Synthesis and Light-Mediated Structural Disruption of an Azobenzene-Containing Helical Poly(isocyanide).

Helical poly(isocyanide)s are an important class of synthetic polymers possessing a static helical structure. Since their initial discovery, numerous examples of these helices have been fabricated. In this contribution, the synthesis of a chiral, azobenzene (azo)-containing isocyanide monomer is reported. Upon polymerization with nickel(II) catalysts, a well-defined circular dichroism (CD) trace is obtained, corresponding to the formation of a right-handed polymeric helix. The helical polymer, dissolved in chloroform and irradiated with UV light (365 nm), undergoes a cis to trans isomerization of the azobenzene side-chains. After the isomerization, a change in conformation of the helix occurs, as evidenced by CD spectroscopy. When the solution is irradiated with LED light, the polymer returns to a right-handed helical conformation. To open up the possibility for chain-end post-polymerization modification of this light-responsive system, an alkyne-functionalized nickel(II) catalyst is also used in the polymerization of the azobenzene monomer, resulting in a stimuli-responsive, terminal-alkyne-containing helical poly(isocyanide).

Synthesis of a Heterotelechelic Helical Poly(methacrylamide) and its Incorporation into a Supramolecular Triblock Copolymer.

We report the first heterotelechelic helical poly(methacrylamide) (PMAc) bearing orthogonal supramolecular binding sites on its chain-ends synthesized through a combination of reversible addition-fragmentation chain-transfer (RAFT) polymerization and thiol-bromo "click" chemistry. The heterotelechelic PMAc was assembled with two monotelechelic polymers featuring different secondary structures, namely a coil-like poly(styrene) and a helical poly(isocyanide), resulting in the formation of a coil-helix-helix supramolecular triblock copolymer through orthogonal metal coordination and hydrogen bonding interactions. Triblock assembly was confirmed through 1H NMR spectroscopy, isothermal titration calorimetry (ITC) and viscometry. The individual polymer blocks retained their secondary structures in the final triblock copolymer, as evidenced by circular dichroism (CD) spectroscopy. Our synthetic strategy expands the toolbox of triblock copolymers featuring structural motifs similar to the ones found in proteins and provides the potential for the development of other complex multifunctional polymeric ensembles.

Supramolecular Multiblock Copolymers Featuring Complex Secondary Structures.

This contribution introduces main-chain supramolecular ABC and ABB'A block copolymers sustained by orthogonal metal coordination and hydrogen bonding between telechelic polymers that feature distinct secondary structure motifs. Controlled polymerization techniques in combination with supramolecular assembly are used to engineer heterotelechelic π-sheets that undergo high-fidelity association with both helical and coil-forming synthetic polymers. Our design features multiple advances to achieve our targeted structures, in particular, those emulating sheet-like structural aspects using poly(p-phenylenevinylene)s (PPVs). To engineer heterotelechelic PPVs in a sheet-like design, we engineer an iterative one-pot cross metathesis-ring-opening metathesis polymerization (CM-ROMP) strategy that affords functionalized Grubbs-II initiators that subsequently polymerize a paracyclophanediene. Supramolecular assembly of two heterotelechelic PPVs is used to realize a parallel π-sheet, wherein further orthogonal assembly with helical motifs is possible. We also construct an antiparallel π-sheet, wherein terminal PPV blocks are adjacent to a flexible coil-like poly(norbornene) (PNB). The PNB is designed, through supramolecular chain collapse, to expose benzene and perfluorobenzene motifs that promote a hairpin turn via charge-transfer-aided folding. We demonstrate that targeted helix-(π-sheet)-helix and helix-(π-sheet)-coil assemblies occur without compromising intrinsic helicity, while both parallel and antiparallel ß-sheet-like structures are realized. Our main-chain orthogonal assembly approach allows the engineering of multiblock copolymer scaffolds featuring diverse secondary structures via the directional assembly of telechelic building blocks. The targeted assemblies, a mix of sequence-defined helix-sheet-coil and helix-sheet-helix architectures, are Nature-inspired synthetic mimics that expose α/ß and α+ß protein classes via de novo design and cooperative assembly strategies.

Supramolecular Diblock Copolymers Featuring Well-defined Telechelic Building Blocks.

We report supramolecular AB diblock copolymers comprised of well-defined telechelic building blocks. Helical motifs, formed via reversible addition-fragmentation chain-transfer (RAFT) or anionic polymerization, are assembled with coil-forming and sheet-featuring blocks obtained via atom-transfer radical polymerization (ATRP) or ring-opening metathesis polymerization (ROMP). Interpolymer hydrogen bonding or metal-coordination achieves dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π-stacked sheets that, on a basic level, mimic protein structural motifs in fully synthetic systems. The intrinsic properties of each block (e.g., circular dichroism and fluorescence) remain unaffected in the wake of self-assembly. This strategy to develop complex synthetic polymer scaffolds from functional building blocks is significant in a field striving to produce architectures reminiscent of biosynthesis, yet fully synthetic in nature. This is the first plug-and-play approach to fabricate hybrid π-sheet/helix, π-sheet/coil, and helix/coil architectures via directional self-assembly.