Contact
    Start Publications Rheological Properties of Lipopolymer-Phospholipid Mixtures at ...
    ←  Publication Finder
    Attension

    Rheological Properties of Lipopolymer-Phospholipid Mixtures at the Air-Water Interface: A Novel Form of Two-Dimensional Physical Gelation

    Year: 2001

    Journal: Macromolecules 2001, 34, 3024-3032, 20111221

    Authors: C. A. Naumann, C. F. Brooks, W. Wiyatno, W. Knoll, G. G. Fuller, and C. W. Frank

    Organizations: Department of Chemical Engineering, Stanford University, Stanford, California 94305-5025; Chemistry Department, IUPUI, 402 N. Blackford Street, Indianapolis, Indiana 46202-32743; and MPI f. Polymerforschung, Mainz, Germany

    Recent surface rheology and film balance experiments on monolayers of PEG lipopolymers at the air-water interface showed that the PEG chains are able to form a quasi-two-dimensional physical polymer network if forced into a highly stretched brushlike configuration. To obtain a deeper understanding of the complex film balance and rheological transition behavior of lipopolymers, we performed surface rheology and film balance experiments on phospholipid (DMPC: 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine)/PEG lipopolymer (DSPE-PEG2000: 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[poly-(ethylene glycol) 2000]) mixtures at the air-water interface. We found that the high-film-pressure transition observed between 40 and 100 mol % lipopolymer at about 20 mN/m, which is related to a first-order-like alkyl chain condensation, is a necessary requirement for the existence of a rheological transition. While the rheological transition appeared at a specific area per lipopolymer of 165 Å2, thereby being independent of the amount of phospholipids incorporated, the area per lipopolymer at the highfilm-pressure transition clearly depends on the lipopolymer-phospholipid molar concentration. Our data clearly support the Flory model of physical gelation, which predicts no thermodynamic transition at the gel point, because the isothermal compressibility and its derivative show no discontinuity at this point. The π-A isothermal behavior at the high-film-pressure transition of the phospholipid/lipopolymer mixtures can be interpreted if we assume that microphase separation occurs between phospholipids and lipopolymers. Our data indicate that the two-dimensional physical network of lipopolymers is formed by two different kinds of associative interactions: (1) microcondensation of alkyl chains of lipopolymers to small clusters; (2) water molecule mediation of the interaction between adjacent PEG clusters via hydrogen bonding.