@article{2959196, title = "Complexation-Driven Mutarotation in Poly(l-proline) Block Copolypeptides", author = "Manos Gkikas and Johannes S. Haataja and Janne Ruokolainen and Hermis Iatrou and Nikolay Houbenov", journal = "Biomacromolecules", year = "2015", volume = "16", number = "11", pages = "3686--3693", publisher = "American Chemical Society (ACS)", issn = "1525-7797, 1526-4602", doi = "10.1021/acs.biomac.5b01198", keywords = "Amino acids; Anionic surfactants; Functional materials; Hydrogen bonds; Molecules; Supramolecular chemistry, Biological functions; Block copolypeptides; Dodecylbenzenesulfonic acid; External stimulus; Helical conformers; Monophosphates; Poly(l lysine); Supramolecular complexation, Biological materials, anionic surfactant; deoxyguanosine phosphate; dodecylbenzenesulfonic acid; poly(levo lysine); poly(levo proline); polylysine; polypeptide; unclassified drug; benzenesulfonic acid derivative; biomaterial; peptide; polylysine; polyproline; surfactant, Article; beta sheet; complex formation; conformational transition; crystal structure; crystallization; cyclization; dissolution; hydrogen bond; hydrophilicity; molecular weight; periodicity; priority journal; static electricity; supramolecular chemistry; chemistry, Benzenesulfonates; Biocompatible Materials; Peptides; Polylysine; Static Electricity; Surface-Active Agents", abstract = "Novel poly(l-lysine)-block-poly(l-proline) (PLL-b-PLP)-based materials with all PLP helical conformers, i.e., PLP II and the rare PLP I are here reported. Electrostatic supramolecular complexation of the adjacent cationic PLL with anionic molecules bearing DNA analogue H-bonding functionalities, such as deoxyguanosine monophosphate (dGMP), preserves the extended PLP II helix, and the complexed molecule is locked and held in position by orthogonal shape-persistent hydrogen-bonded dGMP ribbons and their extended π-stacking. The branched anionic surfactant dodecylbenzenesulfonic acid (DBSA) on the other hand, introduces periodicity frustration and interlayer plasticization, leading to a reversed mutarotation to the more compact PLP I helix by complexation, without external stimuli, and is here reported for the first time. We foresee that our findings can be used as a platform for novel molecularly adaptive functional materials, and could possibly give insight in many proline-related transmembrane biological functions. © 2015 American Chemical Society." }