The sensation of taste is mediated by activation or deactivation of transmembrane pores. Artificial stimulus-responsive pores are enormously appealing as sensor components because changes in their activity are readily detectable in many different ways. However, the detection of multiple components in complex matrices (such as foods) with one pore sensor has so far remained elusive because the specificity necessary for sensing a target compound in complex mixtures is incompatible with the broad applicability needed for the detection of multiple components. Here, we present synthetic pores that, like our tongues, can sense flavours in food and in addition make them visibly detectable. Differential sensing and pattern recognition are solutions based on empirical and biomimetic approaches. They have been explored with synthetic receptor arrays and electronic tongues. In contrast, our approach is non-empirical as it exploits reactive amplifiers that covalently capture elusive analytes after enzymatic signal generation and drag them into synthetic pores for blockage. Reactive amplification proved to be highly sensitive and adaptable to various analytes and pores. Moreover, it can be combined with reactive filtration for minimizing interference. The system was tested on real food samples for detection of sucrose, lactose, lactate, acetate, citrate and glutamate to demonstrate the feasibility of these synthetic pores as universal sensors.
Monomers possessing two functionalities suitable for polymerization are often designed and utilized in syntheses directed to the formation of cross-linked macromolecules. In this review, we give an account of recent developments related to the use of such monomers in cyclopolymerization processes, in order to form linear, soluble macromolecules. These processes can be activated by means of radical, ionic, or transition-metal mediated chain-growth polymerization mechanisms, to achieve cyclic moieties of variable ring size which are embedded within the polymer backbone, driving and tuning peculiar physical properties of the resulting macromolecules. The two functionalities are covalently linked by a "tether", which can be appropriately designed in order to "imprint" elements of chemical information into the polymer backbone during the synthesis and, in some cases, be removed by postpolymerization reactions. The two functionalities can possess identical or even very different reactivities toward the polymerization mechanism involved; in the latter case, consequences and outcomes related to the sequence-controlled, precision synthesis of macromolecules have been demonstrated. Recent advances in new initiating systems and polymerization catalysts enabled the precision syntheses of polymers with regulated cyclic structures by highly regio- and/or stereoselective cyclopolymerization. Cyclopolymerizations involving double cyclization, ring-opening, or isomerization have been also developed, generating unique repeating structures, which can hardly be obtained by conventional polymerization methods.
physical property differentiating two enantiomers is the direction of rotation of the polarized light. Indeed, the manipulation of polarized light, both in the absorbance and emission mode, is useful in a series of technological applications, such as liquid crystal display (LCD) panels, 3D imaging in biological systems, nonlinear optics, spintronic devices. [5-8] Progresses in the field have been boosted by the increased availability of modern spectroscopic methods. For circular dichroism (CD), which relates to ground-state properties, the commercial availability of the spectrophotometer dates back to the 1960s and has enabled in depth studies of the tertiary structure of proteins. In contrast, circularly polarized luminescence (CPL) spectrophotometers have only been recently commercially available. Nevertheless, CPL gives important additional informations, as it provides information on the excited-state, and luminescence is generally more of interest in terms of materials science and devices. [9] Emissive organic materials have been studied for decades. Among these, organic light-emitting diodes (OLEDs) have reached large-scale commercialization, since they show unique technological advantages with respect to previous technologies: energy-saving, low working voltage, high brightness, and contrast display. Polarized emission and CPL has been the subject of increasing interest. Indeed, circularly polarized OLEDs (CP-OLEDs), based on chiral organic chromophores, have been realized and reported in the recent literature. A variety of chiral organic emitters have been proposed for CPL materials. [10] Aggregation-caused quenching (ACQ) of emission is a common problem that can severely limit the performance of (chiral and achiral) fluorophores in the solid state. The field of emissive dyes has been revolutionized in the early 2000s by Tang's group, which introduced the concept, seemingly counterintuitive at the time, of aggregation-induced emission (AIE). Suitable AIE chromophores (AIEgens) can exhibit strong fluorescence emission in aggregated states, despite being nonemissive in solution. [11] The most frequent mechanism for AIE occurs when AIEgens have freely-rotating groups which, upon excitation, relax back through these rotations instead of releasing energy as light. When they aggregate or crystallize, they become emissive through restricted intramolecular rotation (RIR). Since then, the AIE field literally exploded, and several reports have started to appear on chirality-related CPL emissive dyes. [12] Chirality is becoming increasingly important in the design of organic materials with functional properties, when bulk anisotropy is needed. In the past decades, a plethora of chiral organic materials have been studied and developed. Nanostructures have brought substantial advancement to the realization of organic-molecule-based devices, and the possibilities for solid-state light emission are very promising in view of potential applications. Scientific approaches to the realization of chiral emissive materials are ...
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