Combined Small-Angle Neutron Scattering, Diffusion NMR, and Molecular Dynamics Study of a Eutectogel: Illuminating the Dynamical Behavior of Glyceline Confined in Bacterial Cellulose Gels

A deep eutectic solvent (DES) entrapped in a bacterial cellulose (BC) network gives rise to a gelatin-like, self-supported material termed a bacterial cellulose eutectogel (BCEG). Although this novel material holds potential for numerous industrial, environmental, energy, or medical applications, little is known about the structural features or dynamical behavior within a eutectogel. In this work, we employ X-ray diffraction (XRD), nuclear magnetic resonance (NMR), and small-angle neutron scattering (SANS) to probe the structural and diffusive behavior of the prevailing DES glyceline (1:2 molar ratio of choline chloride:glycerol) confined within bacterial cellulose. XRD investigations demonstrate that the bacterial cellulose maintains its crystallinity even as the glyceline content approaches 95 wt % in the BCEG, an outcome corroborated by molecular dynamics (MD) simulations, which suggest minimal changes in the structural features of the cellulose chains due to the presence of glyceline. SANS measurements reveal a significant reduction in the radius of gyration (R-g) for BC in a BCEG compared to its hydrogel analogue, indicating a collapse in the microfibrillar structure that we attribute to removal of waters from the interfibrillar space due to a higher affinity of DES for water than for cellulose. Furthermore, SANS experiments suggest that the vast majority of DES is hosted within large micropores in the BCEG (i.e., mesoscopic confinement). Interestingly, proton NMR experiments disclose faster diffusional rates for choline and glycerol entrapped in a BCEG compared to neat glyceline. MD simulations offer the possible explanation that this diffusional acceleration results from significant migration of chloride from the bulk to cellulose microfibrillar surfaces, thereby reducing hydrogen bonding with choline and glycerol partners. This study provides the first comprehensive investigation into the structure and diffusional dynamics of glyceline within a eutectogel, offering insights into mass transport that should be useful for tailoring these novel materials to potential applications.