Abstract
AbstractDynamic combinatorial chemistry (DCC) is a powerful approach for creating complex chemical systems, giving access to the studies of complexity and exploration of functionality in synthetic systems. However, compared with more advanced living systems, the man‐made chemical systems are still less functional, due to their limited complexity and insufficient kinetic control. Here we start by introducing strategies to enrich the complexity of dynamic combinatorial libraries (DCLs) for exploiting unexpected functions by increasing the species of building blocks and/or templates used. Then, we discuss how dynamic isomerization of photo‐switchable molecules help DCLs increase and alter the systemic complexity in‐situ. Multi‐phase DCLs will also be reviewed to thrive complexity and functionality across the interfaces. Finally, there will be a summary and outlook about remote kinetic control in DCLs that are realized by applying exogenous physical transduction signals of stress, light, heat and ultrasound.
Highlights
Dynamic combinatorial chemistry (DCC) is a powerful approach for creating complex chemical systems, giving access to the studies of complexity and exploration of functionality in synthetic systems
We start by introducing strategies to enrich the complexity of dynamic combinatorial libraries (DCLs) for exploiting unexpected functions by increasing the species of building blocks and/or templates used
Compared with biological systems, the DCC based synthetic systems are still in a primitive evolutionary stage and much less functional. This situation may be ascribed to two reasons: i) the limited complexities in the current DCLs have much less possibilities of producing functional molecules than nature; ii) insufficient kinetic control for amplifying and maintaining the desired function. Facing such complexed challenges arising from the exploration of functional DCLs, we should deliberate our strategies before getting dazzled in the arsenal of DCC
Summary
The species of the building blocks will dictate what types of dynamic covalent reactions are constructing a thermodynamics-governed equilibrating DCL. In the last decade, researchers have gradually discovered that diversifying building blocks to engineer multiple reactions in a single library will dramatically increase the complexity of the library, and provide additional control knobs to the system, promoting the emergence of functions from DCLs at a system level. Li et al reported a dynamic combinatorial strategy for a system giving rise to allosteric synthetic receptors based on the use of two different templates at the same time (Figure 3).[16] Without the introduction of any template into a DCL prepared from a naphthalene derived unsymmetrical dithiol building block 3, the dominant species in the library were [2]catenane isomers interlocked by tetrameric isomers. This work has shed a light on using DCC to achieve batch screening of highly selective ligands/receptors for homologous biomolecules facilely
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