We report the design and synthesis of a biocompatible small-peptide-based compound for the controlled and targeted delivery of encapsulated bioactive metal ions through transformation of the internal nanostructures of its complexes. A tyrosine-based short-peptide amphiphile (sPA) was synthesized and observed to self-assemble into β-sheet-like secondary structures. The self-assembly of the designed sPA was modulated by application of different bioactive transition-metal ions, as was confirmed by spectroscopic and microscopic techniques. These bioactive metal-ion-conjugated sPA hybrid structures were further used to develop antibacterial materials. As a result of the excellent antibacterial activity of zinc ions the growth of clinically relevant bacteria such as Escherichia coli was inhibited in the presence of zinc⋅sPA conjugate. Bacterial testing demonstrated that, due to high biocompatibility with bacterial cells, the designed sPA acted as a metal ion delivery agent and might therefore show great potential in locally addressing bacterial infections.

A photoactivatable dopamine-conjugated platinum(IV) anticancer complex (Pt-DA) has been incorporated into G-quadruplex GK borate hydrogels by using borate ester linkages (Pt-GKB hydrogel). These were characterized by B NMR, attenuated total reflection Fourier transform infrared spectroscopy, circular dichroism, scanning electron microscopy and transmission electron microscopy. Microscopy investigations revealed the transformation of an extended fiber assembly into discrete flakes after incorporation of Pt-DA. Pt-DA showed photocytotoxicity against cisplatin-resistant A2780Cis human ovarian cancer cells (IC 74 μM, blue light) with a photocytotoxic index <2, whereas Pt-GKB hydrogels exhibited more potent photocytotoxicity (IC 3 μM, blue light) with a photocytotoxic index >5. Most notably, Pt-DA and Pt-GKB hydrogels show selective phototoxicity for cancer cells versus normal fibroblast cells (MRC5).

This study demonstrates the beneficial role of di-tryptophan containing short peptide amphiphiles (sPA), for the synthesis and stabilization of AgNPs in the presence of sunlight followed by garlanding of AgNPs along the fibrous network of sPA. Such hybrid structures were precisely and selectively moulded into a nanowreath-type morphology due to the thermoplasmonic effect of AgNPs, and can be used for several bio-nanotechnological applications.

We highlight the structural diversity of strategically designed two short peptide amphiphiles (sPAs) and describe their structure–function relationship studies. The shuffling of two key amino acids, that is, tyrosine and phenylalanine, in a designed sPA lead to a pair of constitutional isomers. Such small and strategic alteration can bring a substantial change in the self‐assembling pattern. Inspired from the naturally occurring metallopeptides, bioactive transition‐metal ions were used for constructing the unusual nanostructures. Use of appropriate metal ions created bigger differences between the properties of these isomers and hence the self‐assembly. Coordination of appropriate transition metal ions modifies the internal nanoscale structures of sPA, thus leading to the formation of vertically stacked terraced layers with decreasing size, which possess a high degree of dimensional regularity. We propose that such metal‐induced terraced nanodome‐like hierarchical self‐assembly may have relevance for specific biotechnology applications.

Transition metal ions mediate the secondary structural transformation of hydrophobized sPA and can be applied to the design and development of stimuli-responsive nanomaterials.