Peptide-Tetrapyrrole Supramolecular Self-Assemblies: State of the Art

Abstract

The covalent and noncovalent association of self-assembling peptides and tetrapyrroles was explored as a way to generate systems that mimic Nature’s functional supramolecular structures. Different types of peptides spontaneously assemble with porphyrins, phthalocyanines, or corroles to give long-range ordered architectures, whose structure is determined by the features of both components. The regular morphology and ordered molecular arrangement of these systems enhance the photochemical properties of embedded chromophores, allowing applications as photo-catalysts, antennas for dye-sensitized solar cells, biosensors, and agents for light-triggered therapies. Chemical modifications of peptide and tetrapyrrole structures and control over the assembly process can steer the organization and influence the properties of the resulting system. Here we provide a review of the field, focusing on the assemblies obtained from different classes of self-assembling peptides with tetrapyrroles, their morphologies and their applications as innovative functional materials.

Veni, Vidi, Vici: Immobilized Peptide-Based Conjugates as Tools for Capture, Analysis, and Transformation

“…In general, recent reports indicate a growing interest in nanostructural forms of metallopeptides. The self-assembly of peptides to form higher order structures is often facilitated by the coordination to metal ions [160]. Rather than bidentate ligands, which are often difficult to synthesize, monodentate aromatic ligands could be applied, arranged by location on the peptide chain and stabilized by hydrogen bond networks [158].…”

Tuning C-Phycocyanin Photoactivity via pH-Mediated Assembly–Disassembly

“…In this sense, C-PC could be utilized in the design of novel pH-responsive fluorescent imaging probes , or 1 O 2 generators to boost photodynamic activities at acidic tumor sites while minimizing phototoxicity to nontarget healthy tissues . Previously, tetrapyrrole-containing proteins, naturally derived or synthetic, have been used to fabricate photosensitizers ,, and fluorescent probes. − In most of these studies, however, external carriers, chemotherapeutic agents, or fluorophores had to be attached in order to gain ROS formation and tumor selectivitythat is, the tetrapyrroles and phycobiliproteins merely functioned as photosensory pigments (light absorbers and emitters). While the referenced cases demonstrate the potential photodynamic applications, the intrinsic photoactivity and tunability of phycobiliproteins, offered by their modular and flexible protein architecture, are overlooked and underutilized.…”

Development of Novel Tetrapyrrole Structure Photosensitizers for Cancer Photodynamic Therapy

“…Since nucleic acids and peptide systems differ in structure, connectivity, stability, solubility, location and availability of functional groups, there are an individual synthetic approaches to the conjugation of porphyrins with each type of biomacromolecules that are being developed. Moreover, such conjugates have various applications, for example, porphyrins associated with DNA (especially cationic porphyrinoids) are used to detect specific secondary structures of nucleic acids, staining nuclei and as antimicrobial chemotherapeutic agents [ 47 ]. Porphyrins can also attach to biomolecules using bio-orthogonal chemistry methods as ON conjugation (attachment of porphyrinoids to sugar ring, attachment of porphyrinoids to nucleobase moiety, porphyrinoid phosphoramidites without nucleoside) or by post-synthesis modifications and subsequent reactions (such as amide combinations, hydrazide-carbonyl reactions, and others).…”