Direct Generation of Polymer Films on Copper Surfaces through Azide‐Alkyne Cycloaddition Reactions between Peptidomimetic Oligomers

Abstract

N‐substituted glycine oligomers, or peptoids, can be used in conjunction with the copper‐catalyzed [3 + 2] cycloaddition of azides and alkynes to generate branched polymer networks. By incorporating both azides and alkynes as side chain functionalities on the oligomer scaffolds, peptoids are able to form cross‐linked macromolecular products. The oligomer starting materials are readily associated onto copper metal sheets, allowing for localized cross‐link proliferation which in turn generates thin film polymer coatings. This novel procedure provides a direct method for the chemical modification of metal surfaces and the formation of mechanically robust sequence‐specific polymer networks.magnified image

Oligo(N-aryl glycines): A New Twist on Structured Peptoids

“…To be effective as protein mimics, however, a class of foldamers must exhibit the ability to support not only structural, but also chemical and functional diversity. Peptoids were among the first sequence-specific oligomers generated in combinatorial library format, as their solid-phase submonomer synthesis protocol facilitates the inclusion of chemically diverse N -alkyl and N -aryl side chains. , This synthetic ease has, in turn, led to the design of peptoids with interesting biological activities and materials properties. , …”

Applications of Orthogonal “Click” Chemistries in the Synthesis of Functional Soft Materials

“…The CuAAC reaction has also been used successfully in the formation of gels and other cross-linked networks. – In 2006, Malkoch and co-workers exploited the click properties of this chemistry in the formation of hydrogels with tunable mechanical properties by cross-linking a dialkynyl PEG with a tetraazide (Scheme ) . Network formation was reported to take place in less than 30 minutes under standard CuAAC conditions, and in under 1 minute when subjected to microwave irradiation.…”

Tricks with clicks: modification of peptidomimetic oligomers via copper-catalyzed azide-alkyne [3 + 2] cycloaddition

“…The authors suggested that these ligation conditions are mild enough to extend to larger carrier proteins that may aid in the development of higher-order carbohydrate-based anticancer therapies. These results, coupled with the reports documenting the synthesis of branched peptidic macrocycles 38 and peptidomimetic polymer matrices, 30,31 indicate that Cu 0 surfaces, supplied as nanoscale copper powder or as copper plates, may generally facilitate CuAAC-mediated ligation of higher-order constructs.…”

“…The Kirshenbaum group reported that azide and alkyne-heterofunctionalized peptoids are able to form thin films on copper surfaces when exposed to CuAAC reaction conditions. 31 Efforts were initiated with the synthesis of peptoid nonamers including azide-and alkyne-functionalized sidechains at multiple sites. o-Nitrophenol and thiourea functionalities were installed to provide a chromophore in the visible region and an anchoring site to a copper surface, respectively.…”