Metallopolymer–Peptide Hybrid Materials: Synthesis and Self‐Assembly of Functional, Polyferrocenylsilane–Tetrapeptide Conjugates

Abstract

Conjugates of poly(ferrocenyldimethylsilane) (PFDMS) with Ac-(GA)(2)-OH, Ac-A(4)-OH, Ac-G(4)-OH and Ac-V(4)-OH have been prepared by reaction of the tetrapeptide units with the amino-terminated metallopolymer. The number average degree of polymerisation (DP(n)) of the PFDMS was approximately 20 and comparable materials with shorter (DP(n) ≈ 10) and/or amorphous chains have been prepared by the same procedure. Poly(ferrocenylethylmethylsilane) (PFEMS) was employed for the latter purpose. All conjugates were characterised by GPC, MALDI-TOF MS, NMR and IR spectroscopy. With the exception of Ac-V(4)-PFDMS(20), all materials exhibited some anti-parallel β-sheet structure in the solid state. The self-assembly of the conjugates was studied in toluene by DLS. The vast majority of the materials, irrespective of peptide sequence or chain crystallinity, afforded fibres consisting of a peptidic core surrounded by a PFS corona. These fibres were found in the form of cross-linked networks by TEM and AFM. The accessibility of the chemically reducing PFS corona has been demonstrated by the localised formation of silver nanoparticles on the surface of the fibres.

Polyferrocenylsilanes: synthesis, properties, and applications

“…This was achieved using two additional steps that were performed in situ and involved the use of dimethylsilacyclobutane (DMSB) and diphenylethylene (DPE). 235,236 Use of hydroxyl-functionalised PFDMS as an initiator for the ROP of D/L-lactide has allowed the preparation of PFDMS-b-PLA (PLA: poly-D/L-lactide). MALDI-TOF analysis of model systems suggested the level of DMSB incorporation was 1-3 repeat units.…”

Hybrid Block Copolymers Constituted by Peptides and Synthetic Polymers: An Overview of Synthetic Approaches, Supramolecular Behavior and Potential Applications

“…One of these examples is the work presented by Manners et al [86] who proposed the study of the self-assembly in organic media of tetrapeptide conjugates with polyferrocenylsilanes (PFSs) of different length. With the exception of the conjugates with longer PFS chains, all the materials exhibited only anti-parallel β-sheet structures in the solid state.…”

Self‐Assembly of Differently Shaped Protein–Polymer Conjugates through Modification of the Bioconjugation Site

“…Rod‐coil, disk‐coil, and dendrimer‐coil block copolymers exhibit highly shifted, asymmetrical phase diagrams and form morphologies not seen in coil–coil systems. Peptide–polymer bioconjugates incorporating simple motifs such as α‐helix, β‐sheet, β‐helix, or cyclopeptide rings self‐assemble into structures dependent on the peptide shape. Globular proteins also have a folded shape, and incorporating them into polymer bioconjugates similarly imparts shape asymmetry.…”