The cooperative assembly of biopolymers and small molecules can yield functional materials with precisely tunable properties. Here, the fabrication, characterization, and use of multicomponent hybrid gels as selective gas sensors are reported. The gels are composed of liquid crystal droplets self-assembled in the presence of ionic liquids, which further coassemble with biopolymers to form stable matrices. Each individual component can be varied and acts cooperatively to tune gels' structure and function. The unique molecular environment in hybrid gels is explored for supramolecular recognition of volatile compounds. Gels with distinct compositions are used as optical and electrical gas sensors, yielding a combinatorial response conceptually mimicking olfactory biological systems, and tested to distinguish volatile organic compounds and to quantify ethanol in automotive fuel. The gel response is rapid, reversible, and reproducible. These robust, versatile, modular, pliant electro-optical soft materials possess new possibilities in sensing triggered by chemical and physical stimuli.
A selective luminescent sensor was fabricated by simply mixing a Tb(iii)-based MOF with polymethylmetahacrylate enabling to detect sub-ppb range of nitroaromatic vapours.
Mixed bisadducts resulting from the sequential addition of a nitrone and an azomethine ylide to the porphyrin macrocycle were efficiently obtained, in a site selective approach.
A novel technique for the creation of metal-organic framework (MOF) films based on soft-imprinting and their use as gas sensors was developed. The microporous MOF material [Zn2(bpdc)2(bpee)] (bpdc = 4,4′-biphenyldicarboxylate; bpee = 1,2-bipyridylethene) was synthesized solvothermally and activated by removing the occluded solvent molecules from its inner channels. MOF particles were characterized by powder X-ray diffraction and fluorescence spectroscopy, showing high crystallinity and intense photoluminescence. Scanning electron microscope images revealed that MOF crystals were mainly in the form of microneedles with a high surface-to-volume ratio, which together with the high porosity of the material enhances its interaction with gas molecules. MOF crystals were soft-imprinted into cellulose acetate (CA) films on quartz at different pressures. Atomic force microscope images of soft-imprinted films showed that MOF crystals were partially embedded into the CA. With this procedure, mechanically stable films were created, with crystals protruding from the CA surface and therefore available for incoming gas molecules. The sensing properties of the films were assessed by exposing them to saturated atmospheres of 2,4-dinitrotoluene, which resulted in a substantial quenching of the fluorescence after few seconds. The soft-imprinted MOF films on CA/quartz exhibit good sensing capabilities for the detection of nitroaromatics, which was attributed to the MOF sensitivity and to the novel and more efficient film processing method based on soft-imprinting.
An efficient strategy was developed to obtain carboxyphenyl porphyrin, chlorins and metal complexes, with potential applications in photonics and biology.
This review provides an overview of the state-of-the-art of OFS based on sol–gel materials for diverse applications with particular emphasis on OFS for structural health monitoring of concrete structures.
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