Secondary interactions involving the main chain. (A) Structural model of an idealized β-sheet, showing conventional main-chain hydrogen bonds (black dashes), C–H···O hydrogen bonds (green dashes), and C5 hydrogen bonds (blue dashes). (B) Structural model of an idealized α-helix, showing main-chain hydrogen bonds (black dashes) and n→π* interactions (blue arrows). (C,D) Orbital overlap that underlies formation of n→π* interactions (C) and C5 hydrogen bonds (D).