Chemical complexity—supramolecular self-assembly of synthetic and biological building blocks in water

Abstract

Aqueous supramolecular chemistry, the non-covalent assembly of simple building blocks into higher ordered architectures in water has received much focus recently. Biological systems are able to form complex, and well-defined microstructures essential to cellular function, and supramolecular chemistry has demonstrated its utility in assembling molecules to form increasingly complex assemblies. This tutorial review will summarise non-covalent building blocks based on both synthetic and biological systems in an aqueous environment, emphasising the complexity of the assemblies formed. Examples of higher ordered assemblies will be highlighted, from supramolecular plastics to spider silks, towards more compartmentalised protocell precursors.

Dynamic Macromolecular Material Design—The Versatility of Cyclodextrin‐Based Host–Guest Chemistry

“…[7] Supramolecular chemistry has-since its conception by Lehn [8] -been amajor influence on the entire field of chemistry and especially on polymer chemistry, [9] particularly for the formation of higher level complex self-assemblies of macromolecules.T he main types of supramolecular interactions utilized in polymer sciences are metal complexes, [10] hydrogen bonding, [11] and inclusion complexes. [12] Common hosts for inclusion complexes in aqueous solution are cucurbiturils, [13] calixarenes, [14] pillararenes, [15] and the frequently utilized cylodextrins (CDs).…”

Structure and growth behavior of centimeter-sized helical oleate assemblies formed with assistance of medium-length carboxylic acids

“…[1][2][3] Research has focused on the spatiotemporal behavior of molecular assembly and, especially, the dynamics of these materials when utilized in life systems 4,5 and soft devices. 6,7 Various experimental and theoretical studies on assembly behavior have been reported and reviewed.…”

Controlling supramolecular polymerization through multicomponent self‐assembly

“…While it is possible to use the toolbox of supramolecular and physical organic chemistry to tune the affinity of a monomer for itself, via molecular design or via concentration and temperature dependent selfassembly, precise engineering of molecular weight, shape, and size of the produced supramolecular polymer remains challenging. This is particularly true for supramolecular polymerizations in water, 30,43 where noncovalent forces like hydrogen bonding and electrostatic interactions are drastically weakened via competitive binding and solvation effects. Water represents a unique medium for self-assembly [44][45][46] and robust supramolecular systems can only be produced by combining weak noncovalent interactions with hydrophobic shielding.…”

“…Water represents a unique medium for self-assembly [44][45][46] and robust supramolecular systems can only be produced by combining weak noncovalent interactions with hydrophobic shielding. 30,43,[47][48][49] Compared to the extraordinary achievements in precision polymer synthesis via living and controlled covalent polymerization processes, [50][51][52][53][54][55][56][57][58][59] supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, sequence and morphology. The discussion in this highlight article is focussed on four strategies that have been developed as promising methodologies to control supramolecular polymerization using two or more building blocks, in order to produce well-defined materials with respect to architecture, size, stability, and stimuliresponsive properties.…”