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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Multiplexed Detection of Analytes on Single Test Strips with Antibody-Gated Indicator-Releasing Mesoporous Nanoparticles

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

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

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

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]

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

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

Loading and Release of Charged and Neutral Fluorescent Dyes into and from Mesoporous Materials: A Key Role for Sensing Applications

The aim of this study is to determine the efficiency of loading and release of several zwitterionic, neutral, anionic and cationic dyes into/from mesoporous nanoparticles to find the optimum loading and release conditions for their application in detection protocols. The loading is carried out for MCM-41 type silica supports suspended in phosphate-buffered saline (PBS) buffer (pH 7.4) or in acetonitrile, involving the dyes (rhodamine B chloride, rhodamine 101 chloride, rhodamine 101 perchlorate, rhodamine 101 inner salt, meso-(4-hydroxyphenyl)-boron–dipyrromethene (BODIPY), sulforhodamine B sodium salt and fluorescein 27). As a general trend, rhodamine-based dyes are loaded with higher efficiency, when compared with BODIPY and fluorescein dyes. Between the rhodamine-based dyes, their charge and the solvent in which the loading process is carried out play important roles for the amount of cargo that can be loaded into the materials. The delivery experiments carried out in PBS buffer at pH 7.4 reveal for all the materials that anionic dyes are more efficiently released compared to their neutral or cationic counterparts. The overall best performance is achieved with the negatively charged sulforhodamine B dye in acetonitrile. This material also shows a high delivery degree in PBS buffer

Loading and Release of Charged and Neutral Fluorescent Dyes into and from Mesoporous Materials: A Key Role for Sensing Applications

The aim of this study is to determine the efficiency of loading and release of several zwitterionic, neutral, anionic and cationic dyes into/from mesoporous nanoparticles to find the optimum loading and release conditions for their application in detection protocols. The loading is carried out for MCM-41 type silica supports suspended in phosphate-buffered saline (PBS) buffer (pH 7.4) or in acetonitrile, involving the dyes (rhodamine B chloride, rhodamine 101 chloride, rhodamine 101 perchlorate, rhodamine 101 inner salt, meso-(4-hydroxyphenyl)-boron–dipyrromethene (BODIPY), sulforhodamine B sodium salt and fluorescein 27). As a general trend, rhodamine-based dyes are loaded with higher efficiency, when compared with BODIPY and fluorescein dyes. Between the rhodamine-based dyes, their charge and the solvent in which the loading process is carried out play important roles for the amount of cargo that can be loaded into the materials. The delivery experiments carried out in PBS buffer at pH 7.4 reveal for all the materials that anionic dyes are more efficiently released compared to their neutral or cationic counterparts. The overall best performance is achieved with the negatively charged sulforhodamine B dye in acetonitrile. This material also shows a high delivery degree in PBS buffer

Toward Luminescent Composites by Phase Transfer of SrF2:Eu3+ Nanoparticles Capped with Hydrophobic Antenna Ligands

Transparent dispersions of hydrophobic SrF2 : Eu3+ nanoparticles in cyclohexane with up to 20% europium were obtained by fluorolytic sol‐gel synthesis followed by phase transfer into cyclohexane through capping with sodium dodecylbenzenesulfonate (SDBS). The particles were characterized by TEM, XRD and DLS as spherical objects with a diameter between 6 and 11 nm in dry state. 1H‐13CP MAS NMR experiments revealed the binding of the anionic sulfonate head group to the particle surface. The particles show bright red luminescence upon excitation of the aromatic capping agents, acting as antennas for an energy transfer from the benzenesulfonate unit to the Eu3+ centers in the particles. This synthesis method overcomes the current obstacle of the fluorolytic sol‐gel synthesis that transparent dispersions can be obtained directly only in hydrophilic solvents. To demonstrate the potential of such hydrophobized alkaline‐earth fluoride particles, transparent luminescent organic‐inorganic composites with 10% SrF2 : Eu3+ embedded into polyTEGDMA, polyBMA, polyBDDMA and polyD3MA, respectively, were prepared, endowing the polymers with the luminescence features of the nanoparticles.Peer Reviewe