ABSTRACT
Here, we show that a poly(ethylene oxide) polymer can be physically cross-linked with silicate nanoparticles (Laponite) to yield highly extensible, bio-nanocomposite fibers that, upon pulling, stretch to extreme lengths and crystallize polymer chains. We find that both, nanometer structures and mechanical properties of the fibers respond to mechanical deformation by exhibiting strain-induced crystallization and high elongation. We explore the structural characteristics using X-ray scattering and the mechanical properties of the dried fibers made from hydrogels in order to determine feasibility for eventual biomedical use and to map out directions for further materials development.
Subject(s)
Nanocomposites/chemistry , Nanofibers/chemistry , Animals , Hydrogels/chemistry , Mice , NIH 3T3 Cells , Polyethylene Glycols/chemistry , Scattering, Small Angle , Silicates/chemistry , X-Ray DiffractionABSTRACT
In an effort to explore new biocompatible substrates for biomedical technologies, we present a structural study on a crosslinked gelatinous protein extracted from marine mussels. Prior studies have shown the importance of iron in protein crosslinking and mussel adhesive formation. Here, the structure and properties of an extracted material were examined both before and after crosslinking with iron. The structures of these protein hydrogels were studied by SEM, SANS, and SAXS. Viscoelasticity was tested by rheological means. The starting gel was found to have a heterogeneous porous structure on a micrometer scale and, surprisingly, a regular structure on the micron to nanometer scale. However disorder, or "no periodic structure", was deduced from scattering on nanometer length scales at very high q. Crosslinking with iron condensed the structure on a micrometer level. On nanometer length scales at high q, small angle neutron scattering showed no significant differences between the samples, possibly due to strong heterogeneity. X-ray scattering also confirmed the absence of any defined periodic structure. Partial crosslinking transformed the viscoelastic starting gel into one with more rigid and elastic properties.
Subject(s)
Biopolymers/chemistry , Cross-Linking Reagents/pharmacology , Hydrogel, Polyethylene Glycol Dimethacrylate/chemical synthesis , Proteins/chemistry , Animals , Hydrogel, Polyethylene Glycol Dimethacrylate/chemistry , Iron/chemistry , Microscopy, Electron, Scanning/methods , Models, Biological , Mytilus edulis/chemistry , Neutron Diffraction/methods , Rheology/methods , Viscosity , X-Ray Diffraction/methodsABSTRACT
We investigate the multilayered structures of poly(ethylene)oxide/montmorillonite nanocomposite films made from solution. The shear orientation of a polymer-clay network in solution combined with simultaneous solvent evaporation leads to supramolecular multilayer formation in the film. The resulting films have highly ordered structures with sheet-like multilayers on the micrometer length scale. The polymer covered clay platelets were found to orient in interconnected blob-like chains and layers on the nanometer length scale. Inside the blobs, scattering experiments indicate the polymer covered and stacked clay platelets oriented in the plane of the film. The polymer is found to be partially crystalline although this is not visible by optical microscopy. Atomic force microscopy suggests that the excess polymer, which is not directly adsorbed to the clay, is wrapped around the stacked platelets building blobs and the polymer also interconnects the polymer-clay layers. Overall our results suggest the re-intercalation of clay platelets in films made from exfoliated polymer-clay solutions as well as the supramolecular order and hierarchical structuring on the nanometer, via micrometer to the centimeter length scale.
