Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems

Abstract

With its focus on synthetic reactions that are highly specific and reliable, 'click' chemistry has become a valuable tool for many scientific research areas and applications. Combining the modular, covalently bonded nature of click-chemistry linkages with an ability to reverse these linkages and reuse the constituent reactants in another click reaction, however, is a feature that is not found in most click reactions. Here we show that triazolinedione compounds can be used in click-chemistry applications. We present examples of simple and ultrafast macromolecular functionalization, polymer-polymer linking and polymer crosslinking under ambient conditions without the need for a catalyst. Moreover, when triazolinediones are combined with indole reaction partners, the reverse reaction can also be induced at elevated temperatures, and the triazolinedione reacted with a different reaction partner, reversibly or irreversibly dependent on its exact nature. We have used this 'transclick' reaction to introduce thermoreversible links into polyurethane and polymethacrylate materials, which allows dynamic polymer-network healing, reshaping and recycling.

Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

“…TADs are one of the most reactive (di)enophiles and show quantitative conversions at room temperature with isolated alkenes or conjugated dienes, respectively in an Alder-ene or Diels-Alder reaction. TAD has recently been applied in a wide range of applications, such as self-healing, 19 surface chemistry, [20][21][22] and post-modification of unsaturated ADMET polymers. 23 This is the first report on the post-modification of PPEs via their internal double bonds for tuning their thermal properties.…”

How Far Are We from Dose On Demand of Short-Lived Radiopharmaceuticals?

“…This structure reacts in a reversible way (using different temperatures, Fig. 6.2) with indoles through an ene click reaction [45]; however, it undergoes fast Diels-Alder reactions with dienes and is widely used in biology for its capacity to bind irreversibly tyrosine residues [46]. Such an approach could be very useful in DOD processes aimed at protein labeling, for which radiolabeled prosthetic groups enabling click chemistry are now widely employed [47].…”

Cu(0)-mediated living radical polymerisation in dimethyl lactamide (DML); an unusual green solvent with limited environmental impact

“…In addition to the control over molecular weight and molecular weight distribution, CRPs gave access to the control of the chain-end functionality allowing, for example, for the coupling between polymer-polymer [28][29][30] and polymerprotein 31,32 . Several bromoisobutyrate derivatives were selected to demonstrate that a wide range of functional group can be inserted at the polymer chain-end ( Figure S8): ethyl-2-bromoisobutyrate (EBiB), cholesteryl-2-bromoisobutyrate (Chol-BiB), pyrenyl-2-bromisiobutyrate (Py-BiB), Nsuccinimidyl-2-bromoisobutyrate (Succ-BiB), 2-bromo-2-methyl propionic acid 2-(3,5-dioxo-10-oxa-4-azatricyclo[5.2.1.02,6]dec-8-en-4-yl) ethyl ester (Mal-BiB), adamantyl-2-bromoisobutyrate (Adam-BiB) and dihydroxypropyl-2-bromoisobutyrate (diOH-BiB).…”