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Temporally controlled cooperative and living supramolecular polymerization by the buffered release of monomers has been recently introduced as an important concept towards obtaining monodisperse and multicomponent self-assembled materials. In synthetic, dynamic supramolecular polymers, this requires efficient design strategies for the dormant, inactive states of the monomers to kinetically retard the otherwise spontaneous nucleation process. However, a generalized design principle for the dormant monomer states to expand the scope of precision supramolecular polymers has not been established yet, due to the enormous differences in the mechanism, energetic parameters of self-assembly and monomer exchange dynamics of the diverse class of supramolecular polymers. Here we report the concept of transient dormant states of monomers generated by redox reactions as a predictive general design to achieve monodisperse supramolecular polymers of electronically active, chromophoric or donor-acceptor, monomers. The concept has been demonstrated with charge-transfer supramolecular polymers with an alternating donor-acceptor sequence. Monodisperse and well-defined self-assembled materials can be obtained by fuel-driven temporally controlled supramolecular polymerization via the buffered release of monomers. Here the authors show that a redox-responsive transient dormant state of monomer generated by redox reaction can lead to supramolecular polymers with low dispersity. [ABSTRACT FROM AUTHOR]

Two new boronic ester conjugated benzophenone derivatives are reported, which exhibit visible afterglow phosphorescence under ambient conditions and solution-processable thin films. The carbonyl group and pinacol moiety in the molecular design play a crucial role to achieve good phosphorescence efficiency in air. [ABSTRACT FROM AUTHOR]

Temporal control of supramolecular assemblies to modulate the structural and transient characteristics of synthetic nanostructures is an active field of research within supramolecular chemistry. Molecular designs to attain temporal control have often taken inspiration from biological assemblies. One such assembly in Nature which has been studied extensively, for its well-defined structure and programmable self-assembly, is the ATP-driven seeded self-assembly of actin. Here we show, in a synthetic manifestation of actin self-assembly, an ATP-selective and ATP-fuelled, controlled supramolecular polymerization of a phosphate receptor functionalised monomer. It undergoes fuel-driven nucleation and seeded growth that provide length control and narrow dispersity of the resultant assemblies. Furthermore, coupling via ATP-hydrolysing enzymes yielded its transient characteristics. These results will usher investigations into synthetic analogues of important biological self-assembly motifs and will prove to be a significant advancement toward biomimetic temporally programmed materials. [ABSTRACT FROM AUTHOR]

Measuring humidity in dynamic situations calls for highly sensitive fast response sensors. Here we report, a humidity sensor fabricated using solution processed supramolecular nanofibres as active resistive sensing material. The nanofibres are built via self- assembly of donor and acceptor molecules (coronene tetracarboxylate and dodecyl methyl viologen respectively) involved in charge transfer interactions. The conductivity of the nanofibre varied sensitively over a wide range of relative humidity (RH) with unprecedented fast response and recovery times. Based on UV-vis, XRD and AFM measurements, it is found that the stacking distance in the nanofibre decreases slightly while the charge transfer band intensity increases, all observations implying enhanced charge transfer interaction and hence the conductivity. It is demonstrated to be as a novel breath sensor which can monitor the respiration rate. Using two humidity sensors, a breath flow sensor was made which could simultaneously measure RH and flow rate of exhaled nasal breath. The integrated device was used for monitoring RH in the exhaled breath from volunteers undergoing exercise and alcohol induced dehydration. [ABSTRACT FROM AUTHOR]

Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways that go beyond traditional concepts of homogeneous and secondary nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from ?-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies. [ABSTRACT FROM AUTHOR]

Temporal control over self-assembly process is a desirable trait in the quest towards adaptable and controllable materials. The ability to devise synthetic ways to control the growth, as well as decay of materials has long been a property which only the biological systems could perform seamlessly. A common synthetic strategy which works on the biological principles such as chemical fuel-driven control over temporal self-assembly profile has not been completely realized synthetically. Here we show, we filled this dearth by showing that a chemical fuel driven self-assembling system can not only be grown in a controlled manner, but it can also result in precise control over the assembly and disassembly kinetics. Herein, we elaborate strategies which clearly show that once a chemical fuel driven self-assembly is established it can be made receptive to multiple molecular cues such that the inherent growth and decay characteristics are programmed into the ensemble. Temporal control over self-assembly processes is a desirable trait for discovering adaptable and controllable materials. Here the authors show that a chemical fuel driven system can not only self-assemble in a controlled manner, but can also result in precise control over the assembly and disassembly kinetics. [ABSTRACT FROM AUTHOR]

The article discusses the concept of amphiphilicity in the advancement in supramolecular chemistry which regain through hydrophobic amphiphiles of molecules. It highlights the use of various techniques to observe alkyl shells including neutron scattering measurements, small-angle X-ray and cryo-transmission electron microscopy. It also cites the benefits of liquid crystallinity for a long-range order in the manipulation of nanometre scale in materials with a monolithic structure.