title: Nanoscale dynamics and aging of fibrous peptide-based gels.
abstract: Solutions of the aromatic dipeptide derivative molecule fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) in dimethyl sulfoxide produce fibrous gels when mixed with water. We study the evolution of density fluctuations of this three-component system using X-ray photon correlation spectroscopy (XPCS) and compare these results to the macroscopic rheology of the gels and optical observations of the microstructure evolution. At the investigated scattering angles, the intensity autocorrelation functions do not follow behavior expected for simple diffusion of individual Fmoc-FF molecules localized within cages of nearest neighbors. Instead, the dynamics are associated with density fluctuations on length scales of ~10-100 nm arising from disaggregation and reformation of fibers, leading to an increasingly uniform network. This process is correlated with the growth of the elastic modulus, which saturates at long times. Autocorrelation functions and relaxation times acquired from XPCS measurements are consistent with relaxation rates of structures at dynamic equilibrium. This study provides further support to the concept of exploring peptide-based gelators as valence-limited patchy particles capable of forming equilibrium gels.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Nikola A
authors.initials: NA
authors.lastname: Dudukovic
authors.affiliation: Department of Chemical and Biological Engineering, University at Buffalo, Buffalo, New York 14222, USA.
authors.forename: Charles F
authors.initials: CF
authors.lastname: Zukoski
mesh_terms: D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004151:Dipeptides; D005449:Fluorenes / Q000737:chemistry; D005782:Gels; D010649:Phenylalanine / Q000031:analogs & derivatives* / Q000737:chemistry; D056951:Photoelectron Spectroscopy; D012212:Rheology
chemical_list: C496789:9-fluorenylmethoxycarbonyl; D004151:Dipeptides; D005449:Fluorenes; D005782:Gels; C026650:phenylalanylphenylalanine; D010649:Phenylalanine; D004121:Dimethyl Sulfoxide