ABSTRACT
Herein, we introduce a new methodology for designing transient organogels that offers tunability of the mechanical properties simply by matching the protective groups of the precursor to that of the solvent. We developed solvent-induced transient materials in which the solvent chemically participates in a set of reactions and actively supports the assembly event. The activation of a single precursor by an acid (accelerator) yields the formation of two distinct gelators and induces gelation. The interconversion cycle is supplied by the secondary solvent (originating from hydrolysis of the primary solvent by the accelerator), which then progressively solubilizes the gel network. We show that this gelation method offers a direct correlation between the mechanical and transient properties by modifying the chemical structure of the precursors and the presence of an accelerator in the system. Such a method paves the way for the design of self-abolishing and mechanically tunable materials for targeted purposes. The biocompatibility and versatility of amino acid-based gelators can offer a wide range of biomaterials for applications requiring a controllable and definite lifetime such as drug delivery platforms exhibiting a burst release or self-abolishing cell culture substrates.
ABSTRACT
The N-fluorenyl-9-methyloxycarbonyl (Fmoc)-protected amino acids have shown high antimicrobial application potential, among which the phenylalanine derivative (Fmoc-F) is the most well-known representative. However, the activity spectrum of Fmoc-F is restricted to Gram-positive bacteria only. The demand for efficient antimicrobial materials expanded research into graphene and its derivatives, although the reported results are somewhat controversial. Herein, we combined graphene oxide (GO) flakes with Fmoc-F amino acid to form Fmoc-F/GO hybrid hydrogel for the first time. We studied the synergistic effect of each component on gelation and assessed the material's bactericidal activity on Gram-negative Escherichia coli (E. coli). GO flakes do not affect Fmoc-F self-assembly per se but modulate the elasticity of the gel and speed up its formation. The hybrid hydrogel affects E. coli survival, initially causing abrupt bacterial death followed by the recovery of the surviving ones due to the inoculum effect (IE). The combination of graphene with amino acids is a step forward in developing antimicrobial gels due to their easy preparation, chemical modification, graphene functionalization, cost-effectiveness, and physicochemical/biological synergy of each component.
ABSTRACT
We report the effects of a laser-oxidized single layer graphene (SLG) surface on the self-assembly of amphiphilic gelator N-fluorenylmethoxycarbonyl-L-phenylalanine (Fmoc-Phe) towards an gel-SLG interface. Laser oxidation modulates the levels of hydrophobicity/hydrophilicity on the SLG surface. Atomic force, scanning electron, helium ion and scattering scanning nearfield optical microscopies (AFM, SEM, HIM, s-SNOM) were employed to assess the effects of surface properties on the secondary and tertiary organization of the formed Fmoc-Phe fibres at the SLG-gel interface. S-SNOM shows sheet-like secondary structures on both hydrophobic/hydrophilic areas of SLG and helical or disordered structures mainly on the hydrophilic oxidized surface. The gel network heterogeneity on pristine graphene was observed at the scale of single fibres by s-SNOM, demonstrating its power as a unique tool to study supramolecular assemblies and interfaces at nanoscale. Our findings underline the sensitivity of assembled structures to surface properties, while our characterization approach is a step forward in assessing surface-gel interfaces for the development of bionic devices.
ABSTRACT
The design of soft biomaterials requires a deep understanding of molecular self-assembly. Here a nanoscale infrared (IR) spectroscopy study of a two-component supramolecular gel is introduced to assess the system's heterogeneity and supramolecular assembly. In contrast to far-field IR spectroscopy, near-field IR spectroscopy revealed differences in the secondary structures of the gelator molecules and non-covalent interactions at three distinct nano-locations of the gel network. A ß-sheet arrangement is dominant in single and parallel fibres with a small proportion of an α-helix present, while the molecular assembly derives from strong hydrogen bonding. However, at the crossing point of two fibres, only the ß-sheet motif is observed, with an intense π-π stacking contribution. Near-field nanospectroscopy can become a powerful tool for the nanoscale distinction of non-covalent interactions, while it is expected to advance the existing spectroscopic assessments of supramolecular gels.
Subject(s)
Biocompatible Materials , Spectroscopy, Near-Infrared , Spectrophotometry, Infrared , Protein Structure, Secondary , Gels/chemistryABSTRACT
A transient organo-gelation system with spatiotemporal dynamic properties is described. Here, the solvent actively controls a complex set of equilibria that underpin the dynamic assembly event. The observed metastability is due to the in situ formation of a secondary solvent, acting as an antagonist against the primary solvent of the organogel.
