Direct Synthesis of Peptide‐Containing Silicones: A New Way to Bioactive Materials

Abstract

As imple and efficient way to synthesize peptidecontaining silicone materials is described. Silicone oils containing ac hosen ratio of bioactive peptides equencesw ere prepared by acid-catalyzed copolymerizationo fd ichlorodimethylsilane, hybrid dichloromethyl peptidosilane, and Si-(vinyl)-or SiH-functionalized monomers. Functionalized silicone oils were first obtained and then, after hydrosilylation cross-linking, bioactive polydimethylsiloxane (PDMS)-based materials were straightforwardly obtained. The introduction of an antibacterialp eptidey ielded PDMS materials showing activity against Staphylococcus aureus. PDMS containing RGD ligands showed improved cell-adhesionp roperties. This generic method was fully compatible with the stabilityo fp eptides and thuso pened the way to the synthesis of aw ide range of biologically active silicones.

New Antiadhesive Hydrophobic Polysiloxanes

“…The degree of conversion was estimated following the relative increase in new signals corresponding to -CH 2 -in the products (3.5 ppm for P-2 and 1.7 ppm for P-3) with respect to the resonances of Si-Me groups in 1 H-NMR spectra. The structure of products was characterized using 13 C and 29 Si-NMR and FTIR spectroscopies. Characteristic vibration modes proved the formation of the secondary amide bonds (amide I band at 1650 cm −1 (ν C = O) and amide II band at 1578 cm −1 (δ NH in plane + ν C-N)) as well as the presence of S-H groups (ν S-H at 2460 cm −1 ) in P-2.…”

“…Composition of reaction mixtures during the synthesis of P-2 and P-3. Liquid state 1 H-, 13 C-and 29 Si-NMR spectra for the functionalized polysiloxanes were recorded in THF-d 8 as a solvent on a Bruker DRX-500 MHz spectrometer, with TMS as the reference (Billerica, MA, USA).…”

“…The premise for this approach was the fact that carboxylic acids, including ibuprofen [25] and acetic acid [26,27], are regarded as non-antibiotic drugs and are well-known for their antimicrobial behaviour. Polysiloxanes with amide linkers in their side chains resemble, to some extent, antibacterial silicones modified with peptides [28,29]. The functionalization of polysiloxanes with mercaptoethyl residues was inspired by the well-known ability of thiols to take part in the disruption of proteins through oxidation into S-S bonds and/or SH-induced S-S interchange reactions [30,31].…”

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

“…For example, mono functionalized dichloromethylsilane bioactive peptides, Ahx-Arg-Arg for antimicrobial purposes and RGD peptide for cell adhesion, were incorporated into a PDMS oil by copolymerization with dichlorodimethylsilane to obtain a bioactive PDMS. [207] Therefore, two different hybrid monomers, dichloromethylvinylsilane or dicholromethylsilane, at various ratio, were also copolymerized with dichlorodimethylsilane, to get modified PDMS multifunctional material by a cross-linking that followed a Karsted catalyst hydrosilylation (Figure 44). One PDMS oil contained the bioactive peptide, an antimicrobial or a cell adhesive peptide along with a vinyl-silane moiety afforded by dichlormethylvinylsilane monomer.…”