Confocal Raman Microscopy of Hybrid-Supported Phospholipid Bilayers within Individual C18-Functionalized Chromatographic Particles

Kitt, Jay P.; Harris, Joel M.

doi:10.1021/acs.langmuir.6b02309

Confocal Raman Microscopy of Hybrid-Supported Phospholipid Bilayers within Individual C₁₈-Functionalized Chromatographic Particles

Journal Article · Fri Aug 05 00:00:00 EDT 2016 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.6b02309· OSTI ID:2480567

Kitt, Jay P. ^[1]; Harris, Joel M. ^[2]

University of Utah, Salt Lake City, UT (United States); University of Utah
University of Utah, Salt Lake City, UT (United States)

Measuring lipid-membrane partitioning of small molecules is critical to predicting bioavailability and investigating molecule-membrane interactions. A stable model membrane for such studies has been developed through assembly of a phospholipid monolayer on n-alkane-modified surfaces. These hybrid-bilayers have recently been generated within n-alkyl-chain (C₁₈) modified porous silica and used in chromatographic retention studies of small molecules. Despite their successful application, determining the structure of hybrid-bilayers within chromatographic silica is challenging, because they reside at buried interfaces within the porous structure. In this work, we employ confocal Raman microscopy to investigate the formation and temperature-dependent structure of hybrid-phospholipid bilayers in C₁₈-modified, porous-silica chromato¬graphic particles. Porous silica provides sufficient surface area within a confocal probe volume centered in an individual particle to readily measure, with Raman microscopy, the formation of an ordered hybrid-bilayer of 1,2-dimyristoyl-sn-glycero-3-phospho¬choline (DMPC) with the surface C₁₈ chains. The DMPC surface density was quantified from the relative Raman scattering intensities of C₁₈ and phospholipid acyl chains and found to be ~40% of a DMPC vesicle membrane. By monitoring Raman spectra acquired versus temperature, the bilayer main phase transition was observed to be broadened and shifted to higher temperature compared to a DMPC vesicle, in agreement with differential scanning calorimetry (DSC) results. Raman scattering of deuterated phospholipid was resolved from protonated C₁₈-chain scattering, showing that the lipid-acyl and C₁₈ chains melt simultaneously in a single phase transition. The surface-density of lipid in the hybrid bilayer, the ordering of both C₁₈ and lipid acyl chains upon bilayer formation, and decoupling of C₁₈ methylene C–H vibrations by deuterated lipid acyl chains all suggest an interdigitated acyl-chain structure. Furthermore, the simultaneous melting of both layers is also consistent with an interdigitated structure, where immobility of surface-grafted C₁₈-chains decreases the cooperativity and increases the melting temperature compared to a vesicle bilayer.

View Accepted Manuscript (DOE)

Research Organization:: University of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480567

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 35 Vol. 32; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Confocal Raman Microscopy of Hybrid-Supported Phospholipid Bilayers within Individual C18-Functionalized Chromatographic Particles

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Confocal Raman Microscopy of Hybrid-Supported Phospholipid Bilayers within Individual C₁₈-Functionalized Chromatographic Particles