Chiral perylene materials by ionic self-assembly

Two chiral complexes (1-SDS and 1-SDBS) were prepared via the ionic self-assembly of a chiral perylene diimide tecton with oppositely charged surfactants. The effect of surfactant tail architecture on the self-assembly properties and supramolecular structure was investigated in detail using UV–vis, IR, circular dichroism, light microscopy, X-ray diffraction studies, and electron microscopy. The results obtained revealed the molecular chirality of the parent perylene tecton could be translated into supramolecular helical chirality of the resulting complexes via primary ionic interactions through careful choice of solvent and concentration. Differing solvent-dependent aggregation behavior was observed for these complexes as a result of the different possible noncovalent interactions via the surfactant alkyl tails. The results presented in this study demonstrate that ionic self-assembly (ISA) is a facile strategy for the production of chiral supramolecular materials based on perylene diimides. The structure–function relationship is easily explored here due to the wide selection and easy availability of common surfactants

Luminescent and Swellable Conjugated Microporous Polymers for Detecting Nitroaromatic Explosives and Removing Harmful Organic Vapors

Four new conjugated microporous polymers (CMPs) were synthesized by a Buchwald–Hartwig (BH) cross-coupling reaction of tri- and tetrafunctionalized precursors to yield materials with tunable surface area and pore size distribution. This approach yielded LPCMP1–4, CMPs with significantly higher Brunauer–Emmett–Teller (BET) surface areas (more than 5 times higher) than other related BH-based CMPs. These CMPs possess not only high BET specific surface areas and high chemical and thermal stabilities, but also exhibit outstanding swellability. To the best of our knowledge, swellable behavior was studied in great detail for CMPs for the first time, with the greatest degree of swelling for methanol reaching 16.5 and 16.3 mL g–1 for LPCMP1 and LPCMP3, respectively. Owing to their excellent swellability, we further studied the adsorption capacity of these CMPs for different toxic organic vapors (including toluene and methanol). LPCMP1 and LPCMP3 adsorbed 124 and 117 mg g–1 toluene, respectively, at saturated vapor pressure. For methanol, the adsorption capacities of LPCMP1 and LPCMP3 were up to 250 and 215 mg g–1, respectively, which are the highest recorded values when compared with published data for CMPs, HCPs, MOFs, and porous carbons. These materials are promising candidates for the removal and elimination of hazardous organic vapors and chemical warfare agents. Moreover, all the polymers show high sensitivity to nitroaromatic explosives. LPCMP2 and LPCMP4 exhibit high selectivity for TNT and may be suitable as new candidates to selectively detect TNT for security or environmental applications

Design and Control of Perylene Supramolecular Polymers through Imide Substitutions

The number and type of new supramolecular polymer (SMP) systems have increased rapidly in recent years. Some of the key challenges faced for these novel systems include gaining full control over the mode of self‐assembly, the creation of novel architectures and exploring functionality. Here, we provide a critical overview of approaches related to perylene‐based SMPs and discuss progress to exert control over these potentially important SMPs through chemical modification of the imide substituents. Imide substitutions affect self‐assembly behaviour orthogonally to the intrinsic optoelectronic properties of the perylene core, making for a valuable approach to tune SMP properties. Several recent approaches are therefore highlighted, with a focus on controlling 1) morphology, 2) H‐ or J‐ aggregation, and 3) mechanism of growth and degree of aggregation using thermodynamic and kinetic control. Areas of potential future exploration and application of these functional SMPs are also explored

Modelling and analysis of pH responsive hydrogels for the development of biomimetic photo-actuating structures

ABSTRACTPhoto-actuating structures inspired by the chemical sensing and signal transmission observed in sun-tracking leaves have recently been proposed by Dicker et al. The proposed light tracking structures are complex, multicomponent material systems, principally composed of a reversible photoacid or base, combined with a pH responsive hydrogel actuator. New modelling and characterization approaches for pH responsive hydrogels are presented in order to facilitate the development of the proposed structures. The model employs Donnan equilibrium for the prediction of hydrogel swelling in systems where the pH change is a variable resulting from the equilibrium interaction of all free and fixed (hydrogel) species. The model allows for the fast analysis of a variety of combinations of material parameters, allowing for the design space for the proposed photo-actuating structures to be quickly established. In addition, experimental examination of the swelling of a polyether-based polyurethane and poly(acrylic acid) interpenetrating network hydrogel is presented. The experiment involves simultaneously performing a titration of the hydrogel, and undertaking digital image correlation (DIC) to determine the hydrogel’s state of swelling. DIC allows for the recording of the hydrogel’s state of swelling with previously unattained levels of resolution. Experimental results provide both model material properties, and a means for model validation.</jats:p

Local and macroscopic electrostatic interactions in single α-helices

The non-covalent forces that stabilise protein structures are not fully understood. One way to address this is to study equilibria between unfolded states and α-helices in peptides. For these, electrostatic forces are believed to contribute, including interactions between: side chains; the backbone and side chains; and side chains and the helix macrodipole. Here we probe these experimentally using designed peptides. We find that both terminal backbone-side chain and certain side chain-side chain interactions (i.e., local effects between proximal charges, or interatomic contacts) contribute much more to helix stability than side chain-helix macrodipole electrostatics, which are believed to operate at larger distances. This has implications for current descriptions of helix stability, understanding protein folding, and the refinement of force fields for biomolecular modelling and simulations. In addition, it sheds light on the stability of rod-like structures formed by single α-helices that are common in natural proteins including non-muscle myosins