Peptide-mediated solution phase graphene exfoliation.

Small-angle neutron scattering (SANS) was used to investigate the size and shape of zwitterionic dodecyl phosphocholine (C12PC) micelles formed at various concentrations above its critical micelle concentration (CMC = 0.91 mM). The predominant spherical shape of micelles is revealed by SANS while the average micellar size was found to be broadly consistent with the hydrodynamic diameters determined by dynamic light scattering (DLS). Cryogenic tunneling electron microscopy (cryo-TEM) shows a uniform distribution of structures, proposing micelle monodispersity ( Supporting Information ). H/D substitution was utilized to selectively label the chain, head, or entire surfactant so that structural distributions within the micellar assembly could be investigated using fully protonated, head-deuterated, and tail-deuterated PC surfactants in D2O and fully deuterated surfactants in H2O. Using the analysis software we have developed, the four C12PC contrasts at a given concentration were simultaneously analyzed using various core-shell models consisting of a hydrophobic core and a shell representing hydrated polar headgroups. Results show that at 10 mM, C12PC micelles can be well represented by a spherical core-shell model with a core radius and shell thicknesses of 16.9 ± 0.5 and 10.2 ± 2.0 Å (total radius 27.1 ± 2.0 Å), respectively, with a surfactant aggregation number of 57 ± 5. As the concentration was increased, the SANS data revealed an increase in core-shell mixing, characterized by the emergence of an intermediate mixing region at the spherical core-shell interface. C12PC micelles at 100 mM were found to have a core radius and shell thicknesses of 19.6 ± 0.5 and 7.8 ± 2.0 Å, with an intermediate mixing region of 3.0 ± 0.5 Å. Further reduction in the shell thickness with concentration was also observed, coupled with an increased mixing of the core and shell regions and a reduction in miceller hydration, suggesting that concentration has a significant influence on surfactant packing and aggregation within micelles.

Cuticular waxes are essential for the well-being of all plants, from controlling the transport of water and nutrients across the plant surface to protecting them against external environmental attacks. Despite their significance, our current understanding regarding the structure and function of the wax film is limited. In this work, we have formed representative reconstituted wax film models of controlled thicknesses that facilitated an ex vivo study of plant cuticular wax film properties by neutron reflection (NR). Triticum aestivum L. (wheat) waxes were extracted from two different wheat straw samples, using two distinct extraction methods. Waxes extracted from harvested field-grown wheat straw using supercritical CO2 are compared with waxes extracted from laboratory-grown wheat straw via wax dissolution by chloroform rinsing. Wax films were produced by spin-coating the two extracts onto silicon substrates. Atomic force microscopy and cryo-scanning electron microscopy imaging revealed that the two reconstituted wax film models are ultrathin and porous with characteristic nanoscale extrusions on the outer surface, mimicking the structure of epicuticular waxes found upon adaxial wheat leaf surfaces. On the basis of solid–liquid and solid–air NR and ellipsometric measurements, these wax films could be modelled into two representative layers, with the diffuse underlying layer fitted with thicknesses ranging from approximately 65 to 70 Å, whereas the surface extrusion region reached heights exceeding 200 Å. Moisture-controlled NR measurements indicated that water penetrated extensively into the wax films measured under saturated humidity and under water, causing them to hydrate and swell significantly. These studies have thus provided a useful structural basis that underlies the function of the epicuticular waxes in controlling the water transport of crops.

By combining experimental measurements and computer simulations, we here show that for the bola-like peptide amphiphiles XI4 X, where X=K, R, and H, the hydrophilic amino acid substitutions have little effect on the β-sheet hydrogen-bonding between peptide backbones. Whereas all of the peptides self-assemble into one dimensional (1D) nanostructures with completely different morphologies, that is, nanotubes and helical nanoribbons for KI4 K, flat and multilayered nanoribbons for HI4 H, and twisted and bilayered nanoribbons for RI4 R. These different 1D morphologies can be explained by the distinct stacking degrees and modes of the three peptide β-sheets along the x-direction (width) and the z-direction (height), which microscopically originate from the hydrogen-bonding ability of the sheets to solvent molecules and the pairing of hydrophilic amino acid side chains between β-sheet monolayers through stacking interactions and hydrogen bonding. These different 1D nanostructures have distinct surface chemistry and functions, with great potential in various applications exploiting the respective properties of these hydrophilic amino acids.

No abstract