Signaling Recognition Events with Fluorescent Sensors and Switches.

The field of chemical sensing is becoming ever more dependent upon novel materials. Polymers, crystals, glasses, particles, and nanostructures have made a profound impact and have endowed modern sensory systems with superior performance. Electronic polymers have emerged as one of the most important classes of transduction materials; they readily transform a chemical signal into an easily measured electrical or optical event. Although our group reviewed this field in 2000,1 the high levels of activity and the impact of these methods now justify a subsequent review as part of this special issue. In this review we restrict our discussions to purely fluorescence-based methods using conjugated polymers (CPs). We further confine our detailed coverage to articles published since our previous review and will only detail earlier research in this Introduction to illustrate fundamental concepts and terminology that underpin the recent literature.

Chemical sensors based on amplifying fluorescent conjugated polymers.

Although the field of polymer solar cell has seen much progress in device performance in the past few years, several limitations are holding back its further development For instance, current high-efficiency (>90%) cells are restricted to material combinations that are based on limited donor polymers and only one specific fullerene acceptor Here we report the achievement of high-performance (efficiencies up to 108%, fill factors up to 77%) thick-film polymer solar cells for multiple polymer:fullerene combinations via the formation of a near-ideal polymer:fullerene morphology that contains highly crystalline yet reasonably small polymer domains This morphology is controlled by the temperature-dependent aggregation behaviour of the donor polymers and is insensitive to the choice of fullerenes The uncovered aggregation and design rules yield three high-efficiency (>10%) donor polymers and will allow further synthetic advances and matching of both the polymer and fullerene materials, potentially leading to significantly improved performance and increased design flexibility

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Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells.

Fluorogenic and chromogenic chemosensors and reagents for anions.

About Supramolecular Assemblies of π-Conjugated Systems

Self-organization that occurs far from thermodynamic equilibrium is ubiquitous in nature but has remained challenging to control in synthetic supramolecular systems. A complex system has now been devised that displays such behaviour. Porphyrin derivative monomers undergo living supramolecular polymerization, a reaction underpinned by the interplay of two supramolecular polymerization pathways.

Living supramolecular polymerization realized through a biomimetic approach

The mechanism of supramolecular polymerization has been elucidated for an archetype organogelator molecule composed of a perylene bisimide aromatic scaffold and two amide substituents. This molecule self-assembles into elongated one-dimensional nanofibers through a cooperative nucleation–growth process. Thermodynamic and kinetic analyses have been applied to discover conditions (temperature, solvent, concentration) where the spontaneous nucleation can be retarded by trapping of the monomers in an inactive conformation, leading to lag times up to more than 1 h. The unique kinetics in the nucleation process was confirmed as a thermal hysteresis in a cycle of assembly and disassembly processes. Under appropriate conditions within the hysteresis loop, addition of preassembled nanofiber seeds leads to seeded polymerization from the termini of the seeds in a living supramolecular polymerization process. These results demonstrate that seeded polymerizations are not limited to special situations where off-pathway...

Mechanism of self-assembly process and seeded supramolecular polymerization of perylene bisimide organogelator.

Positive homotropic allosterism appears in important information transduction processes where chemical and physical signals are efficiently amplified. The phenomena are ubiquitous in nature, but the general methodology for the design of such allosteric systems is not yet established in an artificial system. This account reviews such artificial receptors that can bind guest ions and molecules in a positive allosteric manner and discusses what kinds of factors are indispensable as scaffolds in the design of this novel class of allosteric systems and what common factors are needed to realize the cooperativity. It has been shown that the scaffolds are mostly dynamic and are skillfully combined with the molecular recognition systems so that the subsequent guest binding can occur more favorably than the first guest binding. In addition, it has been suggested that positive homotropic allosterism can be utilized as a new strategy to attain high guest selectivity and guest affinity which cannot be attained by conv...

Positive allosteric systems designed on dynamic supramolecular scaffolds: toward switching and amplification of guest affinity and selectivity.

A Colorimetric and Ratiometric Fluorescent Chemosensor with Three Emission Changes: Fluoride Ion Sensing by a Triarylborane– Porphyrin Conjugate

Molecular self-assembly under kinetic control is expected to yield nanostructures that are inaccessible through the spontaneous thermodynamic process. Moreover, time-dependent evolution, which is reminiscent of biomolecular systems, may occur under such out-of-equilibrium conditions, allowing the synthesis of supramolecular assemblies with enhanced complexities. Here we report on the capacity of a metastable porphyrin supramolecular assembly to differentiate into nanofibre and nanosheet structures. Mechanistic studies of the relationship between the molecular design and pathway complexity in the self-assembly unveiled the energy landscape that governs the unique kinetic behaviour. Based on this understanding, we could control the differentiation phenomena and achieve both one- and two-dimensional living supramolecular polymerization using an identical monomer. Furthermore, we found that the obtained nanostructures are electronically distinct, which illustrates the pathway-dependent material properties.

Masayuki Takeuchi

Papers

Living supramolecular polymerization realized through a biomimetic approach

Mechanism of self-assembly process and seeded supramolecular polymerization of perylene bisimide organogelator.

Positive allosteric systems designed on dynamic supramolecular scaffolds: toward switching and amplification of guest affinity and selectivity.

A Colorimetric and Ratiometric Fluorescent Chemosensor with Three Emission Changes: Fluoride Ion Sensing by a Triarylborane– Porphyrin Conjugate

Control over differentiation of a metastable supramolecular assembly in one and two dimensions.