Fan Zheng,Jun Guo,Abdul Jamil Khan,Pandeng Miao,Feng Zhang
Fluorescent nanostructures have been widely applied to biomedical researches and clinical diagnosis such as biolabeling/imaging/sensing and have even acted as therapy reagents. Peptide-based fluorescent nanostructures attract recent interest from biomedical researchers. Inspired by the natural existence of GHK-Cu complex with a growth factor-like effect in human blood, here we have developed a novel approach for designing nanosensors through the co-assembling of two kinds of biomolecules. By making best use of both π-π stacking between carbon rings and the easy-oxidation property of an important transmitter molecule, dopamine (DA), we successfully built up a supersensitive and robust fluorescent pH nanosensor by co-assembling oxidized DA (DA ox ) with a tripeptide GHK. The GHK-DA ox nanostructures have a quantum yield of 20.82%, which might be the brightest one among all the current co-assembling structures merely through unmodified biomolecules. We envision this approach could open a new avenue for not only hybrid nanostructure construction, but also may inspire the bioengineering of in vivo luminescent probes.
Inspired by the regulation of protein structure and function by metal ions in life, the role of metal coordination in the folding and assembly of peptides has been gradually studied. However, the construction of bioactive supramolecular metallopeptides with synergism between metal coordination and peptide self-assembly remains challenging. This paper reports a bio-inspired peptide derivative (Supra GHK (glycyl- l -histidyl- l -lysine)) bearing a natural-derived GHK tri-peptide motif, which could self-assemble into supramolecular metallopeptide hydrogel (Supra GHK-Cu) after adding Cu 2+ . The addition of Cu 2+ prompts the allosteric effects on the folded structure of Supra GHK, resulting from the participation of atoms on the backbone of the peptide in the chelation. Cu 2+ has a stronger affinity for Supra GHK by bridging two peptide molecules or interacting with one peptide molecule, as confirmed by experimental results and molecular dynamics simulation. Remarkably, due to the formation of supramolecular structures, Supra GHK-Cu possesses excellent resistance against protease degradation. Moreover, it accelerates wound healing more significantly than GHK-Cu by promoting collagen deposition, angiogenesis and cell proliferation. This work not only exemplifies a successful bio-inspired supramolecular metallopeptide hydrogel but also provides a promising alternative strategy to overcome the limitations of traditional bioactive peptides in various biomedical fields.