Graphene Oxide Nanosheets Tailored With Aromatic Dipeptide Nanoassemblies for a Tuneable Interaction With Cell Membranes

Abstract

Engineered graphene-based derivatives are attractive and promising candidates for nanomedicine applications because of their versatility as 2D nanomaterials. However, the safe application of these materials needs to solve the still unanswered issue of graphene nanotoxicity. In this work, we investigated the self-assembly of dityrosine peptides driven by graphene oxide (GO) and/or copper ions in the comparison with the more hydrophobic diphenylalanine dipeptide. To scrutinize the peptide aggregation process, in the absence or presence of GO and/or Cu 2+ , we used atomic force microscopy, circular dichroism, UV-visible, fluorescence and electron paramagnetic resonance spectroscopies. The perturbative effect by the hybrid nanomaterials made of peptide-decorated GO nanosheets on model cell membranes of supported lipid bilayers was investigated. In particular, quartz crystal microbalance with dissipation monitoring and fluorescence recovery after photobleaching techniques were used to track the changes in the viscoelastic properties and fluidity of the cell membrane, respectively. Also, cellular experiments with two model tumour cell lines at a short time of incubation, evidenced the high potential of this approach to set up versatile nanoplatforms for nanomedicine and theranostic applications.

Recent advances of graphene–biomacromolecule nanocomposites in medical applications

“…68 Recently, Trapani et al investigated the perturbation effect of GO nanosheets modified with bistyrosine peptides and diphenyl peptides on lipid bilayer model cell membranes, and demonstrated their enormous potential for nanomedicine and diagnostic therapeutics. 69 Lu and co-workers synthesized melittin-GO nanosheet composites for enhanced antibacterial ability. 70 Yu et al designed multifunctional GO nanosheets modified by actin-targeting peptide (ABP), cell-penetrating peptide (CPP) and transferrin (TF).…”

The Hybrid Nano-Biointerface between Proteins/Peptides and Two-Dimensional Nanomaterials

“…An approach to stabilize FF nanostructures in water is to add GO that slightly affects nanotube morphology, maintaining self-assembly [74]. The comparison between FF and YY nanostructure formation onto GO highlights the effect of biointerface interaction [75]. The hydrophobic FF molecules preferentially gathered at the edges of the nanosheets, which contain a relatively low number of carbonyls, quinones, carboxylic acids, phenols, and lactones.…”

“…Differently, the biphenolic-like YY molecules were found on the basal planes of the nanosheets, where GO is rich in phenol and epoxide groups, and the adsorption of Tyr is expected to be driven by electrostatic interactions and hydrogen bonding. The addition of a divalent cation, such as Cu 2+ , is able to form metal complexes with peptides and tune the formation of FF nanostructures, driving the aggregation on the GO sheets plane [75].…”

Self-Assembling Peptides and Carbon Nanomaterials Join Forces for Innovative Biomedical Applications

“…Antibacterial membranes were developed by combining a self-assembling palmitoyl tetrapeptide with GO flakes [ 134 ]. Self-assembling diphenylalanine was also reported to exert antimicrobial activity through bacterial membrane disruption [ 182 ], and was studied in combination with GO flakes for potential applications in nanomedicine [ 132 ].…”