Signaling in Water by using Displacement Assays. Chemistry - A European Journal, 15(36), 9024-9033. doi:10.1002/chem.200900890Calero, P., Hecht, M., Martínez-Máñez, R., Sancenón, F., Soto, J., Vivancos, J. L., & Rurack, K. (2011). 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D., Aucejo, S., … Garcia, E. (2014). A novel colorimetric sensor array for monitoring fresh pork sausages spoilage. Food Control, 35(1), 166-176. doi:10.1016/j.foodcont.2013.06.043Zaragozá, P., Ros-Lis, J. V., Vivancos, J.-L., & Martínez-Máñez, R. (2015). Proof of concept of using chromogenic arrays as a tool to identify blue cheese varieties. Food Chemistry, 172, 823-830. doi:10.1016/j.foodchem.2014.09.114Aznar, E., Oroval, M., Pascual, L., Murguía, J. R., Martínez-Máñez, R., & Sancenón, F. (2016). Gated Materials for On-Command Release of Guest Molecules. Chemical Reviews, 116(2), 561-718. doi:10.1021/acs.chemrev.5b00456Coll, 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/ar3001469Llopis-Lorente, A., Lozano-Torres, B., Bernardos, A., Martínez-Máñez, R., & Sancenón, F. (2017). Mesoporous silica materials for controlled delivery based on enzymes. Journal of Materials Chemistry B, 5(17), 3069-3083. doi:10.1039/c7tb00348jCasasús, R., Aznar, E., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., & Amorós, P. (2006). New Methods for Anion Recognition and Signaling Using Nanoscopic Gatelike Scaffoldings. Angewandte Chemie International Edition, 45(40), 6661-6664. doi:10.1002/anie.200602045Climent, 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, 122(40), 7439-7441. doi:10.1002/ange.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. 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Surface Enhanced Raman Scattering and Gated Materials for Sensing Applications: The Ultrasensitive Detection ofMycoplasmaand Cocaine. Chemistry - A European Journal, 22(38), 13488-13495. doi:10.1002/chem.201602457Ribes, À., Aznar, E., Bernardos, A., Marcos, M. D., Amorós, P., Martínez-Máñez, R., & Sancenón, F. (2017). Fluorogenic Sensing of Carcinogenic Bisphenol A using Aptamer-Capped Mesoporous Silica Nanoparticles. Chemistry - A European Journal, 23(36), 8581-8584. doi:10.1002/chem.201701024Oroval, M., Coll, C., Bernardos, A., Marcos, M. D., Martínez-Máñez, R., Shchukin, D. G., & Sancenón, F. (2017). Selective Fluorogenic Sensing of As(III) Using Aptamer-Capped Nanomaterials. ACS Applied Materials & Interfaces, 9(13), 11332-11336. doi:10.1021/acsami.6b15164Ribes, À., Santiago-Felipe, S., Bernardos, A., Marcos, M. D., Pardo, T., Sancenón, F., … Aznar, E. (2017). Two New Fluorogenic Aptasensors Based on Capped Mesoporous Silica Nanoparticles to Detect Ochratoxin A. 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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.201100008Pascual, L., El Sayed, S., Marcos, M. D., Martínez-Máñez, R., & Sancenón, F. (2017). Acetylcholinesterase-capped Mesoporous Silica Nanoparticles Controlled by the Presence of Inhibitors. Chemistry - An Asian Journal, 12(7), 775-784. doi:10.1002/asia.201700031Climent, E., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., Rurack, K., & Amorós, P. (2009). The Determination of Methylmercury in Real Samples Using Organically Capped Mesoporous Inorganic Materials Capable of Signal Amplification. Angewandte Chemie, 121(45), 8671-8674. doi:10.1002/ange.200904243Candel, I., Bernardos, A., Climent, E., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., … Parra, M. (2011). 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Chemical Communications, 55(41), 5785-5788. doi:10.1039/c9cc02602aOtri, I., El Sayed, S., Medaglia, S., Martínez‐Máñez, R., Aznar, E., & Sancenón, F. (2019). Simple Endotoxin Detection Using Polymyxin‐B‐Gated Nanoparticles. Chemistry – A European Journal, 25(15), 3770-3774. doi:10.1002/chem.201806306Ribes, À., Santiago-Felipe, S., Aviñó, A., Candela-Noguera, V., Eritja, R., Sancenón, F., … Aznar, E. (2018). Design of oligonucleotide-capped mesoporous silica nanoparticles for the detection of miRNA-145 by duplex and triplex formation. Sensors and Actuators B: Chemical, 277, 598-603. doi:10.1016/j.snb.2018.09.026El Sayed, S., Giménez, C., Aznar, E., Martínez-Máñez, R., Sancenón, F., & Licchelli, M. (2015). Highly selective and sensitive detection of glutathione using mesoporous silica nanoparticles capped with disulfide-containing oligo(ethylene glycol) chains. 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R., Lycoops, J., Jeppesen, J. O., … Guillem, C. (2013). Chromo-Fluorogenic Detection of Nitroaromatic Explosives by Using Silica Mesoporous Supports Gated with Tetrathiafulvalene Derivatives. Chemistry - A European Journal, 20(3), 855-866. doi:10.1002/chem.201302461Aznar, E., Coll, C., Marcos, M. D., Martínez-Máñez, R., Sancenón, F., Soto, J., … Ruiz, E. (2009). Borate-Driven Gatelike Scaffolding Using Mesoporous Materials Functionalised with Saccharides. Chemistry - A European Journal, 15(28), 6877-6888. doi:10.1002/chem.200900090Aznar, E., Villalonga, R., Giménez, C., Sancenón, F., Marcos, M. D., Martínez-Máñez, R., … Amorós, P. (2013). Glucose-triggered release using enzyme-gated mesoporous silica nanoparticles. Chemical Communications, 49(57), 6391. doi:10.1039/c3cc42210kLlopis‐Lorente, A., Villalonga, R., Marcos, M. D., Martínez‐Máñez, R., & Sancenón, F. (2018). 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Angewandte Chemie International Edition, 58(42), 14986-14990. doi:10.1002/anie.20190886

A new class of silica-supported chromo-fluorogenic chemosensors for anion recognition based on a selenourea scaffold

[EN] The first example of a chemosensor (L) containing a selenourea moiety is described here. L is able to colorimetrically sense the presence of CN- and S2- in H2O: MeCN (75 : 25, v/v). Moreover, when L is loaded into functionalised mesoporous silica nanoparticles an increase in the selectivity towards S2- occurs via a selective fluorescence response.The authors thank the financial support from the Fondazione Banco di Sardegna, the Spanish Government, European FEDER funds (project MAT2015-64139-C4-1-R) and the Generalitat Valenciana (project PROMETEOII/2014/047). A. Llopis-Lorente is grateful to the "La Caixa'' Banking Foundation for his PhD fellowship. Dr Tiziana Pivetta is gratefully acknowledged for help with the interpretation of the mass spectra.Casula, A.; Llopis-Lorente, A.; Garau, A.; Isaia, F.; Kubicki, M.; Lippolis, V.; Sancenón Galarza, F.... (2017). A new class of silica-supported chromo-fluorogenic chemosensors for anion recognition based on a selenourea scaffold. 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Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines

Pyrylium-containing mesoporous materials have been used for the chromo-fluorogenic sensing of biogenic amines in an aqueous environment.Amoros del Toro, Pedro Jose, [email protected]

Polymer Composites Containing Gated Mesoporous Materials for On-Command Controlled Release

Polyamidic nanofibrous membranes containing gated silica mesoporous particles, acting as carriers, are described as novel hybrid composite materials for encapsulation and on-command delivery of garlic extracts. The carrier system consists of MCM-41 solids functionalized in the outer surface, with linear polyamines (solid P1) and with hydrolyzed starch (solid P2), both acting as molecular gates. Those particles were adsorbed on electospun nylon-6 nanofibrous membranes yielding to composite materials M1 and M2. FE-SEM analysis confirmed the presence of particles incorporated on the nylon nanofibers. The release of the entrapped molecules (garlic extract) from the P1, P2, M1, and M2 materials was evaluated using cyclic voltammetry measurements. Electrochemical studies showed that at acidic pH P1 and M1 were unable to release their entrapped cargo (closed gate), whereas at neutral pH both materials release their loading (open gate). Dealing with P2 and M2 materials, in the absence of pancreatin a negligible release is observed (closed gate), whereas in the presence of enzyme the load is freely to diffuse to the solution. These newly developed composite nanomaterials, provide a homogeneous easy-to-handle system with controlled delivery and bioactive-protective features, having potential applications on pharmacology, medical and engineering fields.The authors wish to express their gratitude to the Generalitat Valenciana (Grisolia scholarship 2011/012, project PROM-ETEO/2009/016), Spanish Government (MINECO Projects AGL2012-39597-C02-01, AGL2012-39597-C02-02 and MAT2012-38429-C04-01) and the CIBER-BBN for their support. IILA thanks DISTAM and Universita degli di Milano for a specialization scholarship. We would also like to thank the Institut de Ciencia dels Materials (ICMUV) and to the Microscopy Service of the Universitat Politecnica de Valencia for technical support. We thank Roquette for the Glucidex samples.Acosta Romero, C.; Pérez Esteve, E.; Fuenmayor, CA.; Benedetti, S.; Cosio, MS.; Soto Camino, J.; Sancenón Galarza, F.... (2014). Polymer Composites Containing Gated Mesoporous Materials for On-Command Controlled Release. ACS Applied Materials and Interfaces. 6(9):6453-6460. https://doi.org/10.1021/am405939y645364606

Monitoring of chicken meat freshness by means of a colorimetric sensor array

A new optoelectronic nose to monitor chicken meat ageing has been developed. It is based on 16 pigments prepared by the incorporation of different dyes (pH indicators, Lewis acids, hydrogenbonding derivatives, selective probes and natural dyes) into inorganic materials (UVM-7, silica and alumina). The colour changes of the sensor array were characteristic of chicken ageing in a modi¿ed packaging atmosphere (30% CO2¿70% N2). The chromogenic array data were processed with qualitative (PCA) and quantitative (PLS) tools. The PCA statistical analysis showed a high degree of dispersion, with nine dimensions required to explain 95% of variance. Despite this high dimensionality, a tridimensional representation of the three principal components was able to differentiate ageing with 2-day intervals. Moreover, the PLS statistical analysis allows the creation of a model to correlate the chromogenic data with chicken meat ageing. The model offers a PLS prediction model for ageing with values of 0.9937, 0.0389 and 0.994 for the slope, the intercept and the regression coef¿cient, respectively, and is in agreement with the perfect ¿t between the predicted and measured values observed. The results suggest the feasibility of this system to help develop optoelectronic noses that monitor food freshness.Salinas Soler, Y.; Ros-Lis, JV.; Vivancos, J.; Martínez Mañez, R.; Marcos Martínez, MD.; Aucejo Romero, S.; Herranz, N.... (2012). Monitoring of chicken meat freshness by means of a colorimetric sensor array. Analyst. 137(16):3635-3643. doi:10.1039/C2AN35211GS3635364313716Anang, D. M., Rusul, G., Ling, F. H., & Bhat, R. (2010). Inhibitory effects of lactic acid and lauricidin on spoilage organisms of chicken breast during storage at chilled temperature. International Journal of Food Microbiology, 144(1), 152-159. doi:10.1016/j.ijfoodmicro.2010.09.014HINTON, A., & INGRAM, K. D. (2005). 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Inventory of metal complexes circulating in plant fluids: a reliable method based on HPLC coupled with dual elemental and high-resolution molecular mass spectrometric detection.

International audienceDescription of metal species in plant fluids such as xylem, phloem or related saps remains a complex challenge usually addressed either by liquid chromatography-mass spectrometry, X-ray analysis or computational prediction. To date, none of these techniques has achieved a complete and true picture of metal-containing species in plant fluids, especially for the least concentrated complexes. Here, we present a generic analytical methodology for a large-scale (> 10 metals, > 50 metal complexes) detection, identification and semiquantitative determination of metal complexes in the xylem and embryo sac liquid of the green pea, Pisum sativum. The procedure is based on direct injection using hydrophilic interaction chromatography with dual detection by elemental (inductively coupled plasma mass spectrometry) and molecular (high-resolution electrospray mass spectrometry) mass spectrometric detection. Numerous and novel complexes of iron(II), iron(III), copper(II), zinc, manganese, cobalt(II), cobalt(III), magnesium, calcium, nickel and molybdenum(IV) with several ligands including nicotianamine, citrate, malate, histidine, glutamine, aspartic acid, asparagine, phenylalanine and others are observed in pea fluids and discussed. This methodology provides a large inventory of various types of metal complexes, which is a significant asset for future biochemical and genetic studies into metal transport/homeostasis

Low-cost materials for boron adsorption from water

[EN] Knowing the affinity of boron aqueous species for cis-diol organic groups, five different hybrid materials have been prepared by anchoring glucose groups onto the surface of silica matrices with a different surface topology: UVM-7 bimodal mesoporous silica, UVM-11 unimodal non-templated mesoporous silica, commercial silica fume and two silica xerogels with pores within the mesoporous range (13-50 nm). After optimizing the experimental conditions, a comparison was made of the boron adsorption capacities in water. The relationship of the structural and functionalization parameters is discussed and the importance of the surface topology in the final adsorption behaviour is revealed. Hence, despite the UVM-7 based material being the best boron adsorbent, the solid based on one of the xerogels is seen to be a good candidate for preparing low-cost boron adsorbents.Financial support from the Spanish Government (Project MAT2009-14564-C04-01 and MAT2009-14564-C04-04) and the Generalitat Valenciana (Project PROMETEO/2009/016) is gratefully acknowledged. C. S. thanks the MICINN for a predoctoral fellowship.Sanfeliu Cano, C.; Martínez Mañez, R.; Sancenón Galarza, F.; Soto Camino, J.; Puchol, V.; Amoros Del Toro, P.; Marcos Martínez, MD. (2012). Low-cost materials for boron adsorption from water. Journal of Materials Chemistry. 22(48):25362-25372. https://doi.org/10.1039/C2JM32819DS2536225372224

A dual channel sulphur-containing macrocycle functionalised BODIPY probe for the detection of Hg(II) in mixed aqueous solution

We report herein the synthesis and chromo-fluorogenic behaviour of a new probe 1 containing a boron-dipirromethene (BODIPY) unit electronically connected with a dithia-dioxa-aza macrocycle. Acetonitrile and water-acetonitrile 95:5 v/v solutions of the probe showed an ICT band in the visible zone and are nearly non-emissive. When acetonitrile was used as solvent, addition of Hg(II) and trivalent metal cations induced an hypsochromic shift of the absorption band and moderate emission enhancements. A highly selective response was obtained when using competitive media such as wateracetonitrile 95:5 v/v. In this case only Hg(II) induced a hypsochromic shift of the absorption band and a marked emission enhancement.We thank the Spanish Government (MAT2015-64139-C4-1-R) and Generalitat Valenciana (PROMETEOII/2014/047). M. L. P. thanks Generalitat Valenciana for her Grisolia fellowship. Thanks are also due to Fundaça˜o para a Cieˆncia e Tecnologia (Portugal) for financial support to the Portuguese NMR network (PTNMR, Bruker Avance III 400-Univ. Minho), FCT and FEDER (European Fund for Regional Development)-COMPETEQRENEU for financial support to the research centre CQ/UM [PEst-C/ QUI/UI0686/2013 (FCOMP-01-0124-FEDER-037302)], and a postdoctoral grant to R. M. F. Batista (SFRH/BPD/79333/2011).info:eu-repo/semantics/publishedVersio