title: Complexation-Driven Mutarotation in Poly(L-proline) Block Copolypeptides.
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.
authors.affiliation: Chemistry Department, University of Athens , Panepistimiopolis, Zografou, 15771, Athens, Greece.|Molecular Materials, Department of Applied Physics, Aalto University School of Science and Technology (previously Helsinki University of Technology), FIN-00076 Aalto, Espoo, Finland.
authors.forename: Manos
authors.initials: M
authors.lastname: Gkikas
authors.affiliation: Molecular Materials, Department of Applied Physics, Aalto University School of Science and Technology (previously Helsinki University of Technology), FIN-00076 Aalto, Espoo, Finland.|Nanomicroscopy Center, Aalto University School of Science and Technology , FIN-00076 Aalto, Espoo, Finland.
authors.forename: Johannes S
authors.initials: JS
authors.lastname: Haataja
authors.affiliation: Molecular Materials, Department of Applied Physics, Aalto University School of Science and Technology (previously Helsinki University of Technology), FIN-00076 Aalto, Espoo, Finland.|Nanomicroscopy Center, Aalto University School of Science and Technology , FIN-00076 Aalto, Espoo, Finland.
authors.forename: Janne
authors.initials: J
authors.lastname: Ruokolainen
authors.affiliation: Chemistry Department, University of Athens , Panepistimiopolis, Zografou, 15771, Athens, Greece.
authors.forename: Hermis
authors.initials: H
authors.lastname: Iatrou
authors.affiliation: Molecular Materials, Department of Applied Physics, Aalto University School of Science and Technology (previously Helsinki University of Technology), FIN-00076 Aalto, Espoo, Finland.|Nanomicroscopy Center, Aalto University School of Science and Technology , FIN-00076 Aalto, Espoo, Finland.
authors.forename: Nikolay
authors.initials: N
authors.lastname: Houbenov
mesh_terms: D001557:Benzenesulfonates / Q000737:chemistry; D001672:Biocompatible Materials / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*; D011107:Polylysine / Q000737:chemistry; D055672:Static Electricity; D013501:Surface-Active Agents
chemical_list: D001557:Benzenesulfonates; D001672:Biocompatible Materials; D010455:Peptides; D013501:Surface-Active Agents; D011107:Polylysine; C011083:polyproline; C001114:dodecylbenzenesulfonic acid