Films of regenerated silk fibroin (RSF) are usually brittle and weak, which prevents its wide application as a structural material. To improve the mechanical properties of RSF film, uniaxial extension under swollen conditions was employed to introduce preferred orientation of molecular chains of silk fibroin. Such a prestretching treatment resulted in the strain at break, ultimate stress, Young's modulus, and energy to break along the predrawn direction of the RSF film increasing from approximate 5%, 90 MPa, 2.7 GPa, and 2.1 kJ/kg to 35%, 169 MPa, 3.5 GPa, and 38.9 kJ/kg, respectively, which is an attractive combination of strength and toughness. The mechanism of these property enhancements was investigated using techniques such as small-angle X-ray scattering, wide-angle X-ray diffraction, atomic force microscopy, and dynamic mechanical analysis.

Natural polysaccharides play an important role in the formation of nanohydroxyapatite (nHA) crystals in biological systems. In this study, we synthesized nHA crystals in the presence of four polysaccharides, i.e., pectin, carrageenan, chitosan, and amylose, referred as PeHA, CaHA, CsHA, and AmHA, respectively. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscope, and thermogravimetric analysis were used to investigate the formation of nHA crystals. The shape of prepared nHA crystals is needle/rod-like in all cases, whereas the size increases in the order of PeHA, CaHA, CsHA, and AmHA. The presence of polysaccharides induces the heterogeneous nucleation of nHA and further modulates the crystal growth. Our data suggest that the interaction intensity between nHA and polysaccharides is in the decreasing order of PeHA, CaHA, CsHA, and AmHA, resulting in the smallest nHA crystals with pectin. It is also demonstrated that a high polysaccharide concentration and short reaction time are adverse to nHA crystals, especially for the polysaccharides with carboxyl groups. This study can provide insight into the effects of polysaccharides with different chemical functional groups (−COOH, −OSO3H, −NH2, −OH) on the formation of nHA crystals.

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