Stereochemical Effects on the Self-Assembly of Pyrenylalanine-Phenylalanine Dipeptide

Abstract

The design and control of self-assembling biomaterials have significantly attracted attention over the last decades because of their broad ranges of applications. Here, we introduce the self-assembled fibers of the pyrene connected dipeptides, l-pyrenylalanine-l-phenylalanine (l-Pyr-l-Phe) and d-pyrenylalanine-l-phenylalanine (d-Pyr-l-Phe), and their structural analysis using experimental and computational techniques. While l-Pyr-l-Phe self-assembled into solid fibers, d-Pyr-l-Phe self-assembled into hydrogels with different morphologies. Fluorescence spectroscopy revealed monomer and red-shifted excimer emissions of the self-assembled l-Pyr-l-Phe and d-Pyr-l-Phe dipeptide nanostructures, respectively. This result was related to different 13C and 15N solid-state nuclear magnetic resonance (NMR) data on the backbone and side-chains of the self-assembled dipeptides. Molecular dynamics simulations demonstrated detailed information about the chirality effects of the dipeptides on their self-assembled structures.

Self-Assembling Hydrogel Structures for Neural Tissue Repair

“…In peptide-based hydrogels, aromatic compounds are used as gelators, helping form hydrogels that are mechanically stable and biocompatible for various applications such as drug carriers or antifouling/antibacterial gels . Aromatic compounds are used to cap the N-terminus in solid phase peptide synthesis, and can therefore easily be integrated into the material synthesis. , The incorporation of aromatic compounds and oligomers in self-assembling molecules has been explored to make conductive materials for a wide variety of applications such as electronics, optics, optoelectronics, photovoltaics, magnetic and piezoelectric devices, sensors, drug releasing hydrogels, and catalysts. ,,− …”

Biomimetic and Biological Nanoarchitectonics

“…Stereochemical effects on molecular assemblies of dipeptides of pyrenylalanine-phenylalanine dipeptide were investigated by Kawamura and co-workers [ 158 ]. While L-pyrenylalanine-L-phenylalanine is self-assembled into solid fiber structures, hydrogels are formed upon self-assembly of D-pyrenylalanine-L-phenylalanine.…”

“… Pyrene–pyrene interactions between two D-pyrenylalanine-L-phenylalanine dipeptide fibers as suggested by molecular simulation. Reprinted with permission from Reference [ 158 ]. Copyright 2020 Chemical Society of Japan.…”

Photochemical Reaction of Ketoprofen with Proteinogenic Amino Acids

“…Potassium chloride molecules of 79 were also added as the additional salt of 0.15 M concentration. The procedures were basically the same as for the previous paper . The systems were carried out for 200 ns simulation run with 2 fs time steps using periodic boundary conditions with the isothermal–isobaric ensemble at 300 K and 1 bar.…”