Grafting Density-Dependent Phase Transition Mechanism of Thermoresponsive Poly(glycidyl ether) Brushes: A Comprehensive QCM-D Study

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  • Freie Universität Berlin (FU Berlin)
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Original languageEnglish
Pages (from-to)7087-7096
Number of pages10
JournalLangmuir
Volume37
Issue number23
Early online date2 Jun 2021
Publication statusPublished - 15 Jun 2021

Abstract

Thermoresponsive coatings that exhibit "switchable"protein- and cell-adhesive properties are frequently used for the fabrication of cell sheets. Among other architectures, polymer brush coatings have shown to be especially viable due to their distinct phase transition behavior, which can be tailored via a manifold of adjustable brush characteristics, such as the (co)monomer composition, polymer chain length, and grafting density. Brush coatings based on poly(glycidyl ether)s (PGEs) have shown to efficiently mediate cell sheet fabrication when tethered to various tissue culture substrates. Herein, we report the phase transition of self-assembled PGE brushes with respect to polymer molecular weight (M: 10 and 22 kDa) and grafting density (0.07-0.5 chains nm-2) on gold model substrates studied by quasi-static QCM-D temperature ramp measurements. The brush grafting density can be tuned via the applied grafting conditions, and all brushes investigated feature broad phase transition regimes (ΔT ∼15 °C) with volume phase transition temperatures (VPTTs) close to the cloud point temperatures (CPTs) of the PGEs in solution. We further demonstrate that brush coatings with a low grafting density (0.07-0.12 chains nm-2) exhibit a continuous brush-to-mushroom transition, whereas brushes with medium grafting densities (0.3-0.5 chains nm-2) undergo a brush-to-brush transition comprising vertical phase separation during the phase transition progress. These insights help to understand the transition behavior of thin, thermoresponsive brushes prepared via grafting-to strategies and contribute to their rational design for improved functional surfaces.

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Grafting Density-Dependent Phase Transition Mechanism of Thermoresponsive Poly(glycidyl ether) Brushes: A Comprehensive QCM-D Study. / Schweigerdt, Alexander; Heinen, Silke; Stöbener, Daniel D. et al.
In: Langmuir, Vol. 37, No. 23, 15.06.2021, p. 7087-7096.

Research output: Contribution to journalArticleResearchpeer review

Schweigerdt A, Heinen S, Stöbener DD, Weinhart M. Grafting Density-Dependent Phase Transition Mechanism of Thermoresponsive Poly(glycidyl ether) Brushes: A Comprehensive QCM-D Study. Langmuir. 2021 Jun 15;37(23):7087-7096. Epub 2021 Jun 2. doi: 10.1021/acs.langmuir.1c00695
Schweigerdt, Alexander ; Heinen, Silke ; Stöbener, Daniel D. et al. / Grafting Density-Dependent Phase Transition Mechanism of Thermoresponsive Poly(glycidyl ether) Brushes : A Comprehensive QCM-D Study. In: Langmuir. 2021 ; Vol. 37, No. 23. pp. 7087-7096.
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title = "Grafting Density-Dependent Phase Transition Mechanism of Thermoresponsive Poly(glycidyl ether) Brushes: A Comprehensive QCM-D Study",
abstract = "Thermoresponsive coatings that exhibit {"}switchable{"}protein- and cell-adhesive properties are frequently used for the fabrication of cell sheets. Among other architectures, polymer brush coatings have shown to be especially viable due to their distinct phase transition behavior, which can be tailored via a manifold of adjustable brush characteristics, such as the (co)monomer composition, polymer chain length, and grafting density. Brush coatings based on poly(glycidyl ether)s (PGEs) have shown to efficiently mediate cell sheet fabrication when tethered to various tissue culture substrates. Herein, we report the phase transition of self-assembled PGE brushes with respect to polymer molecular weight (M: 10 and 22 kDa) and grafting density (0.07-0.5 chains nm-2) on gold model substrates studied by quasi-static QCM-D temperature ramp measurements. The brush grafting density can be tuned via the applied grafting conditions, and all brushes investigated feature broad phase transition regimes (ΔT ∼15 °C) with volume phase transition temperatures (VPTTs) close to the cloud point temperatures (CPTs) of the PGEs in solution. We further demonstrate that brush coatings with a low grafting density (0.07-0.12 chains nm-2) exhibit a continuous brush-to-mushroom transition, whereas brushes with medium grafting densities (0.3-0.5 chains nm-2) undergo a brush-to-brush transition comprising vertical phase separation during the phase transition progress. These insights help to understand the transition behavior of thin, thermoresponsive brushes prepared via grafting-to strategies and contribute to their rational design for improved functional surfaces. ",
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AU - Schweigerdt, Alexander

AU - Heinen, Silke

AU - Stöbener, Daniel D.

AU - Weinhart, Marie

N1 - Funding Information: A.S. is grateful to Dr. Anna Herrmann for proofreading and helpful comments during the manuscript preparation. We would like to acknowledge the assistance of the Core Facility BioSupraMol supported by the German Research Foundation (DFG). M.W. is grateful for financial support through the BMBF grant FKZ:13 N13523 and the FUB Focus Area NanoScale.

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N2 - Thermoresponsive coatings that exhibit "switchable"protein- and cell-adhesive properties are frequently used for the fabrication of cell sheets. Among other architectures, polymer brush coatings have shown to be especially viable due to their distinct phase transition behavior, which can be tailored via a manifold of adjustable brush characteristics, such as the (co)monomer composition, polymer chain length, and grafting density. Brush coatings based on poly(glycidyl ether)s (PGEs) have shown to efficiently mediate cell sheet fabrication when tethered to various tissue culture substrates. Herein, we report the phase transition of self-assembled PGE brushes with respect to polymer molecular weight (M: 10 and 22 kDa) and grafting density (0.07-0.5 chains nm-2) on gold model substrates studied by quasi-static QCM-D temperature ramp measurements. The brush grafting density can be tuned via the applied grafting conditions, and all brushes investigated feature broad phase transition regimes (ΔT ∼15 °C) with volume phase transition temperatures (VPTTs) close to the cloud point temperatures (CPTs) of the PGEs in solution. We further demonstrate that brush coatings with a low grafting density (0.07-0.12 chains nm-2) exhibit a continuous brush-to-mushroom transition, whereas brushes with medium grafting densities (0.3-0.5 chains nm-2) undergo a brush-to-brush transition comprising vertical phase separation during the phase transition progress. These insights help to understand the transition behavior of thin, thermoresponsive brushes prepared via grafting-to strategies and contribute to their rational design for improved functional surfaces.

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