Abstract
Novel hybrid materials of the PB-b-P(o-Bn-L-Tyr) and PI-b-P(o-Bn-L-Tyr) type (where PB: 1,4/1,2-poly(butadiene), PI: 3,4/1,2/1,4-poly(isoprene) and P(o-Bn-L-Tyr): poly(ortho-benzyl-L-tyrosine)) were synthesized through anionic and ring-opening polymerization under high-vacuum techniques. All final materials were molecularly characterized through infrared spectroscopy (IR) and proton and carbon nuclear magnetic resonance (1H-NMR, 13C-NMR) in order to confirm the successful synthesis and the polydiene microstructure content. The stereochemical behavior of secondary structures (α-helices and β-sheets) of the polypeptide segments combined with the different polydiene microstructures was also studied. The influence of the α-helices and β-sheets, as well as the polydiene chain conformations on the thermal properties (glass transition temperatures, thermal stability, α- and β-relaxation) of the present biobased hybrid copolymers, was investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dielectric spectroscopy (DS). The obtained morphologies in thin films for all the synthesized materials via atomic force microscopy (AFM) indicated the formation of polypeptide fibrils in the polydiene matrix.
Highlights
The synthesis of novel biobased hybrid materials consisting of polydiene and polypeptide components using anionic and ring-opening polymerization under highvacuum techniques was reported
Through infrared spectroscopy (IR) spectroscopy, all wavenumber peaks corresponding to the characteristic chemical groups involved, as well as the existence of principally β-sheets in the polypeptide blocks, were documented
The thermal stability and the glass transition temperatures of all segments were specified through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) experiments
Summary
Polypeptides have recently attracted scientific interest due to their unique thermal, mechanical and self-assembly properties [4,5]. By combining the remarkable structural variety and functionality of polypeptides with the exquisite properties of synthetic polymers, novel biobased hybrid materials can be obtained [3]. The stiff α-helices of the polypeptide segments lead to rod–coil conformations of the final hybrid materials [6,7]. The asymmetry of the stiff rod may possibly induce chemical immiscibility between the two segments consisting of synthetic polymer chains and polypeptide segments, resulting in a higher Flory–Huggins interaction parameter (χ) [8]. The aforementioned class of materials has been investigated in the literature, and the combination of synthetic-biological segments has been referred to as “molecular chimeras” [9,10]
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