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Photopolymerization of Dienoyl Lipids Creates Planar Supported Poly(lipid) Membranes with Retained Fluidity.

ABSTRACT: Polymerization of substrate-supported bilayers composed of dienoylphosphatidylcholine (PC) lipids is known to greatly enhance their chemical and mechanical stability; however, the effects of polymerization on membrane fluidity have not been investigated. Here planar supported lipid bilayers (PSLBs) composed of dienoyl PCs on glass substrates were examined to assess the degree to which UV-initiated polymerization affects lateral lipid mobility. Fluorescence recovery after photobleaching (FRAP) was used to measure the diffusion coefficients (D) and mobile fractions of rhodamine-DOPE in unpolymerized and polymerized PSLBs composed of bis-sorbyl phosphatidylcholine (bis-SorbPC), mono-sorbyl-phosphatidylcholine (mono-SorbPC), bis-dienoyl-phosphatidylcholine (bis-DenPC), and mono-dienoyl phosphatidylcholine (mono-DenPC). Polymerization was performed in both the L? and L? phase for each lipid. In all cases, polymerization reduced membrane fluidity; however, measurable lateral diffusion was retained which is attributed to a low degree of polymerization. The D values for sorbyl lipids were less than those of the denoyl lipids; this may be a consequence of the distal location of polymerizable group in the sorbyl lipids which may facilitate interleaflet bonding. The D values measured after polymerization were 0.1-0.8 of those measured before polymerization, a range that corresponds to fluidity intermediate between that of a L? phase and a L? phase. This D range is comparable to ratios of D values reported for liquid-disordered (Ld) and liquid-ordered (Lo) lipid phases and indicates that the effect of UV polymerization on lateral diffusion in a dienoyl PSLB is similar to the transition from a Ld phase to a Lo phase. The partial retention of fluidity in UV-polymerized PSLBs, their enhanced stability, and the activity of incorporated transmembrane proteins and peptides is discussed.

SUBMITTER: Orosz KS

PROVIDER: S-EPMC4755918 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

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Photopolymerization of Dienoyl Lipids Creates Planar Supported Poly(lipid) Membranes with Retained Fluidity.

Orosz Kristina S KS Jones Ian W IW Keogh John P JP Smith Christopher M CM Griffin Kaitlyn R KR Xu Juhua J Comi Troy J TJ Hall H K HK Saavedra S Scott SS

Langmuir : the ACS journal of surfaces and colloids 20160202 6

Polymerization of substrate-supported bilayers composed of dienoylphosphatidylcholine (PC) lipids is known to greatly enhance their chemical and mechanical stability; however, the effects of polymerization on membrane fluidity have not been investigated. Here planar supported lipid bilayers (PSLBs) composed of dienoyl PCs on glass substrates were examined to assess the degree to which UV-initiated polymerization affects lateral lipid mobility. Fluorescence recovery after photobleaching (FRAP) wa ...[more]

PMID: 26794208

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Project description:We demonstrate antifouling ultrafiltration membranes with retained selectivity and pure water flux through the controlled deposition of zwitterionic polymers and poly(ethylene glycol) (PEG). Molecules for polymerization were immobilized on the membrane's surface yet prevented from attaching to the membrane's pores due to a backflow of nitrogen (N2) gas achieved using an in-house constructed apparatus that we named the polymer prevention apparatus, or "PolyPrev". First, the operating parameters of the PolyPrev were optimized by investigating the polymerization of dopamine, which was selected due to its versatility in enabling further chemical reactions, published metrics for comparison, and its oxidative self-polymerization. Membrane characterization revealed that the polydopamine-modified membranes exhibited enhanced hydrophilicity; moreover, their size selectivity and pure water flux were statistically the same as those of the unmodified membranes. Because it is well documented that polydopamine coatings do not provide a long-lasting antifouling activity, poly(2-methacryloyloxyethyl phosphorylcholine) (polyMPC, Mn = 30 kDa) and succinimidyl-carboxymethyl-ester-terminated PEG ( Mn = 40 kDa) were codeposited while dopamine was polymerizing to generate antifouling membranes. Statistically, the molecular-weight cutoff of the polyMPC- and PEG-functionalized membranes synthesized in the PolyPrev was equivalent to that of the unmodified membranes, and the pure water flux of the PEG membranes was equivalent to that of the unmodified membranes. Notably, membranes prepared in the PolyPrev with polyMPC and PEG decreased bovine serum albumin fouling and Escherichia coli attachment. This study demonstrates that by restricting antifouling chemistries from attaching within the pores of membranes, we can generate high-performance, antifouling membranes appropriate for a wide range of water treatment applications without compromising intrinsic transport properties.

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Photopolymerization of Dienoyl Lipids Creates Planar Supported Poly(lipid) Membranes with Retained Fluidity.

Publications

Photopolymerization of Dienoyl Lipids Creates Planar Supported Poly(lipid) Membranes with Retained Fluidity.

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