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This review highlights how the combination of supramolecular principles and nanoscopic solid structures enables the design of new hybrid sensing ensembles with improved sensitivity and/or selectivity and for the targeting of analytes for which selectivity is hard to achieve by conventional methods. Such ideas are bridging the gap between molecules, materials sciences and nanotechnology. Relevant examples will be detailed, taking into account functional aspects such as (1) enhanced coordination of functionalized solids, (2) enhanced signalling through preorganization, (3) signalling by assemblydisassembly of nanoscopic objects, (4) biomimetic probes utilizing discrimination by polarity and size and (5) distinct switching and gating protocols. These strategies are opening new prospects for sensor research and signalling paradigms at the frontier between nanotechnology, smart materials and supramolecular chemistry.
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.
Supramolecular interactions are vital processes in many chemical sensors, biochemical assays, and other analytical detection schemes. On the background of the current, rapidly developing, and constantly changing requirements for (bio)analytical techniques, the classical molecular host is increasingly overburdened to accomplish a specific analytical task with the desired selectivity and sensitivity. Instead, other signaling strategies have to be conceived that overcome the limits in signal output, dynamic range, or compound targeting, which are imminent to various traditional methods. A very promising approach is the combination of concepts of supramolecular chemistry with nanostructured or nanoscopic inorganic materials, that is, the development of hybrid sensor materials. Such hybrids often lead to improved functionality and enhanced performance, and the present chapter discusses the contributory features in relation to the major aspects, which are related to the enhanced coordination by the preorganization of binding sites, signal amplification by the preorganization on surfaces, aggregation‐mediated signaling, surface‐modification‐based signaling, the tuning of selectivity through polarity and size, and gated signaling.
Gated hybrid delivery systems: En route to sensory materials with inherent signal amplification
(2013)
Hybrid nanoparticles with a large specific surface area are a particularly exciting vehicle for delivery applications. Such highly porous or container-like structures, usually prepared from silica and frequently from gold, can incorporate a large number of chemical substances such as drug and/or indicator molecules. When equipped with a chemically or physically addressable gating function at the openings of the voids, the release of the cargo can be controlled at will. Because many more molecules can be stored as cargo in the pores of the support than there are functional groups as anchoring sites for the gating entities attached to the outer surface (for efficient pore capping), the systems possess inherent features of (signal) amplification. The present article will introduce various design strategies for different types of physical (light, temperature, magnetism) and chemical (pH, metal ions, anion, small organic molecules, enzymes) stimuli in connection with drug and indicator release. We will highlight exciting aspects of combining both features in theranostic applications and will stress which requirements still have to be met by many of the systems to be readily applicable in a sensory context.
Integration of a polymerisable fluorescent urea-nitrobenzoxadiazole monomer 1 into a few-nanometre thin molecularly imprinted polymer (MIP) shell coated onto a 300 nm silica core with the tetrabutylammonium salt of N-carbobenzyloxy-L-phenylalanine (Cbz- or Z-ʟ-Phe) as the imprinted template yields core/shell MIP nanoparticles that respond to the designated analyte with a strong fluorescence increase in the visible spectral range. The system shows promising imprinting and enantioselectivity factors of 3.6 and 1.9 when benzylmethylacrylate (BMA) is used as co-monomer and ethylene glycol dimethacrylate (EDMA) as cross-linker. A second, naphthalimide-based fluorescent urea 2 is employed in the preparation of MIP thin-films and monolithic polymers for separation techniques. Spectroscopic and chromatographic studies of the MIPs with the analytes Z-ʟ-Phe, Z-ʟ-glutamic acid (Z-ʟ-Glu) and penicilin G (PenG) revealed the (enantio)selective discrimination behaviour of these materials.
A naphthalimide-based fluorescent indicator monomer 1 for the integration into chromo- and fluorogenic molecularly imprinted polymers (MIPs) was synthesized and characterized. The monomer was equipped with a urea binding site to respond to carboxylate-containing guests with absorption and fluorescence changes, namely a bathochromic shift in absorption and fluorescence quenching. Detailed spectroscopic analyses of the title compound and various models revealed the signaling mechanism. Titration studies employing benzoate and Z-ʟ-phenylalanine (Z-ʟ-Phe) suggest that indicator monomers such as the title compound undergo a mixture of deprotonation and complex formation in the presence of benzoate but yield hydrogen-bonded complexes, which are desirable for the molecular imprinting process, with weakly basic guests like Z-ʟ-Phe. Compound 1 could be successfully employed in the synthesis of monolithic and thin-film MIPs against Z-ʟ-Phe, Z-L-glutamic acid, and penicillin G. Chromatographic assessment of the selectivity features of the monoliths revealed enantioselective discrimination and clear imprinting effects. Immobilized on glass coverslips, the thin-film MIPs of 1 displayed a clear signaling behavior with a pronounced enantioselective fluorescence quenching dependence and a promising discrimination against cross-analytes.
Nitroaromaten und insbesondere Trinitrotoluol (TNT) sind weit verbreitete Spreng- und Umweltschadstoffe. Die größte Herausforderung bei der Detektion von TNT in der Gasphase ist der geringe Dampfdruck. Derzeit werden vielerorts günstige, schnelle, handliche und einfach zu bedienende Alternativen zur klassischen TNT-Analytik entwickelt. Aktuell existieren keine einheitlichen Richtlinien für Sprengstoffsensoren. Hier wird die Entwicklung eines Messplatzes zur Validierung von Sprengstoffsensoren sowie die Erprobung eines kompakten Mustersensors vorgestellt.