The Taming of the Maleimide: Fabrication of Maleimide‐Containing ‘Clickable’ Polymeric Materials

Abstract

Functional polymers are widely employed in various areas of biomedical sciences. In order to tailor them for desired applications, facile and efficient functionalization of these polymeric materials under mild and benign conditions is important. Polymers containing reactive maleimide groups can be employed for such applications since they provide an excellent handle for conjugation of thiol- and diene-containing molecules and biomolecules. Until recently, fabrication of maleimide containing polymeric materials has been challenging due to the interference from the highly reactive double bond. A Diels-Alder/retro Diels-Alder reaction sequence based strategy to transiently mask the maleimide group provides access to such polymeric materials. In this personal account, we summarize contributions from our group towards the fabrication and functionalization of maleimide-containing polymeric materials over the past decade.

Multifunctional and Transformable ‘Clickable’ Hydrogel Coatings on Titanium Surfaces: From Protein Immobilization to Cellular Attachment

“…In particular, the Huisgen 1,3-dipolar cycloaddition [ 29 ], strain-promoted (3+2) azide−alkyne cycloaddition [ 30 , 31 ], radical-mediated thiol-ene [ 32 , 33 ] and thiol-yne [ 34 , 35 ] reactions, Michael additions [ 36 ] and Diels–Alder [ 37 , 38 , 39 , 40 ] reactions have been widely used for immobilization of (bio)molecules on a wide variety of polymeric interfaces. Among all ‘clickable’ units, the maleimide functional group attracts attention due to their facile reaction with thiol- and furan-containing molecules under mild conditions [ 41 , 42 , 43 , 44 ]. We have earlier reported maleimide-containing polymers [ 45 , 46 ], surfaces [ 47 , 48 , 49 , 50 ] and bulk hydrogels [ 51 ] for biomolecular immobilization [ 52 , 53 ].…”

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

“…Polymers bearing maleimide groups are attractive scaffolds for chemical modifications as maleimide group undergoes a set of interesting reactions such as furan‐maleimide Diels–Alder reaction, anthracene‐maleimide Diels–Alder reaction, thiol‐maleimide Michael addition reaction, metal‐free azide‐maleimide 1,3‐dipolar cycloaddition click reaction, and crosslinking under photochemical and thermal conditions . Thus, there is a strong interest in the chemistry of polymers possessing maleimide functional group(s) either at the chain end(s) or as pendant groups …”

“…[27][28][29] Thus, there is a strong interest in the chemistry of polymers possessing maleimide functional group(s) either at the chain end(s) or as pendant groups. [30][31][32][33] synthetic route involving use of commercially available raw materials and the presence of cardo phthalimidine moiety which is reported to impart improved solubility characteristics to resulting polymers without sacrificing thermal properties are attractive assets of PPH-MA. Aromatic polyesters bearing pendant maleimide groups were synthesized by low temperature solution polycondensation of PPH-MA with aromatic diacid chlorides namely, isophthaloyl chloride (IPC), terephthaloyl chloride (TPC) and a mixture of IPC:TPC (50:50 mol %).…”

Maleimidophenyl isocyanates as postpolymerization modification agents and their applications in the synthesis of block copolymers

“…Although postpolymerization modifications using maleimides as the scaffold have been widely studied, little has been reported on the one‐pot postpolymerization introduction of maleimides in polymer chains. The easy introduction of maleimide moieties in common polymer chains, that is, those easily synthesized or commercially available, would provide powerful scaffolds and building blocks for the rapid construction of macromonomers and block copolymers.…”