Theoretical models predict that a variety of self-assembled structures of closely packed spherical particles may result when they are confined in a cylindrical domain. In the present work we demonstrate for the first time that the polymer-coated nanoparticles confined in the self-assembled cylindrical domains of a block copolymer pack in helical morphology, where we can isolate individual fibers filled with helically arranged nanoparticles. This finding provides unique possibilities for fundamental as well as application-oriented research in similar directions.

Self-assembled hydrogen-bonded networks of the polysaccharide pectin, a mechanically functional component of plant cell walls, have been of recent interest as biomimetic exemplars of physical gels, and the microrheological and strain-stiffening behaviors have been previously investigated. Despite this detailed rheological characterization of preformed gels, little is known about the fundamental arrangement of the polymers into cross-linking junction zones, the size of these bonded regions, and the resultant network architecture in these hydrogen-bonded materials, especially in contrast to the plethora of such information available for their well-known calcium-assembled counterparts. In this work, in concert with pertinent rheological measurements, an in-depth structural study of the hydrogen-bond-mediated gelation of pectins is provided. Gels were realized by using glucona-delta-lactone to decrease the pH of solutions of pectic polymers that had a (blockwise) low degree of methylesterification. Small-angle X-ray scattering and transmission electron microscopy were utilized to access structural information on length scales on the order of nanometers to hundreds of nanometers, while complementary mechanical properties were measured predominantly using small amplitude oscillatory shear rheology.

Metal-oxygen bonding of the Ce-doped LaCoO3 system remains largely unexplored despite extensive studies on its magnetic properties. Here, we investigate the structure and local structure of nanoscale La1-xCexCoO3, with x = 0, 0.2, and 0.4, using the Rietveld refinement and synchrotron X-ray absorption techniques, complemented by topological analysis of experimental electron density and electron energy distribution. The Rietveld refinement results show that LaCoO3 subject to Ce addition is best interpretable by a model of cubic symmetry in contrast to the pristine LaCoO3, conventionally described by either a monoclinic model or a rhombohedral model. Ce4+/Co2+ are more evidently compatible dopants than Ce3+ for insertion into the main lattice. X-ray absorption data evidence the partially filled La 5d-band of the pristine LaCoO3 in accordance with the presence of La–O bonds with the shared-type atomic interaction. With increasing x, the increased Ce spectroscopic valence and enhanced La–O ionic bonding are noticeable. Characterization of the local structures around Co species also provides evidence to support the findings of the Rietveld refinement analysis.

No abstract