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

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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 -