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Role of Oxide Surface Chemistry and Phospholipid Phase on Adsorption and Self-Assembly: Isotherms and Atomic Force Microscopy

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Department of Geology and Geophysics, 1215 West Dayton Street, Department of Surgical Sciences, 2015 Linden Drive, Department of Chemistry, 1101 University Avenue, University of Wisconsin, Madison, Wisconsin 53706
* Corresponding author. Tel: 608-262-4972. Fax: 608-262-0693. Email: [email protected]
†Department of Geology and Geophysics.
‡Department of Surgical Sciences.
§Department of Chemistry.
∥Current address: 645 Science Drive, Madison, Wisconsin 53711.
Cite this: J. Phys. Chem. C 2009, 113, 6, 2187–2196
Publication Date (Web):January 12, 2009
https://doi.org/10.1021/jp807680d
Copyright © 2009 American Chemical Society

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    Abstract

    We have examined the effects of metal oxide surface chemistry and lipid phase on phospholipid adsorption affinity and self-assembly. Adsorption isotherms of ditridecanoylphosphocholine (DTPC) at 40 °C and pH 7.2 on quartz (α-SiO2), rutile (α-TiO2), and corundum (α-Al2O3) particle suspensions indicated oxide-dependent adsorption affinity that decreased as rutile > corundum ≅ quartz at low concentrations and corundum > rutile ≅ quartz at higher concentrations. Significantly, atomic force microscopy of DTPC and dipalmitoylphosphocholine (DPPC) at high concentration on planar oxide surfaces at 25 °C in liquid-crystal and gel phases, respectively, also showed oxide-specific adsorption. Multiple bilayers formed on corundum (100), indicating greater coverage compared to single bilayers, bilayer patches, or supported vesicle layers on the negatively charged surfaces of mica (001), rutile (100), and amorphous silica glass (fused quartz plate). Thus, the amount and self-assembly of adsorbed phospholipid was found to be oxide-dependent regardless of the lipid phase. Significantly, both experimental methods show multiple bilayer formation as a unique feature of the positively charged alumina surface. The observed oxide affinity sequences are interpreted as controlled by van der Waals and electrostatic forces between the oxide surface and the negatively charged (−R(PO4)R′−) portion of the phosphocholine headgroup. Our results have implications for the interactions of amphiphilic molecules with mineral surfaces in diverse biogeochemical, biomedical, and industrial processes, including membrane-bound biomineralization, cell membrane stability during early evolution of life, organic matter burial in ocean sediments, the design of supported lipid bilayers and biomimetic cell membranes for medical implant devices, enhanced oil recovery, and ore extraction by froth flotation.

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