International audienceIn the present paper, we show that the saturated form of acidic sophorolipids, a family of industrially scaled bolaform microbial glycolipids, unexpectedly forms chiral nanofibers only at pH below 7.5. In particular, we illustrate that this phenomenon derives from a subtle cooperative effect of molecular chirality, hydrogen bonding, van der Waals forces and steric hindrance. The pH-responsive behaviour was shown by Dynamic Light Scattering (DLS), pH-titration and Field Emission Scanning Electron Microscopy (FE-SEM) while the nanoscale chirality was evidenced by Circular Dichroism (CD) and cryo Transmission Electron Microscopy (cryo-TEM). The packing of sophorolipids within the ribbons was studied using Small Angle Neutron Scattering (SANS), Wide Angle X-ray Scattering (WAXS) and 2D H-1-H-1 through-space correlations via Nuclear Magnetic Resonance under very fast (67 kHz) Magic Angle Spinning (MAS-NMR)
The micellar structure of sophorolipids, a glycolipid bolaamphiphile, is analyzed using a combination of small-angle X-ray scattering (SAXS), small-angle neutron scattering (SANS), and molecular dynamics (MD) simulations. Numerical modeling of SAXS curves shows that micellar morphology in the noncharged system (pH< 5) is made of prolate ellipsoids of revolution with core-shell morphology. Opposed to most surfactant systems, the hydrophilic shell has a nonhomogeneous distribution of matter: the shell thickness in the axial direction of the ellipsoid is found to be practically zero, while it measures about 12 Å at its cross-section, thus forming a "coffee bean"-like shape. The use of a contrast-matching SANS experiment shows that the hydrophobic component of sophorolipids is actually distributed in a narrow spheroidal region in the micellar core. These data seem to indicate a complex distribution of sophorolipids within the micelle, divided into at least three domains: a pure hydrophobic core, a hydrophilic shell, and a region of less defined composition in the axial direction of the ellipsoid. To account for these results, we make the hypothesis that sophorolipid molecules acquire various configurations within the micelle including bent and linear, crossing the micellar core. These results are confirmed by MD simulations which do show the presence of multiple sophorolipid configurations when passing from spherical to ellipsoidal aggregates. Finally, we also used Rb(+) and Sr(2+) counterions in combination with anomalous SAXS experiments to probe the distribution of the COO(-) group of sophorolipids upon small pH increase (5 < pH < 7), where repulsive intermicellar interactions become important. The poor ASAXS signal shows that the COO(-) groups are rather diffused in the broad hydrophilic shell rather than at the outer micellar/water interface.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.