A New Way to Silicone‐Based Peptide Polymers

We describe a new class of silicone-containing peptide polymers obtained by a straightforward polymeri- zation in water using tailored chlorodimethylsilyl peptide blocks as monomeric units. This general strategy is applicable to any type of peptide sequences, yielding linear or branched polymer chains composed of well-defined peptide sequences. Hybrid copolymers composed of biomimetic and synthetic elements gather considerable attention as they open new and exciting perspectives both in the biomaterial and biomedical fields. Peptide-based hybrid copolymers are a class of biomimetic materials that significantly become important because of their specific properties such as biocompatibility, biodegradability, and bioactivity. (1-3) Recent studies focused on the preparation of well-defined homopolypeptides, (4) block copolypeptides (5-8, 9) or more controlled architectures such as comb-like peptide polymers prepared by polymerization of original N-carboxyanhydride bearing a peptide sequence. (10) A second trend has emerged to yield hybrids of peptide and synthetic polymer, mainly with poly(ethylene glycol) and either (meth)acrylic chains (11) or with silica matrixes. (12-14) On the other hand, silicones, also referred as polysiloxanes, have a long track record as industrial biocompatible, bioinert, and biodurable materials. (15) Silicones have been widely used since the 60s in medicine as orthopedics, catheters, drains, shunts, extra corporeal equipments, implants, and as injectable fluids for soft-tissue augmentation. (16) However, these last proper- ties are not sufficient for the more demanding tissue- engineering applications where additional bioactivity is required. This can be achieved by using organic-inorganic hybrids. For example, sugar-silicone or poly(l-lactic acid) (PLLA)-silicone hybrids have been reported for cell recog- nition and bone tissue regeneration. (17-19) The association of silicone and peptides has also been proposed for improved cell-material interactions purposes but it has been mostly