Micro- and nanostructures fabricated from biological building blocks have attracted tremendous attention owing to their potential for application in biology and in nanotechnology. Many biomolecules, including peptides and proteins, can interact and self-assemble into highly ordered supramolecular architectures with functionality. By imitating the processes where biological peptides or proteins are assembled in nature, one can delicately design and synthesize various peptide building blocks composed of several to dozens of amino acids for the creation of biomimetic or bioinspired nanostructured materials. This tutorial review aims to introduce a new kind of peptide building block, the diphenylalanine motif, extracted with inspiration of a pathogenic process towards molecular self-assembly. We highlight recent and current advances in fabrication and application of diphenylalanine-based peptide nanomaterials. We also highlight the preparation of such peptide-based nanostructures as nanotubes, spherical vesicles, nanofibrils, nanowires and hybrids through self-assembly, the improvement of their properties and the extension of their applications.

Self-assembling systems play a significant role in physiological functions and have therefore attracted tremendous attention due to their great potential for applications in energy, biomedicine and nanotechnology. Peptides, consisting of amino acids, are among the most popular building blocks and programmable molecular motifs. Nanostructures and materials assembled using peptides exhibit important potential for green-life new technology and biomedical applications mostly because of their bio-friendliness and reversibility. The formation of these ordered nanostructures pertains to the synergistic effect of various intermolecular non-covalent interactions, including hydrogen-bonding, π-π stacking, electrostatic, hydrophobic, and van der Waals interactions. Therefore, the self-assembly process is mainly driven by thermodynamics; however, kinetics is also a critical factor in structural modulation and function integration. In this review, we focus on the influence of thermodynamic and kinetic factors on structural assembly and regulation based on different types of peptide building blocks, including aromatic dipeptides, amphiphilic peptides, polypeptides, and amyloid-relevant peptides.

Photothermal agents can harvest light energy and convert it into heat, offering a targeted and remote-controlled way to destroy carcinomatous cells and tissues. Inspired by the biological organization of polypeptides and porphyrins in living systems, here we have developed a supramolecular strategy to fabricate photothermal nanodots through peptide-modulated self-assembly of photoactive porphyrins. The self-assembling nature of porphyrins induces the formation of J-aggregates as substructures of the nanodots, and thus enables the fabrication of nanodots with totally inhibited fluorescence emission and singlet oxygen production, leading to a high light-to-heat conversion efficiency of the nanodots. The peptide moieties not only provide aqueous stability for the nanodots through hydrophilic interactions, but also provide a spatial barrier between porphyrin groups to inhibit the further growth of nanodots through the strong π-stacking interactions. Thermographic imaging reveals that the conversion of light to heat based on the nanodots is efficient in vitro and in vivo, enabling the nanodots to be applied for photothermal acoustic imaging and antitumor therapy. Antitumor therapy results show that these nanodots are highly biocompatible photothermal agents for tumor ablation, demonstrating the feasibility of using bioinspired nanostructures of self-assembling biomaterials for biomedical photoactive applications.

An injectable and self-healing collagen-gold hybrid hydrogel is spontaneously formed by electrostatic self-assembly and subsequent biomineralization. It is demonstrated that such collagen-based hydrogels may be used as an injectable material for local delivery of therapeutic agents, showing enhanced antitumor efficacy.

Manganese oxides are of considerable importance in technological applications, including ion-exchange, molecular adsorption, catalysis, and electrochemical supercapacitors owing to their structural flexibility combined with novel chemical and physical properties. [1][2][3][4][5] Up to now, various nanostructures of MnO 2 , such as nanoparticles, [6] nanorods/-belts/-wires/-tubes/-fibers, [7][8][9][10][11] nanosheets, [12] mesoporous/molecular sieves and branched structures, [13,14] urchins/orchids, and other hierarchical structures [15] have been synthesized by different methods.Over the past years, fabrication of hierarchical hollow nanostructures has attracted significant interest because of their widespread potential applications in catalysis, drug delivery, acoustic insulation, photonic crystals, [16][17][18][19][20] and other areas. Until now, the general approach for preparation of hollow structures has involved the use of various removable or sacrificial templates, referred to as "hard", such as monodispersed silica, [21,22] polymer latex spheres [23] and reducing metal nanoparticles, [24] as well as "soft" ones, for example, emulsion droplets/ micelles [25] and gas bubbles. [26] Furthermore, lots of one-pot template-free methods for generating hollow inorganic microand nanostructures have been developed employing novel mechanisms, including the nanoscale corrosion-based insideout evacuation [27] and Kirkendall effect. [28] Recently, rhombododecahedral silver cages have been prepared by self-assembly coupled with the precursor crystal-templating approach. [29] By treating the external morphologies of hollow structures, unique properties can be obtained. [30] Thus, it is desirable to develop easy methods to control the morphologies of assembled systems with well-defined hierarchical structures. Herein, we report a simple controlled preparation of hierarchical hollow microspheres and microcubes of MnO 2 nanosheets through self-assembly with an intermediate crystaltemplating process. As shown in Figure 1, the synthesis is performed by a three-step process. Particularly, discrete spherical and cubic hollow MnO 2 nanostructures with controlled morphologies can be prepared by changing the morphologies of MnCO 3 precursors, which can be simply obtained by adding the (NH 4 ) 2 SO 4 solution in the reaction system, and the thicknesses of the shells of hierarchical hollow nanostructures can be adjusted easily by the relative quantities of KMnO 4 reacted followed by selective removal of MnCO 3 crystal template with HCl. When used as adsorbent in waste-water treatment, as-prepared MnO 2 with a hierarchical hollow nanostructure exhibited a good ability to remove organic pollutant.Some related chemical reactions are shown as follows. The main chemical reaction (1) can be formulated with two half reactions. On the basis of the value of E°, the standard Gibbs free energy change DG°of reaction (1) could be estimated as -99.0 kJ mol -1 , implying strong tendency for reaction (1) to progress toward the right-hand side. As ...

Tremendous interest in self-assembly of peptides and proteins towards functional nanomaterials has been inspired by naturally evolving self-assembly in biological construction of multiple and sophisticated protein architectures in organisms. Self-assembled peptide and protein nanoarchitectures are excellent promising candidates for facilitating biomedical applications due to their advantages of structural, mechanical, and functional diversity and high biocompability and biodegradability. Here, this review focuses on the self-assembly of peptides and proteins for fabrication of phototherapeutic nanomaterials for antitumor photodynamic and photothermal therapy, with emphasis on building blocks, non-covalent interactions, strategies, and the nanoarchitectures of self-assembly. The exciting antitumor activities achieved by these phototherapeutic nanomaterials are also discussed in-depth, along with the relationships between their specific nanoarchitectures and their unique properties, providing an increased understanding of the role of peptide and protein self-assembly in improving the efficiency of photodynamic and photothermal therapy.

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Peptide-tuned self-assembly of functional components offers a strategy towards improved properties and unique functions of materials, but the requirement of many different functions and a lack of understanding of complex structures present a high barrier for applications. Herein, we report a photosensitive drug delivery system for photodynamic therapy (PDT) by a simple dipeptide- or amphiphilic amino-acid-tuned self-assembly of photosensitizers (PSs). The assembled nanodrugs exhibit multiple favorable therapeutic features, including tunable size, high loading efficiency, and on-demand drug release responding to pH, surfactant, and enzyme stimuli, as well as preferable cellular uptake and biodistribution. These features result in greatly enhanced PDT efficacy in vitro and in vivo, leading to almost complete tumor eradication in mice receiving a single drug dose and a single exposure to light.