Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules

Kenichi Nagase, Jun Kobayashi, Akihiko Kikuchi, Yoshikatsu Akiyama, Hideko Kanazawa, Teruo Okano

Research output: Contribution to journalArticle

109 Citations (Scopus)

Abstract

Dense poly(N-isopropylacrylamide) (PIPAAm) brushes were created on silica bead surfaces by surface-initiated atom transfer radical polymerization (ATRP). Interfacial properties of PIPAAm brushes were characterized by thermoresponisve interaction with biomolecules. The grafted amounts of PIPAAm on silica bead surfaces exceeded that from previously reported polymer-hydrogel-modified silica beads prepared by conventional radical polymerization by nearly 1 order of magnitude. Temperature-dependent chromatographic interactions with soluble analytes were modulated by changing the grafted PIPAAm chain lengths. Short PIPAAm-grafted silica beads produce insufficient dehydration and chain aggregation to separate steroids using weak hydrophobic interactions. In contrast, broad unresolved peaks were observed on silica beads column grafted with long PIPAAm chains due to steroid partitioning into thick, densely grafted PIPAAm brush layers. Thus, silica beads column grafted with PIPAAm chains of proper length can demonstrate baseline separation of steroids with relatively high resolution among the tested columns. Relatively longer retention times for steroid analytes were observed on all columns compared to those previously reported for other PIPAAm-grafted silica beads. This indicates that densely PIPAAm-grafted chains enable control of strong hydrophobic interactions with steroids by changing the column temperature. Densely grafted PIPAAm columns were also successful in separating two peptides into two peaks as the column temperature was increased to 40°C. This provides an effective separation alternative for peptides using substantial hydrophobicity without modification of hydrophobic surfaces and/or low mobile phase pH. In conclusion, densely PIPAAm-grafted surfaces exhibit strong, reversible temperature-modulated hydrophobic interactions, facilitating baseline separations of steroids and peptides in aqueous milieu without changes in the mobile phase pH and high ionic strength.

Original languageEnglish
Pages (from-to)9409-9415
Number of pages7
JournalLangmuir
Volume23
Issue number18
DOIs
Publication statusPublished - 2007 Aug 28

Fingerprint

brushes
Biomolecules
Brushes
steroids
beads
Polymers
Silica
Modulation
silicon dioxide
modulation
Silicon Dioxide
polymers
Peptides
peptides
Steroids
interactions
polymerization
Temperature
temperature
Atom transfer radical polymerization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules. / Nagase, Kenichi; Kobayashi, Jun; Kikuchi, Akihiko; Akiyama, Yoshikatsu; Kanazawa, Hideko; Okano, Teruo.

In: Langmuir, Vol. 23, No. 18, 28.08.2007, p. 9409-9415.

Research output: Contribution to journalArticle

Nagase, Kenichi ; Kobayashi, Jun ; Kikuchi, Akihiko ; Akiyama, Yoshikatsu ; Kanazawa, Hideko ; Okano, Teruo. / Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules. In: Langmuir. 2007 ; Vol. 23, No. 18. pp. 9409-9415.
@article{57d17bdf265c4dc197b1eba4519b939c,
title = "Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules",
abstract = "Dense poly(N-isopropylacrylamide) (PIPAAm) brushes were created on silica bead surfaces by surface-initiated atom transfer radical polymerization (ATRP). Interfacial properties of PIPAAm brushes were characterized by thermoresponisve interaction with biomolecules. The grafted amounts of PIPAAm on silica bead surfaces exceeded that from previously reported polymer-hydrogel-modified silica beads prepared by conventional radical polymerization by nearly 1 order of magnitude. Temperature-dependent chromatographic interactions with soluble analytes were modulated by changing the grafted PIPAAm chain lengths. Short PIPAAm-grafted silica beads produce insufficient dehydration and chain aggregation to separate steroids using weak hydrophobic interactions. In contrast, broad unresolved peaks were observed on silica beads column grafted with long PIPAAm chains due to steroid partitioning into thick, densely grafted PIPAAm brush layers. Thus, silica beads column grafted with PIPAAm chains of proper length can demonstrate baseline separation of steroids with relatively high resolution among the tested columns. Relatively longer retention times for steroid analytes were observed on all columns compared to those previously reported for other PIPAAm-grafted silica beads. This indicates that densely PIPAAm-grafted chains enable control of strong hydrophobic interactions with steroids by changing the column temperature. Densely grafted PIPAAm columns were also successful in separating two peptides into two peaks as the column temperature was increased to 40°C. This provides an effective separation alternative for peptides using substantial hydrophobicity without modification of hydrophobic surfaces and/or low mobile phase pH. In conclusion, densely PIPAAm-grafted surfaces exhibit strong, reversible temperature-modulated hydrophobic interactions, facilitating baseline separations of steroids and peptides in aqueous milieu without changes in the mobile phase pH and high ionic strength.",
author = "Kenichi Nagase and Jun Kobayashi and Akihiko Kikuchi and Yoshikatsu Akiyama and Hideko Kanazawa and Teruo Okano",
year = "2007",
month = "8",
day = "28",
doi = "10.1021/la700956b",
language = "English",
volume = "23",
pages = "9409--9415",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "18",

}

TY - JOUR

T1 - Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules

AU - Nagase, Kenichi

AU - Kobayashi, Jun

AU - Kikuchi, Akihiko

AU - Akiyama, Yoshikatsu

AU - Kanazawa, Hideko

AU - Okano, Teruo

PY - 2007/8/28

Y1 - 2007/8/28

N2 - Dense poly(N-isopropylacrylamide) (PIPAAm) brushes were created on silica bead surfaces by surface-initiated atom transfer radical polymerization (ATRP). Interfacial properties of PIPAAm brushes were characterized by thermoresponisve interaction with biomolecules. The grafted amounts of PIPAAm on silica bead surfaces exceeded that from previously reported polymer-hydrogel-modified silica beads prepared by conventional radical polymerization by nearly 1 order of magnitude. Temperature-dependent chromatographic interactions with soluble analytes were modulated by changing the grafted PIPAAm chain lengths. Short PIPAAm-grafted silica beads produce insufficient dehydration and chain aggregation to separate steroids using weak hydrophobic interactions. In contrast, broad unresolved peaks were observed on silica beads column grafted with long PIPAAm chains due to steroid partitioning into thick, densely grafted PIPAAm brush layers. Thus, silica beads column grafted with PIPAAm chains of proper length can demonstrate baseline separation of steroids with relatively high resolution among the tested columns. Relatively longer retention times for steroid analytes were observed on all columns compared to those previously reported for other PIPAAm-grafted silica beads. This indicates that densely PIPAAm-grafted chains enable control of strong hydrophobic interactions with steroids by changing the column temperature. Densely grafted PIPAAm columns were also successful in separating two peptides into two peaks as the column temperature was increased to 40°C. This provides an effective separation alternative for peptides using substantial hydrophobicity without modification of hydrophobic surfaces and/or low mobile phase pH. In conclusion, densely PIPAAm-grafted surfaces exhibit strong, reversible temperature-modulated hydrophobic interactions, facilitating baseline separations of steroids and peptides in aqueous milieu without changes in the mobile phase pH and high ionic strength.

AB - Dense poly(N-isopropylacrylamide) (PIPAAm) brushes were created on silica bead surfaces by surface-initiated atom transfer radical polymerization (ATRP). Interfacial properties of PIPAAm brushes were characterized by thermoresponisve interaction with biomolecules. The grafted amounts of PIPAAm on silica bead surfaces exceeded that from previously reported polymer-hydrogel-modified silica beads prepared by conventional radical polymerization by nearly 1 order of magnitude. Temperature-dependent chromatographic interactions with soluble analytes were modulated by changing the grafted PIPAAm chain lengths. Short PIPAAm-grafted silica beads produce insufficient dehydration and chain aggregation to separate steroids using weak hydrophobic interactions. In contrast, broad unresolved peaks were observed on silica beads column grafted with long PIPAAm chains due to steroid partitioning into thick, densely grafted PIPAAm brush layers. Thus, silica beads column grafted with PIPAAm chains of proper length can demonstrate baseline separation of steroids with relatively high resolution among the tested columns. Relatively longer retention times for steroid analytes were observed on all columns compared to those previously reported for other PIPAAm-grafted silica beads. This indicates that densely PIPAAm-grafted chains enable control of strong hydrophobic interactions with steroids by changing the column temperature. Densely grafted PIPAAm columns were also successful in separating two peptides into two peaks as the column temperature was increased to 40°C. This provides an effective separation alternative for peptides using substantial hydrophobicity without modification of hydrophobic surfaces and/or low mobile phase pH. In conclusion, densely PIPAAm-grafted surfaces exhibit strong, reversible temperature-modulated hydrophobic interactions, facilitating baseline separations of steroids and peptides in aqueous milieu without changes in the mobile phase pH and high ionic strength.

UR - http://www.scopus.com/inward/record.url?scp=34548522886&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34548522886&partnerID=8YFLogxK

U2 - 10.1021/la700956b

DO - 10.1021/la700956b

M3 - Article

VL - 23

SP - 9409

EP - 9415

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 18

ER -