Ji Hun Park

Quantum chemical simulations were conducted to elucidate the electronic structure of the 2‐azaallenyl radical cation, a key intermediate in several [3 + 2]‐cycloadditions initiated by the oxidation of 2H‐azirine. We propose one additional Lewis structure in resonance with the commonly accepted two Lewis structures for the model system of 1,3‐diphenyl‐2‐azaallenyl radical cation, drawn from comprehensive theoretical data including molecular shape, bond order analysis, partial atomic charges, and spin densities. In addition to the ground state chemistry, the chemical structure of excited state species can be also understood with these three Lewis structures. Theoretical data imply that a newly suggested one mainly accounts for the ground state structure, and the excited state structure is better represented by the previously reported ones. Our claim is further bolstered by the prediction of the excited state geometries of the dicationic and neutral species. This research presents the extended set of Lewis structures for a better understanding electronic structure of 2‐azaallenyl radical cation.

This review introduces multifaceted mutual interactions between molecules containing a catechol moiety and aggregation‐prone proteins. The complex relationships between these two molecular species have previously been elucidated primarily in a unidirectional manner, as demonstrated in cases involving the development of catechol‐based inhibitors for amyloid aggregation and the elucidation of the role of functional amyloid fibers in melanin biosynthesis. This review aims to consolidate scattered clues pertaining to catechol‐based amyloid inhibitors, functional amyloid scaffold of melanin biosynthesis, and chemically designed peptide fibers for providing chemical insights into the role of the local three‐dimensional orientation of functional groups in manifesting such interactions. These orientations may play crucial, yet undiscovered, roles in various supramolecular structures.