title: Supramolecular self-assembly and radical kinetics in conducting self-replicating nanowires.
abstract: By using a combination of experimental and theoretical tools, we elucidate unique physical characteristics of supramolecular triarylamine nanowires (STANWs), their packed structure, as well as the entire kinetics of the associated radical-controlled supramolecular polymerization process. AFM, small-angle X-ray scattering, and all-atomic computer modeling reveal the two-columnar "snowflake" internal structure of the fibers involving the π-stacking of triarylamines with alternating handedness. The polymerization process and the kinetics of triarylammonium radicals formation and decay are studied by UV-vis spectroscopy, nuclear magnetic resonance and electronic paramagnetic resonance. We fully describe these experimental data with theoretical models demonstrating that the supramolecular self-assembly starts by the production of radicals that are required for nucleation of double-columnar fibrils followed by their growth in double-strand filaments. We also elucidate nontrivial kinetics of this self-assembly process revealing sigmoid time dependency and complex self-replicating behavior. The hierarchical approach and other ideas proposed here provide a general tool to study kinetics in a large number of self-assembling fibrillar systems.
authors.affiliation: Institut Charles Sadron , CNRS, 23 rue du Loess, BP 84047, 67034 Strasbourg Cedex 2, France.
authors.forename: Irina
authors.initials: I
authors.lastname: Nyrkova
authors.forename: Emilie
authors.initials: E
authors.lastname: Moulin
authors.forename: Joseph J
authors.initials: JJ
authors.lastname: Armao
authors.forename: Mounir
authors.initials: M
authors.lastname: Maaloum
authors.forename: Benoît
authors.initials: B
authors.lastname: Heinrich
authors.forename: Michel
authors.initials: M
authors.lastname: Rawiso
authors.forename: Frédéric
authors.initials: F
authors.lastname: Niess
authors.forename: Juan-Jose
authors.initials: JJ
authors.lastname: Cid
authors.forename: Nicolas
authors.initials: N
authors.lastname: Jouault
authors.forename: Eric
authors.initials: E
authors.lastname: Buhler
authors.forename: Alexander N
authors.initials: AN
authors.lastname: Semenov
authors.forename: Nicolas
authors.initials: N
authors.lastname: Giuseppone
keywords: fibrils; light-triggered self-assembly; self-replication; supramolecular polymers; triarylamines