Assembly of Phospholipids Modified with Poly(Ethylene Glycol) at AqueousLiquid Crystal Interfaces: Phase Segregation of Phospholipid Mixtures Driven by Nematic Ordering Michael I. Kinsinger, a David M. Lynn* a,b and Nicholas L. Abbott* Department of Chemical and Biological Engineering and Department of Chemistry, University of Wisconsin – Madison, 1415 Engineering Drive, Madison, Wisconsin 53706

We demonstrate that the assembly of an amphiphilic polyamine on the interfaces of micrometer-sized droplets of a thermotropic liquid crystal (LC) dispersed in aqueous solutions can be used to facilitate the immobilization of LC droplets on chemically functionalized surfaces. Polymer 1 was designed to contain both hydrophobic (alkyl-functionalized) and hydrophilic (primary and tertiary amine-functionalized) side chain functionality. The assembly of this polymer at the interfaces of aqueous dispersions of LC droplets was achieved by the spontaneous adsorption of polymer from aqueous solution. Polymer adsorption triggered transitions in the orientational ordering of the LCs, as observed by polarized light and bright-field microscopy. We demonstrate that the presence of polymer 1 on the interfaces of these droplets can be exploited to immobilize LC droplets on planar solid surfaces through covalent bond formation (e.g., for surfaces coated with polymer multilayers containing reactive azlactone functionality) or through electrostatic interactions (e.g., for surfaces coated with multilayers containing hydrolyzed azlactone functionality). The characterization of immobilized LC droplets by polarized, fluorescence, and laser scanning confocal microscopy revealed the general spherical shape of the polymer-coated LC droplets to be maintained after immobilization, and that immobilization led to additional ordering transitions within the droplets that were dependent on the nature of the surfaces with which they were in contact. Polymer 1-functionalized LC droplets were not immobilized on polymer multilayers treated with poly(ethylene imine) (PEI). We demonstrate that the ability to design surfaces that promote or prevent the immobilization of polymer-functionalized LC droplets can be exploited to pattern the immobilization of LC droplets on surfaces. The results of this investigation provide the basis of an approach that could be used to tailor the properties of dispersed LC emulsions and to immobilize these droplets on functional surfaces of interest in a broad range of fundamental and applied contexts.

We report that homogeneous Langmuir monolayers formed from mixtures of dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine conjugated to poly(ethylene glycol) (Mw = 2000 g mol−1, DPPE-PEG2000), when transferred onto interfaces formed between aqueous phases and nematic liquid crystals (LCs), phase separate in a manner that leads to patterned orientations of the LCs. Quantitative fluorescence microscopy establishes that the patterned orientations of the LCs correspond to coexisting interfacial phases that differ in total lipid density as well as lipid composition. Subsequent investigation determined that the interfacial phase separation of lipid is driven by the combined influence of the nematic ordering of the LC and the interactions between the PEG chains of DPPE-PEG2000. The latter effects impact the packing of the lipid monolayer and thus its interaction with the LC. In contrast to the phase separation of PEG-lipids within Langmuir films, where the repulsive interactions between PEG chains suppress phase separation at high interfacial densities of lipid, the results of our study indicate that repulsive interactions between PEG chains promote the phase separation of lipid at the aqueous–LC interface. Our results reveal a fundamentally new mechanism leading to control of the interfacial phase behavior of PEG-lipids, and suggest new principles for manipulation of the organization of multi-component lipid assemblies at interfaces.

We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that: (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4'-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4'-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones.

We report the design of an amphiphilic polyamine (polymer 1) based on poly(2-alkenyl azlactone) that strongly couples the formation of polyelectrolyte complexes at aqueous/liquid crystal (LC) interfaces to ordering transitions in the LC. We demonstrate that the addition of a strong anionic polyelectrolyte to aqueous solutions in contact with polymer 1-laden LC interfaces (prepared by Langmuir-Schaefer transfer of monolayers of polymer 1 onto micrometer-thick films of nematic LC) triggers ordering transitions in the LCs. We further demonstrate that changes in the ordering of the LCs (i) are driven by electrostatic interactions between the polyelectrolytes, (ii) involve multivalent interactions between the polyelectrolytes, and (iii) are triggered by reorganization of the hydrophobic side chains of amphiphilic polymer 1 upon formation of the interfacial complexes. The results presented in this paper lead us to conclude that ordering transitions in LCs can be used to provide insights into the structure and dynamics of interfacial complexes formed between polyelectrolytes.

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTDiffusion-Controlled Polymer−Polymer Reactions in Bulk: Novel Strategy for Model Experiments and Reactive Compatibilization Using Polymers Synthesized via Controlled Radical PolymerizationMaisha K. Gray, Michael I. Kinsinger, and John M. TorkelsonView Author Information Department of Materials Science & Engineering and Department of Chemical Engineering, Northwestern University, Evanston, Illinois 60208 Cite this: Macromolecules 2002, 35, 22, 8261–8264Publication Date (Web):September 27, 2002Publication History Received23 July 2002Published online27 September 2002Published inissue 1 October 2002https://doi.org/10.1021/ma0211838Copyright © 2002 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views251Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (60 KB) Get e-AlertsSUBJECTS:Aromatic compounds,Fluorescence,Fluorescence detection,Hydrocarbons,Polymers Get e-Alerts