Reaction behaviour of peptide-based single thiol-thioesters exchange reaction substrate in the presence of externally added thiols

Identification of patterns in chemical reaction pathways aids in the effective design of molecules for specific applications. Here, we report on model reactions with a water-soluble single thiol-thioester exchange (TTE) reaction substrate, which was designed taking in view biological and medical applications. This substrate consists of the thio-depsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) and does not yield foul-smelling thiol exchange products when compared with aromatic thiol containing single TTE substrates. TDP generates an α,ω-dithiol crosslinker in situ in a ‘pseudo intramolecular’ TTE. Competitive intermolecular TTE of TDP with externally added “basic” thiols increased the crosslinker concentration whilst “acidic” thiols decreased its concentration. TDP could potentially enable in situ bioconjugation and crosslinking applications. Graphic abstract The competition between ‘pseudo intramolecular’ and intermolecular exchange of a peptide-based thiol-thioester exchange (TTE) substrate can be used to control the relative amount of final exchange products based on size and pKa values of externally added thiols. Potential application of this system can be seen in the development of TTE substrates for the rapid identification of thiols by dynamic combinatorial screening.

Enhancing the toughness of composites via dynamic thiol–thioester exchange (TTE) at the resin–filler interface

An adaptive interface employing thiol-thioester exchange (TTE) at the resin-filler interface is introduced to promote interfacial stress relaxation and improve the mechanical performance of thermosetting composites.

Production of dynamic lipid bilayers using the reversible thiol–thioester exchange reaction

Coupling of phospholipid precursors using the reversible thiol–thioester exchange reaction enables downstream remodeling and functionalization.

A user's guide to the thiol-thioester exchange in organic media: scope, limitations, and applications in material science

The dynamic exchange of thiols and thioesters in organic media was explored, leading to room temperature plasticity in crosslinked polymers.

Recyclable and repolymerizable thiol–X photopolymers

Truly recyclable and repolymerizable photopolymers were achieved by utilizing thiol–ene polymerization and thiol–thioester exchange reactions.