title: Effect of Molecular Architecture of PDMAEMA-POEGMA Random and Block Copolymers on Their Adsorption on Regenerated and Anionic Nanocelluloses and Evidence of Interfacial Water Expulsion.
abstract: Block copolymers of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) with varying block sizes were synthesized by consecutive reversible addition-fragmentation chain transfer (RAFT) polymerization and then exposed to cellulose substrates with different anionic charge density. The extent and dynamics of quaternized PDMAEMA-b-POEGMA adsorption on regenerated cellulose, cellulose nanofibrils (CNF), and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNF) was determined by using electromechanical and optical techniques, namely, quartz crystal microbalance (QCM-D) and surface plasmon resonance (SPR), respectively. PDMAEMA-b-POEGMA equilibrium adsorption increased with the anionic charge of cellulose, an indication of electrostatic interactions. Such an observation was further confirmed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Depending on their architecture, adsorption on TOCNF of some of the PDMAEMA-b-POEGMA copolymers produced a significant reduction in QCM frequency, as expected from large mass uptake, while surprisingly, other copolymers induced the opposite effect. This latter, remarkable behavior was ascribed to coupled water expulsion from the interface upon charge neutralization of anionic surface sites with adsorbing cationic polymer segments. These observations were further investigated with SPR and QCM-D measurements using deuterium oxide solvent exchange to determine the amount of coupled water at the TOCNF-block copolymer interface. Finally, random copolymers with similar composition adsorbed to a larger extent compared to the respective block copolymers, revealing the effect of adsorbed loops and tails as well as hydration.
authors.affiliation: Biobased Colloids and Materials group (BiCMat), Department of Forest Products Technology, School of Chemical Technology, Aalto University , FI-00076, Espoo, Finland.
authors.forename: Maija
authors.initials: M
authors.lastname: Vuoriluoto
authors.affiliation: Biobased Colloids and Materials group (BiCMat), Department of Forest Products Technology, School of Chemical Technology, Aalto University , FI-00076, Espoo, Finland.|VTT, Technical Research Centre of Finland , Biologinkuja 7, P.O. Box 1000, FIN-02044 VTT, Finland.
authors.forename: Hannes
authors.initials: H
authors.lastname: Orelma
authors.affiliation: Biobased Colloids and Materials group (BiCMat), Department of Forest Products Technology, School of Chemical Technology, Aalto University , FI-00076, Espoo, Finland.
authors.forename: Leena-Sisko
authors.initials: LS
authors.lastname: Johansson
authors.affiliation: DWI - Leibniz-Institute for Interactive Materials Research , Forckenbeckstr. 50, D-52056 Aachen, Germany.
authors.forename: Baolei
authors.initials: B
authors.lastname: Zhu
authors.affiliation: Department of Applied Physics, School of Science, Aalto University , FI-00076, Espoo, Finland.
authors.forename: Mikko
authors.initials: M
authors.lastname: Poutanen
authors.affiliation: DWI - Leibniz-Institute for Interactive Materials Research , Forckenbeckstr. 50, D-52056 Aachen, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Walther
authors.affiliation: Biobased Colloids and Materials group (BiCMat), Department of Forest Products Technology, School of Chemical Technology, Aalto University , FI-00076, Espoo, Finland.
authors.forename: Janne
authors.initials: J
authors.lastname: Laine
authors.affiliation: Biobased Colloids and Materials group (BiCMat), Department of Forest Products Technology, School of Chemical Technology, Aalto University , FI-00076, Espoo, Finland.
authors.forename: Orlando J
authors.initials: OJ
authors.lastname: Rojas