Effect of side chain phenyl group on the self‐assembled morphology of dipeptide hydrazides

Abstract

We report self-assembled nanostructures of dipeptides hydrazides, in which alanine and/or phenylalanine are employed as components to investigate the effect of the side chain phenyl group on the morphology of self-assembled nanostructures. We demonstrated that the dimensions of the self-assembled nanostructures can vary from 1D (fiber and tubular) to 2D (sheet) solely by adjusting the position of the side chain phenyl group in the simple molecular scaffold of the dipeptide hydrazides. This study highlights the significance and potential of systematic investigations for finetuning the morphology of aqueous self-assembled structures of the dipeptide hydrazides with the aim of exploring functional soft nanomaterials.

Formation of Supramolecular Nanostructures through in Situ Self‐Assembly and Post‐Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

“…Figure 3C displays the circular dichroism (CD) spectra of NPmoc−F/F−NHNH 2 before and after the formation of the hydrogel (unfortunately, the NPmoc−F/F−NH 2 hydrogel was too turbid to measure its CD spectra). As shown in Figure 3C, a rather broad but significantly enhanced negative CD signal at around 300 nm, which could be attributed to the nitrophenyl moiety, [2e,14] appeared after the hydrogel formation. This CD signal suggests the chiral orientation and J ‐type aggregation of the nitrophenyl moiety in the self‐assembled structures, [15] since the absorption band shifted to longer wavelength compared with that of an aqueous mixture of NPmoc−F and F−NHNH 2 before hydrogel formation (Figure S4).…”

“…To circumvent the solubility issue, we conjugated the hydrazide group with saccharides [2a] or a hydrophilic benzaldehyde, [2d] which enabled the modulation of the water solubility and the realization of stimuli responsiveness. In addition, we investigated a simple molecular design for the construction of one‐dimensional fibrous or two‐dimensional planar supramolecular architectures by adjusting the number and position of the phenyl group in a dipeptide hydrazide scaffold [2e] …”

Self-Assembly Dipeptide Hydrogel: The Structures and Properties

“…They have found out that the disaccharide structures (epimer or glycosidic-bond geometry) have a significant effect on the formation ability of the hydrogel and the morphology of the self-assembled structures. The hydrazide group C-terminal modified p-nitro-phenylmethoxycarbonyl (NPmoc)-based dipeptide NPmoc-Phe-Ala-NHNH 2 could form a hydrogel, while the others like NPmoc-Ala-Phe-NHNH 2 , NPmoc-Phe-Phe-NHNH 2, and NPmoc-Ala-Ala-NHNH 2 failed to form hydrogel at the same conditions ( Ohtomi et al, 2020 ). Their results also indicated that adjusting the side chain phenyl group position in the dipeptide hydrazides could vary the dimensions of the self-assembled nanostructures from 1D (fiber and tubular) to 2D (sheet).…”

Supramolecular Architectures of Nucleic Acid/Peptide Hybrids

“…Since the discovery of self-assembly ability of the FF dipeptide to form nanotubes in water [ 78 ], it has been used as a promising motif to design self-assembling molecules [ 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 ]. Thus, the design of a covalently conjugated hybrid containing the FF dipeptide and an oligo DNA (ssDNA: 5′-CTCTCTCTCTTT-3′, 12 nt), that is, ssDNA 12 -FF ( Figure 10 A), was expected, followed by an investigation of the formations of their corresponding supramolecular architectures [ 91 ].…”