By adjusting the solution pH value below the isoelectric point (pI) of silk fibroin (SF) protein, the SF was in the cation state and it could interact strongly with unmodified anionic montmorillonite (MMT) surface. In this way, novel SF-MMT nanocomposites with good clay dispersion were successfully obtained, which were confirmed by X-ray diffraction and transmission electron microscopy. Further 1H CRAMPS and 13C CP/MAS NMR experimental results revealed that beta-sheet content of SF was remarkably enhanced for nanocomposite prepared below the pI of SF (SF-MMTA) due to the strong interaction between MMT and SF. In SF-MMTA nanocomposite, clay layers acting as an efficient nucleator could efficiently enhance the beta-sheet crystallization. On the contrary, SF preserved the native random coil conformation in SF-MMTN nanocomposites due to the weak interaction between MMT and SF. A tentative model was suggested and used to explain the mechanism of clay dispersion and conformational transition of silk protein.

In this work, the effect of poly(ethylene oxide) (PEO) molecular weight in blends of epoxy (ER) and PEO on the miscibility, inter-chain weak interactions and local dynamics were systematically investigated by multi-frequency temperature modulation DSC and solid-state NMR techniques. We found that the molecular weight (M(w)) of PEO was a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interactions between PEO and ER. A critical PEO molecular weight (M(crit)) around 4.5k was found. PEO was well miscible with ER when the molecular weight was below M(crit), where the chain motion of PEO was restricted due to strong inter-chain hydrogen bonding interactions. However, for the blends with high molecular weight PEO (M(w) > M(crit)), the miscibility between PEO and ER was poor, and most of PEO chains were considerably mobile. Finally, polarization inversion spin exchange at magic angle (PISEMA) solid-state NMR experiment further revealed the different mobility of the PEO in ER/PEO blends with different molecular weight of PEO at molecular level. Based on the DSC and NMR results, a tentative model was proposed to illustrate the miscibility in ER/PEO blends.