title: Self-construction of supramolecular polyrotaxane films by an electrotriggered morphogen-driven process.
abstract: The design of films using a one-pot process has recently attracted increasing interest in the field of polymer thin film formation. Herein we describe the preparation of one-pot supramolecular polyrotaxane (PRX) films using the morphogen-driven self-construction process. This one-pot buildup strategy where the film growth is triggered by the electrochemical formation and diffusion of a catalyst in close vicinity of the substrate has recently been introduced by our group. A one-pot mixture was used that contained (i) poly(acrylic acid) (PAA) functionalized by azide groups grafted on the polymer chain through oligo(ethylene glycol) (EG) arms, leading to PAA-EG13-N3, (ii) cyclodextrins (α and β CD), as macrocycles that can be threaded along EG arms, (iii) alkyne-functionalized stoppers (ferrocene or adamantane), to cap the PRX assembly by click chemistry, and (iv) copper sulfate. The one-pot mixture solution was brought into contact with a gold electrode. Cu(I), the morphogen, was generated electrochemically from Cu(II) at the electrode/one-pot solution interface. This electrotriggered click reaction leads to the capping of polypseudorotaxane yielding to PRXs. The PRXs can self-assemble through lateral supramolecular interactions to form aggregates and ensure the cohesion of the film. The film buildup was investigated using different types of CD and alkyne functionalized stoppers. Supramolecular PRX aggregates were characterized by X-ray diffraction measurements. The film topographies were imaged by atomic force microscopy. The influence of the concentration in CD and the presence of a competitor were studied as well. The stability of the resulting film was tested in contact with 8 M urea and during the electrochemical oxidation of ferrocene.
authors.affiliation: INSERM, UMR-S 1121, Biomatériaux et Bioingénierie, 11 rue Humann, F-67085 Strasbourg Cedex, France.
authors.forename: Gaulthier
authors.initials: G
authors.lastname: Rydzek
authors.forename: Tony
authors.initials: T
authors.lastname: Garnier
authors.forename: Pierre
authors.initials: P
authors.lastname: Schaaf
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Voegel
authors.forename: Bernard
authors.initials: B
authors.lastname: Senger
authors.forename: Benoît
authors.initials: B
authors.lastname: Frisch
authors.forename: Youssef
authors.initials: Y
authors.lastname: Haikel
authors.forename: Corinne
authors.initials: C
authors.lastname: Petit
authors.forename: Guy
authors.initials: G
authors.lastname: Schlatter
authors.forename: Loïc
authors.initials: L
authors.lastname: Jierry
authors.forename: Fouzia
authors.initials: F
authors.lastname: Boulmedais
mesh_terms: D057930:Click Chemistry; D003505:Cyclodextrins / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods*; D004566:Electrodes; D018625:Microscopy, Atomic Force; D015394:Molecular Structure; D020442:Poloxamer / Q000737:chemistry*; D043862:Rotaxanes / Q000737:chemistry*
chemical_list: D003505:Cyclodextrins; D043862:Rotaxanes; C475673:polyrotaxane; D020442:Poloxamer