Interfacial Diels–Alder Reaction between Furan-Functionalized Polymer Coatings and Maleimide-Terminated Poly(ethylene glycol)

Abstract

Surface functionalization is an interesting way to elaborate new smart materials. In this work, a two-step surface modification, based on pulsed plasma polymerization, was used to design functional surfaces able to react by Diels−Alder reaction (a diene−dienophile cycloaddition). The reactivity of furan-functionalized (diene) surfaces with a maleimide-derivative (dienophile) was studied. The determination of the rate constants led to the determination of the activation energy, the enthalpy of activation, and the entropy of activation. These results were then compared to those obtained in solution. For the first time, it was possible to understand the role played by molecule confinement (close to the surface) on the Diels−Alder reactivity.

Self-assembly using a retro Diels-Alder reaction

“…The Diels-Alder (DA) and retro Diels-Alder (rDA) reactions have found great utility in synthetic and materials chemistry. The dynamic and reversible nature of the DA-rDA pathway has been elegantly employed to design diverse functional systems including self-healing 45 , surface modi cation 46 , controlled release 47 , antibody-drug conjugate 48 and sol-gel transformation 49 . Owing to synthetic ease and facile reaction considerations, furan and maleimide derivatives have been extensively used as respective dienes and dienophiles in DA reactions.…”

Unique combination of spatial and temporal control of maleic anhydride plasma polymerization

“…Maleic anhydride plasma polymers have, for instance, been used to control the interactions between cells/bacteria with a surface, [ 33 ] to get hydrophilic textiles, [ 34 ] to serve as a matrix for the synthesis of nanoparticles [ 35 ] or simply to be an efficient ground layer for subsequent postmodification, especially by vapor‐phase aminolysis reactions mainly to control adhesion properties. [ 36–38 ] For these applications, preserving reactive anhydride groups is crucial but challenging. Even at relatively low input energies, anhydride groups can be easily fragmented, compromising the final use of the polymer thin film.…”

Using TOF-SIMS Spectrometry to Study the Kinetics of the Interfacial Retro Diels–Alder Reaction

“…The unique thermoreversible character of this reaction allows the formation (Diels-Alder reaction) and dissociation (retro Diels-Alder reaction) of an adduct with a simple change of temperature and without any side reactions [5]. However, despite the importance of these reactions, the study of kinetics and thermodynamics of DA reactions occurring at interfaces has only been reported in a few contributions [6,7].…”