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Abstract By combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli‐responsive polymers, we show that MBBs with randomly grafted poly(n‐butyl acrylate) and pH‐responsive poly(2‐(N,N‐diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH‐responsive emulsifiers. Water‐in‐toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water‐insoluble, and the MBBs desorbed from the interface, causing de‐emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications.
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Worm-globule transition of amphiphilic pH-responsive heterografted bottlebrushes at air–water interface
Heterografted molecular bottlebrushes (MBBs) with side chains composed of poly(n-butyl acrylate) (PnBA) and pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA, pKa = 7.4) have been shown to be efficient, robust, and responsive emulsifiers. However, it remains unknown how they respond to external stimuli at interfaces. In this work, the shape-changing behavior of six hetero- and homografted MBBs at air–water interfaces in response to pH changes and lateral compression was investigated using a Langmuir–Blodgett trough and atomic force microscopy. At a surface pressure of 0.5 mN m−1, PDEAEMA-containing MBBs showed no worm-globule transitions when the pH was increased from 4.0 to 10.0, at which PDEAEMA becomes insoluble in water. Upon lateral compression at pH 4.0, MBBs with a mole fraction of PDEAEMA side chains (xPDEAEMA) < 0.50 underwent pronounced worm-globule shape transitions; there was an increasing tendency for bottlebrushes to become connected with increasing xPDEAEMA. At xPDEAEMA = 0.76, the molecules remained wormlike even at high compression. These observations were presumably caused by the increased electrostatic repulsion between protonated PDEAEMA side chains in the subphase with increasing xPDEAEMA, hindering the shape change. At pH 10.0, MBBs with xPDEAEMA < 0.50 showed a lower tendency to change their wormlike morphologies upon compression than at pH 4.0. No shape transition was observed when xPDEAEMA > 0.50, attributed to the relatively high affinity toward water and the rigidity of PDEAEMA. This study revealed the shape-changing behavior of amphiphilic pH-responsive MBBs at air–water interfaces, which could be useful for future design of multicomponent MBBs for potential applications.
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- Award ID(s):
- 2004564
- PAR ID:
- 10517223
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 20
- Issue:
- 6
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 1224 to 1235
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3SM01635H
