Hierarchical Assembly of Branched Supramolecular Polymers from (Cyclic Peptide)–Polymer Conjugates

Abstract

We report the synthesis and assembly of (N-methylated cyclic peptide)-polymer conjugates for which the cyclic peptide is attached to either the α- or both α- and ω- end groups of a polymer. A combination of chromatographic, spectroscopic, and scattering techniques reveals that the assembly of the conjugates follows a two-level hierarchy, initially driven by H-bond formation between two N-methylated cyclic peptides, followed by unspecific, noncovalent aggregation of this peptide into small domains that behave as branching points and lead to the formation of branched supramolecular polymers.

Top-down mass spectrometry of hybrid materials with hydrophobic peptide and hydrophilic or hydrophobic polymer blocks

“…6 Literature about the molecular structure characterization of hybrid materials is limited. 42 Finally the self-assembly of polyacrylate and polyacrylamide-peptide conjugates has been investigated by NMR, 44 GPC, 44,45 FTIR, [45][46][47][48] transmission electron microscopy 47,48 as well as electron 46 and X-ray 48 diffraction measurements. 24 Peptide-poly-(ethylene glycol) (PEG) conjugates have been analyzed more widely by a variety of methods, including proton NMR, 1,40,41 GPC, 41 FTIR, 41 MALDI-ToF-MS, 1,40 Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) 42,43 and electrospray ionization coupled with quadrupole/time-of-flight (Q/ToF) ion mobility mass spectrometry (IM-MS).…”

“…24 Peptide-poly-(ethylene glycol) (PEG) conjugates have been analyzed more widely by a variety of methods, including proton NMR, 1,40,41 GPC, 41 FTIR, 41 MALDI-ToF-MS, 1,40 Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) 42,43 and electrospray ionization coupled with quadrupole/time-of-flight (Q/ToF) ion mobility mass spectrometry (IM-MS). 42 Finally the self-assembly of polyacrylate and polyacrylamide-peptide conjugates has been investigated by NMR, 44 GPC, 44,45 FTIR, [45][46][47][48] transmission electron microscopy 47,48 as well as electron 46 and X-ray 48 diffraction measurements.…”

Bottom-up strategies for the synthesis of peptide-based polymers

“…As example, cyclic peptides bearing azide moiety at their side chain, usually due to the incorporation of Lys(N3) residue, and displaying self-assembly properties were conjugated with the alkyne functions of a poly(n-butyl acrylate) or poly(hydroxy ethyl acrylate) in order to self-assemble into well-structured nanotubes. [104][105][106][107] Poly(2-hydroxyethyl methacrylate) (PHEMA) was copolymerized with propargyl acrylate leading to p(HEMA-co-PgA), a copolymer wearing an alkyne function on its pendant chain. This alkyne function was reacted by CuAAC with the azide function of a fluorescent RGD peptide.…”

Polymerizations by RAFT: Developments of the Technique and Its Application in the Synthesis of Tailored (Co)polymers

“…There are several detailed and tutorial reviews on the subject that interested readers could refer to refs. [205–211]. Here we would only focus on the latest work reported on the conjugates containing self‐assembling peptides governing the self‐assembly of the peptide–polymer conjugates.…”