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Because of their recent interest towards dynamic combinatorial systems, chemists have to challenge their capacity to analyse complex mixtures of components exchanging their molecular fragments over time. Here we present, by a selection of practical examples from the literature, how chromatographic, spectroscopic, and microscopic techniques, as well as theoretical modelling and statistical data treatment, are instrumental in this new research area which is of significance at the interfaces with molecular biology and materials science.

Review: report on a synthetic strategy that allows the separation of enantiomerically ure planar chiral rotaxanes; 10 refs.

Thanks to their intrinsic network topologies, dynamic combinatorial libraries (DCLs) represent new tools for investigating fundamental aspects related to self-organization and adaptation processes. Very recently the first examples integrating self-replication features within DCLs have pushed even further the idea of implementing dynamic combinatorial chemistry (DCC) towards minimal systems capable of self-construction and/or evolution. Indeed, feedback loop processes – in particular in the form of autocatalytic reactions – are keystones to build dynamic supersystems which could possibly approach the roots of “Darwinian” evolvability at mesoscale. This topic of current interest also shows significant potentialities beyond its fundamental character, because truly smart and autonomous materials for the future will have to respond to changes of their environment by selecting and by exponentially amplifying their fittest constituents.

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