Amplified responsiveness of multi-layered, polymer grafts: Synergy between brushes and hydrogels

S.N. Ramakrishna, Marco Cirelli, Ernst S. Kooij, M.K. Gunnewiek, Edmondo Maria Benetti

Research output: Contribution to journalArticleAcademicpeer-review

17 Citations (Scopus)
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Abstract

The responsive properties of surface-grafted polymer films in aqueous media can be amplified by covalently layering thermosensitive brushes and hydrogels. This was demonstrated by synthesizing layers of linear poly(N-isopropylacrylamide) (PNIPAM) brushes, alternating with cross-linked, poly(hydroxyethyl)methacrylate (PHEMA) hydrogels via sequential surface-initiated atom-transfer radical polymerization (SI-ATRP) steps. Below the lower critical solution temperature (LCST) of PNIPAM, brush/hydrogel multilayered films swell similarly to linear PNIPAM homopolymer brushes, as measured by liquid ellipsometry. In contrast, above the LCST, the PHEMA hydrogel interlayer acts as stiffening element within the collapsed multilayered film, as monitored by atomic force microscopy (AFM) nanoindentation and lateral force microscopy (LFM). This translates into a 10-fold increase in Young’s modulus by the collapsed, layered films compared to PNIPAM homopolymer analogues. The (macro)molecular continuity between the brush main chains and hydrogel constituents thus enables a chemically robust layering to form graded, quasi-3D grafted polymer architectures, which display a concerted and amplified temperature-triggered transition.
Original languageEnglish
Pages (from-to)7106-7116
JournalMacromolecules
Volume48
Issue number19
DOIs
Publication statusPublished - 24 Sep 2015

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Hydrogels
Graft copolymers
Brushes
Hydrogel
Homopolymerization
Atom transfer radical polymerization
Ellipsometry
Nanoindentation
Polymer films
Superconducting transition temperature
Macros
Atomic force microscopy
Microscopic examination
Polymers
Elastic moduli
poly-N-isopropylacrylamide
Temperature
Liquids

Keywords

  • IR-99583
  • METIS-314194

Cite this

Ramakrishna, S.N. ; Cirelli, Marco ; Kooij, Ernst S. ; Gunnewiek, M.K. ; Benetti, Edmondo Maria. / Amplified responsiveness of multi-layered, polymer grafts: Synergy between brushes and hydrogels. In: Macromolecules. 2015 ; Vol. 48, No. 19. pp. 7106-7116.
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abstract = "The responsive properties of surface-grafted polymer films in aqueous media can be amplified by covalently layering thermosensitive brushes and hydrogels. This was demonstrated by synthesizing layers of linear poly(N-isopropylacrylamide) (PNIPAM) brushes, alternating with cross-linked, poly(hydroxyethyl)methacrylate (PHEMA) hydrogels via sequential surface-initiated atom-transfer radical polymerization (SI-ATRP) steps. Below the lower critical solution temperature (LCST) of PNIPAM, brush/hydrogel multilayered films swell similarly to linear PNIPAM homopolymer brushes, as measured by liquid ellipsometry. In contrast, above the LCST, the PHEMA hydrogel interlayer acts as stiffening element within the collapsed multilayered film, as monitored by atomic force microscopy (AFM) nanoindentation and lateral force microscopy (LFM). This translates into a 10-fold increase in Young’s modulus by the collapsed, layered films compared to PNIPAM homopolymer analogues. The (macro)molecular continuity between the brush main chains and hydrogel constituents thus enables a chemically robust layering to form graded, quasi-3D grafted polymer architectures, which display a concerted and amplified temperature-triggered transition.",
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Amplified responsiveness of multi-layered, polymer grafts: Synergy between brushes and hydrogels. / Ramakrishna, S.N.; Cirelli, Marco; Kooij, Ernst S.; Gunnewiek, M.K.; Benetti, Edmondo Maria.

In: Macromolecules, Vol. 48, No. 19, 24.09.2015, p. 7106-7116.

Research output: Contribution to journalArticleAcademicpeer-review

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T1 - Amplified responsiveness of multi-layered, polymer grafts: Synergy between brushes and hydrogels

AU - Ramakrishna, S.N.

AU - Cirelli, Marco

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AU - Benetti, Edmondo Maria

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N2 - The responsive properties of surface-grafted polymer films in aqueous media can be amplified by covalently layering thermosensitive brushes and hydrogels. This was demonstrated by synthesizing layers of linear poly(N-isopropylacrylamide) (PNIPAM) brushes, alternating with cross-linked, poly(hydroxyethyl)methacrylate (PHEMA) hydrogels via sequential surface-initiated atom-transfer radical polymerization (SI-ATRP) steps. Below the lower critical solution temperature (LCST) of PNIPAM, brush/hydrogel multilayered films swell similarly to linear PNIPAM homopolymer brushes, as measured by liquid ellipsometry. In contrast, above the LCST, the PHEMA hydrogel interlayer acts as stiffening element within the collapsed multilayered film, as monitored by atomic force microscopy (AFM) nanoindentation and lateral force microscopy (LFM). This translates into a 10-fold increase in Young’s modulus by the collapsed, layered films compared to PNIPAM homopolymer analogues. The (macro)molecular continuity between the brush main chains and hydrogel constituents thus enables a chemically robust layering to form graded, quasi-3D grafted polymer architectures, which display a concerted and amplified temperature-triggered transition.

AB - The responsive properties of surface-grafted polymer films in aqueous media can be amplified by covalently layering thermosensitive brushes and hydrogels. This was demonstrated by synthesizing layers of linear poly(N-isopropylacrylamide) (PNIPAM) brushes, alternating with cross-linked, poly(hydroxyethyl)methacrylate (PHEMA) hydrogels via sequential surface-initiated atom-transfer radical polymerization (SI-ATRP) steps. Below the lower critical solution temperature (LCST) of PNIPAM, brush/hydrogel multilayered films swell similarly to linear PNIPAM homopolymer brushes, as measured by liquid ellipsometry. In contrast, above the LCST, the PHEMA hydrogel interlayer acts as stiffening element within the collapsed multilayered film, as monitored by atomic force microscopy (AFM) nanoindentation and lateral force microscopy (LFM). This translates into a 10-fold increase in Young’s modulus by the collapsed, layered films compared to PNIPAM homopolymer analogues. The (macro)molecular continuity between the brush main chains and hydrogel constituents thus enables a chemically robust layering to form graded, quasi-3D grafted polymer architectures, which display a concerted and amplified temperature-triggered transition.

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