Shape-Shifting Peptide Nanomaterials: Surface Asymmetry Enables pH-Dependent Formation and Interconversion of Collagen Tubes and Sheets.

The fabrication of dynamic, transformable biomaterials that respond to environmental cues represents a significant step forward in the development of synthetic materials that rival their highly functional, natural counterparts. Here, we describe the design and synthesis of crystalline supramolecular architectures from charge-complementary heteromeric pairs of collagen-mimetic peptides (CMPs). Under appropriate conditions, CMP pairs spontaneously assemble into either 1D ultraporous (pore diameter >100 nm) tubes or 2D bilayer nanosheets due to the structural asymmetry that arises from heteromeric self-association. Crystalline collagen tubes represent a heretofore unobserved morphology of this common biomaterial. In-depth structural characterization from a suite of biophysical methods, including TEM, AFM, high-resolution cryo-EM, and SAXS/WAXS measurements, reveals that the sheet and tube assemblies possess a similar underlying lattice structure. The experimental evidence suggests that the tubular structures are a consequence of the self-scrolling of incipient 2D layers of collagen triple helices and that the scrolling direction determines the formation of two distinct structural isoforms. Furthermore, we show that nanosheets and tubes can spontaneously interconvert through manipulation of the assembly pH and systematic adjustment of the CMP sequence. Altogether, we establish initial guidelines for the construction of dynamically responsive 1D and 2D assemblies that undergo a structurally programmed morphological transition.

Dehydration, dehydroxylation, and rehydroxylation of single-walled aluminosilicate nanotubes.

Single-walled metal oxide (aluminosilicate) nanotubes are excellent candidates for addressing the long-standing issue of functionalizing nanotube interiors, due to their high surface reactivity and controllable dimensions. However, functionalization of the nanotube interior is impeded by its high surface silanol density (9.1 -OH/nm(2)) and resulting hydrophilicity. Controlled dehydration of the nanotubes is critical for the success of functionalization efforts. We employ a range of solid-state characterization tools to elucidate dehydration and dehydroxylation phenomena in the nanotubes as a function of heat treatment up to 450 degrees C. Vibrational spectroscopy (Fourier transform infrared, FT-IR), thermogravimetric analysis-mass spectrometry (TGA-MS), nitrogen physisorption, solid-state NMR, and X-ray diffraction (XRD) reveal that a completely dehydrated condition is achieved at 250 degrees C under vacuum and that the maximum pore volume is achieved at 300 degrees C under vacuum due to partial dehydroxylation of the dehydrated nanotube. Beyond 300 degrees C, further dehydroxylation partially disorders the nanotube wall structure. However, a unique rehydroxylation mechanism can partially reverse these structural changes upon re-exposure to water vapor. Finally, detailed XRD simulations and experiments allow further insight into the nanotube packing, the dimensions, and the dependence of nanotube XRD patterns on the water content.