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

Maija Vuoriluoto, Hannes Orelma, Leena-Sisko Johansson, Baolei Zhu, Mikko Poutanen, Andreas Walther, Janne Laine, Orlando J. Rojas

    Research output: Contribution to journalArticleScientificpeer-review

    17 Citations (Scopus)

    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.
    Original languageEnglish
    Pages (from-to)15275-15286
    JournalThe Journal of Physical Chemistry B
    Volume119
    Issue number49
    DOIs
    Publication statusPublished - 2015
    MoE publication typeA1 Journal article-refereed

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    expulsion
    oxidized cellulose
    block copolymers
    cellulose
    Cellulose
    Block copolymers
    copolymers
    Adsorption
    adsorption
    Copolymers
    Water
    Surface plasmon resonance
    water
    Deuterium Oxide
    Methyl Ethers
    Methacrylates
    Quartz crystal microbalances
    surface plasmon resonance
    Coulomb interactions
    Charge density

    Cite this

    @article{0085544f3ef84d41a809033893df4447,
    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.",
    author = "Maija Vuoriluoto and Hannes Orelma and Leena-Sisko Johansson and Baolei Zhu and Mikko Poutanen and Andreas Walther and Janne Laine and Rojas, {Orlando J.}",
    note = "SDA: SHP: Bioeconomy",
    year = "2015",
    doi = "10.1021/acs.jpcb.5b07628",
    language = "English",
    volume = "119",
    pages = "15275--15286",
    journal = "The Journal of Physical Chemistry B",
    issn = "1520-6106",
    publisher = "American Chemical Society ACS",
    number = "49",

    }

    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. / Vuoriluoto, Maija; Orelma, Hannes; Johansson, Leena-Sisko; Zhu, Baolei; Poutanen, Mikko; Walther, Andreas; Laine, Janne; Rojas, Orlando J.

    In: The Journal of Physical Chemistry B, Vol. 119, No. 49, 2015, p. 15275-15286.

    Research output: Contribution to journalArticleScientificpeer-review

    TY - JOUR

    T1 - 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

    AU - Vuoriluoto, Maija

    AU - Orelma, Hannes

    AU - Johansson, Leena-Sisko

    AU - Zhu, Baolei

    AU - Poutanen, Mikko

    AU - Walther, Andreas

    AU - Laine, Janne

    AU - Rojas, Orlando J.

    N1 - SDA: SHP: Bioeconomy

    PY - 2015

    Y1 - 2015

    N2 - 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.

    AB - 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.

    U2 - 10.1021/acs.jpcb.5b07628

    DO - 10.1021/acs.jpcb.5b07628

    M3 - Article

    VL - 119

    SP - 15275

    EP - 15286

    JO - The Journal of Physical Chemistry B

    JF - The Journal of Physical Chemistry B

    SN - 1520-6106

    IS - 49

    ER -