Red or Blue? Gold Nanoparticles in Colorimetric Sensing

Gold nanoparticles (AuNPs) have been extensively used for the design of colorimetric sensors and probes due to their interesting photophysical properties. In particular, their surface plasmon resonance (SPR) is influenced not only by the size but also by the shape or the properties of the matrix surrounding the nanoparticles. This SPR band is sensitive to the proximity of other nanoparticles, and thus, analyte-triggered aggregation of AuNPs results in an important bathochromic shift of the SPR band and a change in the color of the solution from red to blue due to interparticle surface plasmon coupling. The selectivity of the AuNPs-based sensors toward the different analytes will depend on the recognition properties of the molecules attached to the surface of the nanoparticles. In this chapter, a selection of biologically active molecules has been considered as analytes: neurotransmitters, nerve agents, pesticides, and carboxylates of biological interest

BODIPY Core as Signaling Unit in Chemosensor Design

BODIPY derivatives possess unique photophysical properties and for these reasons, they have been used in numerous fields. Among the different applications, they are used in designing chemosensors that has increased in the last years. Here, we report several strategies and examples for detecting analytes of different characteristics: cations, anions, and hazardous and pollutant neutral molecules using BODIPY core as signaling unit

A New Simple Chromo-fluorogenic Probe for NO2 Detection in Air

[EN] A new chromo-fluorogenic probe, consisting of a biphenyl derivative containing both a silylbenzyl ether and a N,N-dimethylamino group, for NO2 detection in the gas phase has been developed. A clear colour change from colourless to yellow together with an emission quenching was observed when the probe reacted with NO2. A limit of detection to the naked eye of about 0.1 ppm was determined and the system was successfully applied to the detection of NO2 in realistic atmospheric conditions.We thank the Spanish Government (MAT2012‐38429‐C04) and Generalitat Valenciana (PROMETEOII/2014/047) for support. SCSIE (Universidad de Valencia) is gratefully acknowledged for all the equipment employed. We thank Dr. A. Múñoz from the CEAM (Valencia‐Spain) for her help for the development of the measures in real environment.Juarez, LA.; Costero, AM.; Sancenón Galarza, F.; Martínez-Máñez, R.; Parra Álvarez, M.; Gaviña Costero, P. (2015). A New Simple Chromo-fluorogenic Probe for NO2 Detection in Air. Chemistry - A European Journal. 21(24):8720-8722. doi:10.1002/chem.201500608S87208722212

A New Environmentally-Friendly Colorimetric Probe for Formaldehyde Gas Detection under Real Conditions

[EN] A new environmentally-friendly, simple, selective and sensitive probe for detecting formaldehyde, based on naturally-occurring compounds, through either colorimetric or fluorescence changes, is described. The probe is able to detect formaldehyde in both solution and the gas phase with limits of detection of 0.24 mM and 0.7 ppm, respectively. The probe has been tested to study formaldehyde emission in contaminated real atmospheres. The supported probe is easy to use and to dispose, and is safe and suitable as an individual chemodosimeter.This research was funded by the Spanish Government (projects MAT2015-64139-C4-4-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047).Martínez-Aquino, C.; Costero, AM.; Gil Grau, S.; Gaviña, P. (2018). A New Environmentally-Friendly Colorimetric Probe for Formaldehyde Gas Detection under Real Conditions. Molecules. 23(10). https://doi.org/10.3390/molecules23102646S2310https://mcgroup.co.uk/news/20140627/formaldehyde-production-exceed-52-mln-tonnes.htmlGoris, J. A., Ang, S., & Navarro, C. (1998). Laboratory Safety: Minimizing the Toxic Effects of Formaldehyde. Laboratory Medicine, 29(1), 39-43. doi:10.1093/labmed/29.1.39Luo, W., Li, H., Zhang, Y., & Ang, C. Y. . (2001). Determination of formaldehyde in blood plasma by high-performance liquid chromatography with fluorescence detection. Journal of Chromatography B: Biomedical Sciences and Applications, 753(2), 253-257. doi:10.1016/s0378-4347(00)00552-1ROCHA, F., COELHO, L., LOPES, M., CARVALHO, L., FRACASSIDASILVA, J., DOLAGO, C., & GUTZ, I. (2008). Environmental formaldehyde analysis by active diffusive sampling with a bundle of polypropylene porous capillaries followed by capillary zone electrophoretic separation and contactless conductivity detection. Talanta, 76(2), 271-275. doi:10.1016/j.talanta.2008.02.037Korpan, Y. I., Gonchar, M. V., Sibirny, A. A., Martelet, C., El’skaya, A. V., Gibson, T. D., & Soldatkin, A. P. (2000). Development of highly selective and stable potentiometric sensors for formaldehyde determination. Biosensors and Bioelectronics, 15(1-2), 77-83. doi:10.1016/s0956-5663(00)00054-3Dong, S., & Dasgupta, P. K. (1986). Solubility of gaseous formaldehyde in liquid water and generation of trace standard gaseous formaldehyde. Environmental Science & Technology, 20(6), 637-640. doi:10.1021/es00148a016MITSUBAYASHI, K., NISHIO, G., SAWAI, M., SAITO, T., KUDO, H., SAITO, H., … MARTY, J. (2008). A bio-sniffer stick with FALDH (formaldehyde dehydrogenase) for convenient analysis of gaseous formaldehyde. Sensors and Actuators B: Chemical, 130(1), 32-37. doi:10.1016/j.snb.2007.07.086DEMKIV, O., SMUTOK, O., PARYZHAK, S., GAYDA, G., SULTANOV, Y., GUSCHIN, D., … GONCHAR, M. (2008). Reagentless amperometric formaldehyde-selective biosensors based on the recombinant yeast formaldehyde dehydrogenase. Talanta, 76(4), 837-846. doi:10.1016/j.talanta.2008.04.040Dennison, M. J., Hall, J. M., & Turner, A. P. F. (1996). Direct monitoring of formaldehyde vapour and detection of ethanol vapour using dehydrogenase-based biosensors. The Analyst, 121(12), 1769. doi:10.1039/an9962101769Wang, X., Si, Y., Mao, X., Li, Y., Yu, J., Wang, H., & Ding, B. (2013). Colorimetric sensor strips for formaldehyde assay utilizing fluoral-p decorated polyacrylonitrile nanofibrous membranes. The Analyst, 138(17), 5129. doi:10.1039/c3an00812fPinheiro, H. L. ., de Andrade, M. V., de Paula Pereira, P. A., & de Andrade, J. B. (2004). Spectrofluorimetric determination of formaldehyde in air after collection onto silica cartridges coated with Fluoral P. Microchemical Journal, 78(1), 15-20. doi:10.1016/j.microc.2004.02.017Antwi-Boampong, S., Peng, J. S., Carlan, J., & BelBruno, J. J. (2014). A Molecularly Imprinted Fluoral-P/Polyaniline Double Layer Sensor System for Selective Sensing of Formaldehyde. IEEE Sensors Journal, 14(5), 1490-1498. doi:10.1109/jsen.2014.2298872Xu, Z., Chen, J., Hu, L.-L., Tan, Y., Liu, S.-H., & Yin, J. (2017). Recent advances in formaldehyde-responsive fluorescent probes. Chinese Chemical Letters, 28(10), 1935-1942. doi:10.1016/j.cclet.2017.07.018Brewer, T. F., & Chang, C. J. (2015). An Aza-Cope Reactivity-Based Fluorescent Probe for Imaging Formaldehyde in Living Cells. Journal of the American Chemical Society, 137(34), 10886-10889. doi:10.1021/jacs.5b05340Roth, A., Li, H., Anorma, C., & Chan, J. (2015). A Reaction-Based Fluorescent Probe for Imaging of Formaldehyde in Living Cells. Journal of the American Chemical Society, 137(34), 10890-10893. doi:10.1021/jacs.5b05339Li, J.-B., Wang, Q.-Q., Yuan, L., Wu, Y.-X., Hu, X.-X., Zhang, X.-B., & Tan, W. (2016). A two-photon fluorescent probe for bio-imaging of formaldehyde in living cells and tissues. The Analyst, 141(11), 3395-3402. doi:10.1039/c6an00473cTang, Y., Kong, X., Xu, A., Dong, B., & Lin, W. (2016). Development of a Two-Photon Fluorescent Probe for Imaging of Endogenous Formaldehyde in Living Tissues. Angewandte Chemie International Edition, 55(10), 3356-3359. doi:10.1002/anie.201510373He, L., Yang, X., Liu, Y., Kong, X., & Lin, W. (2016). A ratiometric fluorescent formaldehyde probe for bioimaging applications. Chemical Communications, 52(21), 4029-4032. doi:10.1039/c5cc09796gSingha, S., Jun, Y. W., Bae, J., & Ahn, K. H. (2017). Ratiometric Imaging of Tissue by Two-Photon Microscopy: Observation of a High Level of Formaldehyde around Mouse Intestinal Crypts. Analytical Chemistry, 89(6), 3724-3731. doi:10.1021/acs.analchem.7b00044Song, H., Rajendiran, S., Kim, N., Jeong, S. K., Koo, E., Park, G., … Yoon, S. (2012). A tailor designed fluorescent ‘turn-on’ sensor of formaldehyde based on the BODIPY motif. Tetrahedron Letters, 53(37), 4913-4916. doi:10.1016/j.tetlet.2012.06.117Zhou, Y., Yan, J., Zhang, N., Li, D., Xiao, S., & Zheng, K. (2018). A ratiometric fluorescent probe for formaldehyde in aqueous solution, serum and air using aza-cope reaction. Sensors and Actuators B: Chemical, 258, 156-162. doi:10.1016/j.snb.2017.11.043Chaiendoo, K., Sooksin, S., Kulchat, S., Promarak, V., Tuntulani, T., & Ngeontae, W. (2018). A new formaldehyde sensor from silver nanoclusters modified Tollens’ reagent. Food Chemistry, 255, 41-48. doi:10.1016/j.foodchem.2018.02.030Fauzia, V., Nurlely, Imawan, C., Narayani, N. M. M. S., & Putri, A. E. (2018). A localized surface plasmon resonance enhanced dye-based biosensor for formaldehyde detection. Sensors and Actuators B: Chemical, 257, 1128-1133. doi:10.1016/j.snb.2017.11.031El 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.6b03224Li, Z., Xue, Z., Wu, Z., Han, J., & Han, S. (2011). Chromo-fluorogenic detection of aldehydes with a rhodamine based sensor featuring an intramolecular deoxylactam. Organic & Biomolecular Chemistry, 9(22), 7652. doi:10.1039/c1ob06448gGuglielmino, M., Allouch, A., Serra, C. A., & Calvé, S. L. (2017). Development of microfluidic analytical method for on-line gaseous Formaldehyde detection. Sensors and Actuators B: Chemical, 243, 963-970. doi:10.1016/j.snb.2016.11.093Xia, H., Hu, J., Tang, J., Xu, K., Hou, X., & Wu, P. (2016). A RGB-Type Quantum Dot-based Sensor Array for Sensitive Visual Detection of Trace Formaldehyde in Air. Scientific Reports, 6(1). doi:10.1038/srep36794Feng, L., Musto, C. J., & Suslick, K. S. (2010). A Simple and Highly Sensitive Colorimetric Detection Method for Gaseous Formaldehyde. Journal of the American Chemical Society, 132(12), 4046-4047. doi:10.1021/ja910366pGuo, X.-L., Chen, Y., Jiang, H.-L., Qiu, X.-B., & Yu, D.-L. (2018). Smartphone-Based Microfluidic Colorimetric Sensor for Gaseous Formaldehyde Determination with High Sensitivity and Selectivity. Sensors, 18(9), 3141. doi:10.3390/s18093141He, L., Yang, X., Ren, M., Kong, X., Liu, Y., & Lin, W. (2016). An ultra-fast illuminating fluorescent probe for monitoring formaldehyde in living cells, shiitake mushrooms, and indoors. Chemical Communications, 52(61), 9582-9585. doi:10.1039/c6cc04254fGangopadhyay, A., Maiti, K., Ali, S. S., Pramanik, A. K., Guria, U. N., Samanta, S. K., … Mahapatra, A. K. (2018). A PET based fluorescent chemosensor with real time application in monitoring formaldehyde emissions from plywood. Analytical Methods, 10(24), 2888-2894. doi:10.1039/c8ay00514aLin, Q., Fan, Y.-Q., Gong, G.-F., Mao, P.-P., Wang, J., Guan, X.-W., … Wei, T.-B. (2018). Ultrasensitive Detection of Formaldehyde in Gas and Solutions by a Catalyst Preplaced Sensor Based on a Pillar[5]arene Derivative. ACS Sustainable Chemistry & Engineering, 6(7), 8775-8781. doi:10.1021/acssuschemeng.8b01124Cox, E. D., & Cook, J. M. (1995). The Pictet-Spengler condensation: a new direction for an old reaction. Chemical Reviews, 95(6), 1797-1842. doi:10.1021/cr00038a004Jonsson, G., Launosalo, T., Salomaa, P., Walle, T., Sjöberg, B., Bunnenberg, E., … Records, R. (1966). Fluorescence Studies on Some 6,7-Substituted 3,4-Dihydroisoquinolines Formed from 3-Hydroxytyramine (Dopamine) and Formaldehyde. Acta Chemica Scandinavica, 20, 2755-2762. doi:10.3891/acta.chem.scand.20-2755BJÖRKLUND, A., EHINGER, B., & FALCK, B. (1968). A METHOD FOR DIFFERENTIATING DOPAMINE FROM NORADRENALINE IN TISSUE SECTIONS BY MICROSPECTROFLUOROMETRY. Journal of Histochemistry & Cytochemistry, 16(4), 263-270. doi:10.1177/16.4.263Stöckigt, J., Antonchick, A. P., Wu, F., & Waldmann, H. (2011). The Pictet-Spengler Reaction in Nature and in Organic Chemistry. Angewandte Chemie International Edition, 50(37), 8538-8564. doi:10.1002/anie.201008071Allou, L., El Maimouni, L., & Le Calvé, S. (2011). Henry’s law constant measurements for formaldehyde and benzaldehyde as a function of temperature and water composition. Atmospheric Environment, 45(17), 2991-2998. doi:10.1016/j.atmosenv.2010.05.04

Resorcinol Functionalized Gold Nanoparticles for Formaldehyde Colorimetric Detection

[EN] Gold nanoparticles functionalized with resorcinol moieties have been prepared and used for detecting formaldehyde both in solution and gas phases. The detection mechanism is based on the color change of the probe upon the aggregation of the nanoparticles induced by the polymerization of the resorcinol moieties in the presence of formaldehyde. A limit of detection of 0.5 ppm in solution has been determined. The probe can be deployed for the detection of formaldehyde emissions from composite wood boards.We thank the Spanish Government (projects MAT2015-64139-C4-4-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and the Generalitat Valenciana (project PROMETEOII/2014/047) for support.Martínez-Aquino, C.; Costero, AM.; Gil Grau, S.; Gaviña, P. (2019). Resorcinol Functionalized Gold Nanoparticles for Formaldehyde Colorimetric Detection. Nanomaterials. 9(2):1-9. https://doi.org/10.3390/nano9020302S1992Salthammer, T. (2013). Formaldehyde in the Ambient Atmosphere: From an Indoor Pollutant to an Outdoor Pollutant? Angewandte Chemie International Edition, 52(12), 3320-3327. doi:10.1002/anie.201205984Bruemmer, K. J., Brewer, T. F., & Chang, C. J. (2017). Fluorescent probes for imaging formaldehyde in biological systems. Current Opinion in Chemical Biology, 39, 17-23. doi:10.1016/j.cbpa.2017.04.010Lang, I., Bruckner, T., & Triebig, G. (2008). Formaldehyde and chemosensory irritation in humans: A controlled human exposure study. Regulatory Toxicology and Pharmacology, 50(1), 23-36. doi:10.1016/j.yrtph.2007.08.012IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Vol. 100F (2012). Chemical Agents and Related Occupations: Formaldehydehttps://monographs.iarc.fr/wp-content/uploads/2018/06/mono100F-29.pdfChung, P.-R., Tzeng, C.-T., Ke, M.-T., & Lee, C.-Y. (2013). Formaldehyde Gas Sensors: A Review. Sensors, 13(4), 4468-4484. doi:10.3390/s130404468Soman, A., Qiu, Y., & Chan Li, Q. (2008). HPLC-UV Method Development and Validation for the Determination of Low Level Formaldehyde in a Drug Substance. Journal of Chromatographic Science, 46(6), 461-465. doi:10.1093/chromsci/46.6.461Risholm-Sundman, M., Larsen, A., Vestin, E., & Weibull, A. (2007). Formaldehyde emission—Comparison of different standard methods. Atmospheric Environment, 41(15), 3193-3202. doi:10.1016/j.atmosenv.2006.10.079Kim, S., & Kim, H.-J. (2005). Comparison of standard methods and gas chromatography method in determination of formaldehyde emission from MDF bonded with formaldehyde-based resins. Bioresource Technology, 96(13), 1457-1464. doi:10.1016/j.biortech.2004.12.003Yeh, T.-S., Lin, T.-C., Chen, C.-C., & Wen, H.-M. (2013). Analysis of free and bound formaldehyde in squid and squid products by gas chromatography–mass spectrometry. Journal of Food and Drug Analysis, 21(2), 190-197. doi:10.1016/j.jfda.2013.05.010Toews, J., Rogalski, J. C., Clark, T. J., & Kast, J. (2008). Mass spectrometric identification of formaldehyde-induced peptide modifications under in vivo protein cross-linking conditions. Analytica Chimica Acta, 618(2), 168-183. doi:10.1016/j.aca.2008.04.049Zhou, X., Lee, S., Xu, Z., & Yoon, J. (2015). Recent Progress on the Development of Chemosensors for Gases. Chemical Reviews, 115(15), 7944-8000. doi:10.1021/cr500567rZhou, Y., Yan, J., Zhang, N., Li, D., Xiao, S., & Zheng, K. (2018). A ratiometric fluorescent probe for formaldehyde in aqueous solution, serum and air using aza-cope reaction. Sensors and Actuators B: Chemical, 258, 156-162. doi:10.1016/j.snb.2017.11.043Chaiendoo, K., Sooksin, S., Kulchat, S., Promarak, V., Tuntulani, T., & Ngeontae, W. (2018). A new formaldehyde sensor from silver nanoclusters modified Tollens’ reagent. Food Chemistry, 255, 41-48. doi:10.1016/j.foodchem.2018.02.030El 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.6b03224Martínez-Aquino, C., Costero, A., Gil, S., & Gaviña, P. (2018). A New Environmentally-Friendly Colorimetric Probe for Formaldehyde Gas Detection under Real Conditions. Molecules, 23(10), 2646. doi:10.3390/molecules23102646Guo, X.-L., Chen, Y., Jiang, H.-L., Qiu, X.-B., & Yu, D.-L. (2018). Smartphone-Based Microfluidic Colorimetric Sensor for Gaseous Formaldehyde Determination with High Sensitivity and Selectivity. Sensors, 18(9), 3141. doi:10.3390/s18093141Gangopadhyay, A., Maiti, K., Ali, S. S., Pramanik, A. K., Guria, U. N., Samanta, S. K., … Mahapatra, A. K. (2018). A PET based fluorescent chemosensor with real time application in monitoring formaldehyde emissions from plywood. Analytical Methods, 10(24), 2888-2894. doi:10.1039/c8ay00514aBi, A., Yang, S., Liu, M., Wang, X., Liao, W., & Zeng, W. (2017). Fluorescent probes and materials for detecting formaldehyde: from laboratory to indoor for environmental and health monitoring. RSC Advances, 7(58), 36421-36432. doi:10.1039/c7ra05651fSaha, K., Agasti, S. S., Kim, C., Li, X., & Rotello, V. M. (2012). Gold Nanoparticles in Chemical and Biological Sensing. Chemical Reviews, 112(5), 2739-2779. doi:10.1021/cr2001178Mayer, K. M., & Hafner, J. H. (2011). Localized Surface Plasmon Resonance Sensors. Chemical Reviews, 111(6), 3828-3857. doi:10.1021/cr100313vKong, B., Zhu, A., Luo, Y., Tian, Y., Yu, Y., & Shi, G. (2011). Sensitive and Selective Colorimetric Visualization of Cerebral Dopamine Based on Double Molecular Recognition. Angewandte Chemie International Edition, 50(8), 1837-1840. doi:10.1002/anie.201007071Ma, P., Liang, F., Wang, D., Yang, Q., Ding, Y., Yu, Y., … Wang, X. (2014). Ultrasensitive determination of formaldehyde in environmental waters and food samples after derivatization and using silver nanoparticle assisted SERS. Microchimica Acta, 182(3-4), 863-869. doi:10.1007/s00604-014-1400-9Wen, G., Liang, X., Liang, A., & Jiang, Z. (2015). Gold Nanorod Resonance Rayleigh Scattering-Energy Transfer Spectral Determination of Trace Formaldehyde with 4-Amino-3-Hydrazino-5-Mercap-1,2,4-Triazole. Plasmonics, 10(5), 1081-1088. doi:10.1007/s11468-015-9893-6Fauzia, V., Nurlely, Imawan, C., Narayani, N. M. M. S., & Putri, A. E. (2018). A localized surface plasmon resonance enhanced dye-based biosensor for formaldehyde detection. Sensors and Actuators B: Chemical, 257, 1128-1133. doi:10.1016/j.snb.2017.11.031Al-Muhtaseb, S. A., & Ritter, J. A. (2003). Preparation and Properties of Resorcinol-Formaldehyde Organic and Carbon Gels. Advanced Materials, 15(2), 101-114. doi:10.1002/adma.200390020Martí, A., Costero, A. M., Gaviña, P., & Parra, M. (2015). Selective colorimetric NO(g) detection based on the use of modified gold nanoparticles using click chemistry. Chemical Communications, 51(15), 3077-3079. doi:10.1039/c4cc10149aGodoy-Reyes, T. M., Llopis-Lorente, A., Costero, A. M., Sancenón, F., Gaviña, P., & Martínez-Máñez, R. (2018). Selective and sensitive colorimetric detection of the neurotransmitter serotonin based on the aggregation of bifunctionalised gold nanoparticles. Sensors and Actuators B: Chemical, 258, 829-835. doi:10.1016/j.snb.2017.11.181Lewicki, J. P., Fox, C. A., & Worsley, M. A. (2015). On the synthesis and structure of resorcinol-formaldehyde polymeric networks – Precursors to 3D-carbon macroassemblies. Polymer, 69, 45-51. doi:10.1016/j.polymer.2015.05.016Martí, A., Costero, A. M., Gaviña, P., Gil, S., Parra, M., Brotons-Gisbert, M., & Sánchez-Royo, J. F. (2013). Functionalized Gold Nanoparticles as an Approach to the Direct Colorimetric Detection of DCNP Nerve Agent Simulant. European Journal of Organic Chemistry, 2013(22), 4770-4779. doi:10.1002/ejoc.201300339Appendino, G., Minassi, A., Daddario, N., Bianchi, F., & Tron, G. C. (2002). Chemoselective Esterification of Phenolic Acids and Alcohols. Organic Letters, 4(22), 3839-3841. doi:10.1021/ol0266471Haiss, W., Thanh, N. T. K., Aveyard, J., & Fernig, D. G. (2007). Determination of Size and Concentration of Gold Nanoparticles from UV−Vis Spectra. Analytical Chemistry, 79(11), 4215-4221. doi:10.1021/ac0702084Liu, X., Atwater, M., Wang, J., & Huo, Q. (2007). Extinction coefficient of gold nanoparticles with different sizes and different capping ligands. Colloids and Surfaces B: Biointerfaces, 58(1), 3-7. doi:10.1016/j.colsurfb.2006.08.00

Towards the fluorogenic detection of peroxide explosives through host-guest chemistry

[EN] Two dansyl-modified beta-cyclodextrin derivatives (1 and 2) have been synthesized as host-guest sensory systems for the direct fluorescent detection of the peroxide explosives diacetone diperoxide (DADP) and triacetone triperoxide (TATP) in aqueous media. The sensing is based on the displacement of the dansyl moiety from the cavity of the cyclodextrin by the peroxide guest resulting in a decrease of the intensity of the fluorescence of the dye. Both systems showed similar fluorescent responses and were more sensitive towards TATP than DADP.We thank the Spanish Government (MAT2015-64139-C4-4-R) and Generalitat Valenciana (PROMETEOII/2014/047) for financial support.Almenar, E.; Costero, AM.; Gaviña, P.; Gil Grau, S.; Parra Álvarez, M. (2018). Towards the fluorogenic detection of peroxide explosives through host-guest chemistry. Royal Society Open Science. 5(4). https://doi.org/10.1098/rsos.171787S54Dubnikova, F., Kosloff, R., Almog, J., Zeiri, Y., Boese, R., Itzhaky, H., … Keinan, E. (2005). Decomposition of Triacetone Triperoxide Is an Entropic Explosion. Journal of the American Chemical Society, 127(4), 1146-1159. doi:10.1021/ja0464903Fitzgerald, M., & Bilusich, D. (2011). Sulfuric, Hydrochloric, and Nitric Acid-Catalyzed Triacetone Triperoxide (TATP) Reaction Mixtures: An Aging Study. Journal of Forensic Sciences, 56(5), 1143-1149. doi:10.1111/j.1556-4029.2011.01806.xMatyáš, R., Pachman, J., & Ang, H.-G. (2009). Study of TATP: Spontaneous Transformation of TATP to DADP - Full Paper. Propellants, Explosives, Pyrotechnics, 34(6), 484-488. doi:10.1002/prep.200800043Matyas, R., Pachman, J., & Ang, H.-G. (2008). Study of TATP: Spontaneous Transformation of TATP to DADP. Propellants, Explosives, Pyrotechnics, 33(2), 89-91. doi:10.1002/prep.200700247Wang, J. (2007). Electrochemical Sensing of Explosives. Electroanalysis, 19(4), 415-423. doi:10.1002/elan.200603748Bauer, C., Willer, U., Lewicki, R., Pohlkötter, A., Kosterev, A., Kosynkin, D., … Schade, W. (2009). A Mid-infrared QEPAS sensor device for TATP detection. Journal of Physics: Conference Series, 157, 012002. doi:10.1088/1742-6596/157/1/012002Widmer, L., Watson, S., Schlatter, K., & Crowson, A. (2002). Development of an LC/MS method for the trace analysis of triacetone triperoxide (TATP). The Analyst, 127(12), 1627-1632. doi:10.1039/b208350gZhang, Y., Ma, X., Zhang, S., Yang, C., Ouyang, Z., & Zhang, X. (2009). Direct detection of explosives on solid surfaces by low temperature plasma desorption mass spectrometry. The Analyst, 134(1), 176-181. doi:10.1039/b816230aGirotti, S., Ferri, E., Maiolini, E., Bolelli, L., D’Elia, M., Coppe, D., & Romolo, F. S. (2011). A quantitative chemiluminescent assay for analysis of peroxide-based explosives. Analytical and Bioanalytical Chemistry, 400(2), 313-320. doi:10.1007/s00216-010-4626-3Walter, M. A., Panne, U., & Weller, M. G. (2011). A Novel Immunoreagent for the Specific and Sensitive Detection of the Explosive Triacetone Triperoxide (TATP). Biosensors, 1(3), 93-106. doi:10.3390/bios1030093Sella, E., & Shabat, D. (2008). Self-immolative dendritic probe for direct detection of triacetone triperoxide. Chemical Communications, (44), 5701. doi:10.1039/b814855dGermain, M. E., & Knapp, M. J. (2008). Turn-on Fluorescence Detection of H2O2and TATP. Inorganic Chemistry, 47(21), 9748-9750. doi:10.1021/ic801317xLin, H., & Suslick, K. S. (2010). A Colorimetric Sensor Array for Detection of Triacetone Triperoxide Vapor. Journal of the American Chemical Society, 132(44), 15519-15521. doi:10.1021/ja107419tLi, Z., Bassett, W. P., Askim, J. R., & Suslick, K. S. (2015). Differentiation among peroxide explosives with an optoelectronic nose. 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Colorimetric detection of normetanephrine, a pheochromocytoma biomarker, using bifunctionalised gold nanoparticles

[EN] A simple and effective colorimetric method for the detection of normetanephrine (NMN), an O-methylated metabolite of norepinephrine, using functionalised gold nanoparticles is described. This metabolite is an important biomarker in the diagnosis of adrenal tumours such as pheocromocytoma or paraganglioma. The colorimetric probe consists of spherical gold nanoparticles (AuNPs) functionalised with two different ligands, which specifically recognize different functional groups in normetanephrine. Thus, a benzaldehyde-terminated ligand was used for the recognition of the amino alcohol moiety in NMN, by forming the corresponding oxazolidine. On the other hand, N-acetyl-cysteine was chosen for the recognition of the phenolic hydroxyl group through the formation of hydrogen bonds. The selective double molecular recognition between the probe and the hydroxyl and the amino-alcohol moieties of normetanephrine led to interparticle-crosslinking aggregation resulting in a change in the color of the solution, from red to blue, which could be observed by naked eye. The probe was highly selective towards normetanephrine and no color changes were observed in the presence of other neurotransmitter metabolites such as homovanillic acid (HVA) (dopamine metabolite), 5-hydroxyindoleacetic acid (5-HIAA) (serotonin metabolite), or other biomolecules present in urine such as glucose (Glc), uric acid (U.A), and urea. Finally, the probe was evaluated in synthetic urine with constituents that mimic human urine, where a limit of detection of 0.5 mu M was achieved.Financial support from the Spanish Government (project MAT2015-64139-C4) and Generalitat Valenciana (Project PROMETEOII/2014/047 and AICO/2017/093) is gratefully acknowledged. T. Godoy-Reyes is grateful to Generalitat Valenciana for her Santiago Grisolia fellowship.Godoy-Reyes, TM.; Costero, AM.; Gaviña, P.; Martínez-Máñez, R.; Sancenón Galarza, F. (2019). Colorimetric detection of normetanephrine, a pheochromocytoma biomarker, using bifunctionalised gold nanoparticles. Analytica Chimica Acta. 1056:146-152. https://doi.org/10.1016/j.aca.2019.01.003S146152105

Detection and discrimination of organophosphorus pesticides in water by using a colorimetric probe array

[EN] Detection and discrimination of several organophosphorus pesticides in water using a colorimetric probe array containing twelve dyes has been achieved. A clear discrimination for malathion, leptophos, dichlorvos, dibrom and diazinon was observed. The array was used to determine the concentration of diazinon in orange leavesThe financial support from the Spanish Government (project MAT2012-38429-C04), the Generalitat Valenciana (project PROM-ETEO/2009/016) and the Universitat Politecnica de Valencia (project ref. 2711) is gratefully acknowledged. SCSIE (Universidad de Valencia) is also acknowledged for all the equipment employed.Ferri, D.; Gaviña, P.; Costero, AM.; Parra, M.; Vivancos, J.; Martínez-Máñez, R. (2014). Detection and discrimination of organophosphorus pesticides in water by using a colorimetric probe array. Sensors and Actuators B Chemical. 202:727-731. https://doi.org/10.1016/j.snb.2014.06.011S72773120

A Colorimetric Probe for the Selective Detection of Norepinephrine Based on a Double Molecular Recognition with Functionalized Gold Nanoparticles

[EN] A simple colorimetric probe for the selective and sensitive detection of neurotransmitter norepinephrine (NE), an important biomarker in the detection of tumors such as pheochromocytoma and paraganglioma, is described. The sensing strategy is based on the use of spherical gold nanoparticles functionalized with benzaldehyde and boronic acid-terminated moieties. A double molecular recognition involving on one hand the aromatic aldehyde and the aminoalcohol group of NE, and on the other hand the boronic acid and the catechol moiety of the neurotransmitter, results in analyte triggered aggregation of the gold nanoparticles, leading to a bathochromic shift of the SPR band in the UV-vis spectrum of the probe and a clear change in the color of the solution from red to blue. Probe P1 shows a remarkable selectivity toward NE versus other catecholamine neurotransmitters (dopamine and epinephrine) and selected biomolecules (S-HIAA, L-Tyr, glucose, uric acid, Lys and glutamic acid). Moreover, a linear response to NE in the 0-1 mu M concentration range was observed and a limit of detection of 0.07 mu M in aqueous media was determined by UV-vis spectroscopy. The sensitivity of the probe toward NE in synthetic urine was also evaluated. In this medium, a limit of detection of 0.09 mu M was obtained which falls within the range of clinical interestFinancial support from the Spanish Government (Projects MAT2015-64139-C4-1-R and MAT2015-64139-C4-4-R) and the Generalitat Valencia (Projects PROMETEOII/2014/047 and AICO/2017/093) is gratefully acknowledged. T. Godoy-Reyes is grateful to the Generalitat Valenciana for her Santiago Grisolia fellowship.Godoy-Reyes, TM.; Costero, AM.; Gaviña, P.; Martínez-Máñez, R.; Sancenón Galarza, F. (2019). A Colorimetric Probe for the Selective Detection of Norepinephrine Based on a Double Molecular Recognition with Functionalized Gold Nanoparticles. ACS Applied Nano Materials. 2(3):1367-1373. https://doi.org/10.1021/acsanm.8b02254S136713732

Nerve agent simulant detection by using chromogenic triaryl methane cation probes

Two triaryl methane cations have been used as probes for colorimetric detection of nerve agent simulants. Buffered mixed aqueous solutions of 1 and 2 showed bathochromic shifts in the presence of DCNP (diethylcyanophosphonate) and DCP (diethylchlorophosphate). The colour modulation can be observed to the naked eye. Appropriate mechanisms for the recognition event are proposed. © 2012 Elsevier Ltd.We thank the Spanish Government (projects MAT2009-14564-C01 and MAT2009-14564-C03) and the Generalitat Valenciana (project PROMETEO/2009/016) for support. R.G. is grateful to the Spanish Government for a fellowship. S.R. is grateful to the Generalitat Valenciana for a fellowship. SCSIE (Universidad de Valencia) is gratefully acknowledged for all the equipment employed.Gotor Candel, RJ.; Royo Calvo, S.; Costero Nieto, AM.; Parra Álvarez, M.; Gil Grau, S.; Martínez Mañez, R.; Sancenón Galarza, F. (2012). Nerve agent simulant detection by using chromogenic triaryl methane cation probes. Tetrahedron. 68(41):8612-8616. https://doi.org/10.1016/j.tet.2012.07.091S86128616684