Reactions in Dynamic Self-Assemblies

The dynamic processes in self-assemblies are involved in numerous domains that span throughout the modern aspects of chemical sciences, going from fundamental investigations into the origin of life to the most striking technological applications in medicine or electronics. This chapter aims at providing the reader with a brief overview of the concepts that link chemical reactivity with dynamic templates and catalysts made of large supramolecular assemblies. Specifically, we discuss kinetic and thermodynamic aspects of selected examples depending on (i) the nature of the matrix — that is, micelles, vesicles, liquid crystals, and gels; (ii) the nature of their constituents — that is, surfactants, block copolymers, bioactive macromolecules; and (iii) the nature of the chemical transformations that are performed — that is, reaction of small organic molecules, biomolecules, polymerizations, nanoparticle formation, and also reactions that involve the constituents of the matrix themselves as observed, for instance, in self-reproducing systems. In each section, we combine original papers that paved the field together with more recent works of particular interest; several reviews are also referenced to help in accessing a more comprehensive literature.

Keywords: self-assembly; supramolecular chemistry; micelles; vesicles; surfactants; block copolymers; peptides; liquid crystals; gels; mesophases; nanostructuration; nanoreactors; materials synthesis; catalysis; polymerization; self-replication; dynamic combinatorial chemistry; chemical evolution