pH-responsive brush-modified silica hybrids synthesized by surface-initiated ARGET ATRP

Benjamin T. Cheesman; Joshua D. Willott; Grant B. Webber; Steve Edmondson; Erica J. Wanless

doi:10.1021/mz3003566

pH-responsive brush-modified silica hybrids synthesized by surface-initiated ARGET ATRP

Benjamin T. Cheesman, Joshua D. Willott, Grant B. Webber, Steve Edmondson, Erica J. Wanless^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

46 Citations (Scopus)

Abstract

Brush-modified silica hybrids have been synthesized by growing poly(2-(diethylamino)ethyl methacrylate) (poly(DEA)) brushes on 120 nm diameter silica particles by surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). This is the first report of using SI-ARGET ATRP to synthesize poly(DEA) brushes. The kinetics of poly(DEA) brush growth in 4:1 v/v ethanol/water was monitored. The hydrodynamic diameter of the resulting brush-modified particles was dependent on the solution pH due to the weak polybasic nature of the brushes. Below the pK_a of poly(DEA), the hydrodynamic diameter of the brush-modified particles increased with decreasing pH as a consequence of brush protonation, rearrangement and solvent uptake. This pH-response of the brushes was reversible and the hybrid particles exhibited significant hydrodynamic volume changes of up to 200% when the solution pH was cycled from pH 7 to pH 4. (Chemical Equation Presented).

Original language	English
Pages (from-to)	1161-1165
Number of pages	5
Journal	ACS macro letters
Volume	1
Issue number	10
DOIs	https://doi.org/10.1021/mz3003566
Publication status	Published - 16 Oct 2012
Externally published	Yes

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10.1021/mz3003566

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title = "pH-responsive brush-modified silica hybrids synthesized by surface-initiated ARGET ATRP",

abstract = "Brush-modified silica hybrids have been synthesized by growing poly(2-(diethylamino)ethyl methacrylate) (poly(DEA)) brushes on 120 nm diameter silica particles by surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). This is the first report of using SI-ARGET ATRP to synthesize poly(DEA) brushes. The kinetics of poly(DEA) brush growth in 4:1 v/v ethanol/water was monitored. The hydrodynamic diameter of the resulting brush-modified particles was dependent on the solution pH due to the weak polybasic nature of the brushes. Below the pKa of poly(DEA), the hydrodynamic diameter of the brush-modified particles increased with decreasing pH as a consequence of brush protonation, rearrangement and solvent uptake. This pH-response of the brushes was reversible and the hybrid particles exhibited significant hydrodynamic volume changes of up to 200% when the solution pH was cycled from pH 7 to pH 4. (Chemical Equation Presented).",

author = "Cheesman, {Benjamin T.} and Willott, {Joshua D.} and Webber, {Grant B.} and Steve Edmondson and Wanless, {Erica J.}",

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T1 - pH-responsive brush-modified silica hybrids synthesized by surface-initiated ARGET ATRP

AU - Cheesman, Benjamin T.

AU - Willott, Joshua D.

AU - Webber, Grant B.

AU - Edmondson, Steve

AU - Wanless, Erica J.

PY - 2012/10/16

Y1 - 2012/10/16

N2 - Brush-modified silica hybrids have been synthesized by growing poly(2-(diethylamino)ethyl methacrylate) (poly(DEA)) brushes on 120 nm diameter silica particles by surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). This is the first report of using SI-ARGET ATRP to synthesize poly(DEA) brushes. The kinetics of poly(DEA) brush growth in 4:1 v/v ethanol/water was monitored. The hydrodynamic diameter of the resulting brush-modified particles was dependent on the solution pH due to the weak polybasic nature of the brushes. Below the pKa of poly(DEA), the hydrodynamic diameter of the brush-modified particles increased with decreasing pH as a consequence of brush protonation, rearrangement and solvent uptake. This pH-response of the brushes was reversible and the hybrid particles exhibited significant hydrodynamic volume changes of up to 200% when the solution pH was cycled from pH 7 to pH 4. (Chemical Equation Presented).

AB - Brush-modified silica hybrids have been synthesized by growing poly(2-(diethylamino)ethyl methacrylate) (poly(DEA)) brushes on 120 nm diameter silica particles by surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). This is the first report of using SI-ARGET ATRP to synthesize poly(DEA) brushes. The kinetics of poly(DEA) brush growth in 4:1 v/v ethanol/water was monitored. The hydrodynamic diameter of the resulting brush-modified particles was dependent on the solution pH due to the weak polybasic nature of the brushes. Below the pKa of poly(DEA), the hydrodynamic diameter of the brush-modified particles increased with decreasing pH as a consequence of brush protonation, rearrangement and solvent uptake. This pH-response of the brushes was reversible and the hybrid particles exhibited significant hydrodynamic volume changes of up to 200% when the solution pH was cycled from pH 7 to pH 4. (Chemical Equation Presented).

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SN - 2161-1653

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pH-responsive brush-modified silica hybrids synthesized by surface-initiated ARGET ATRP

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