Abstract
Solid supported polymer membranes as scaffold for the insertion of functional biomolecules provide the basis for mimicking natural membranes. They also provide the means for unraveling biomolecule-membrane interactions and engineering platforms for biosensing. Vesicle fusion is an established procedure to obtain solid supported lipid bilayers but the more robust polymer vesicles tend to resist fusion and planar membranes rarely form. Here, we build on vesicle fusion to develop a refined and efficient way to produce solid supported membranes based on poly(dimethylsiloxane)-poly(2-methyl-2-oxazoline) (PMOXA-b-PDMS-b-PMOXA) amphiphilic triblock copolymers. We first create thiol-bearing polymer vesicles (polymersomes) and anchor them on a gold substrate. An osmotic shock then provokes polymersome rupture and drives planar film formation. Prerequisite for a uniform amphiphilic planar membrane is the proper combination of immobilized polymersomes and osmotic shock conditions. Thus, we explored the impact of the hydrophobic PDMS block length of the polymersome on the formation and the characteristics of the resulting solid supported polymer assemblies by quarz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). When the PDMS block is short enough, attached polymersomes restructure in response to osmotic shock, resulting in a uniform planar membrane. Our approach to rapidly form planar polymer membranes by vesicle fusion brings many advantages to the development of synthetic planar membranes for bio-sensing and biotechnological applications.
Highlights
Solid supported synthetic membranes play an important role in many scientific and technological processes
We investigated the formation of solid supported polymer membranes on gold coated surfaces governed by the following steps: (i) self-assembly of thiol-bearing polymersomes; (ii) polymersome immobilization on the surface via thiol–gold chemistry; and (iii) polymersome rupture induced by osmotic shock and subsequent polymer assembly rearrangement resulting in polymer membrane formation
We showed that the chain length of the block-copolymers, in particular the hydrophobic PDMS block, from which the polymersomes are formed is crucial for their later rupture which in turn is a prerequisite for establishing planar membranes on solid support
Summary
Solid supported synthetic membranes play an important role in many scientific and technological processes. Due to their enhanced mechanical stability and lifetimes,[1,2,3,4,5] these platforms, as a whole, are ideal candidates for complex applications such as for sensing specific biomolecules, studying physical membrane properties, and insertion of transmembrane proteins into synthetic mebranes.[1,2,3,4,5] In practice, these platforms consist of an ultra-thin synthetic membrane (10–20 nm), self-assembled from amphiphilic molecules such as phospholipids or block copolymers, which is attached to a solid substrate, e.g. coated or bare silica, glass, and mica. Solid supported membranes are attractive for research and engineering mainly for two reasons They can serve as matrix for mimicking natural membranes, offering a valuable tool to 6944 | Nanoscale, 2021, 13, 6944–6952. Creating a solid supported polymer membrane via induced-polymersome fusion, albeit challenging, is worth striving for
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