Polymerization of monomeric lipids in an assembly proceeds in a
linear or cross-linking
manner depending on the number of polymerizable groups per monomeric
lipid. Lipids that contain a
single reactive moiety in either of the hydrophobic tails or associated
with the hydrophillic head group
yield linear polymers. Polymerization of lipids with reactive
groups in each hydrophobic tail generally
yield cross-linked polymeric networks. This report describes three
approaches to the characterization of
the gel point for polymerizations constrained by the two-dimensional
nature of lipid bilayers. The gel
point for two-dimensional lipid assemblies was determined by
correlation of the onset of significant changes
in the physical properties of the polymerized bilayers with the bilayer
composition. The properties
examined in this study were the lateral diffusion of a small molecule
probe of the bilayer, the stability
of polymerized bilayer vesicles in the presence of surfactants, and the
solubility of lipid polymers isolated
from the bilayers after removal of water. Each of the three
methods used indicated that a substantial
mole fraction (0.25−0.35) of the bis-substituted lipid was necessary
to cause cross-linking of the bilayer.
The general agreement between the methods provides confidence that
these results accurately indicate
the relative inefficiency of the cross-linking process in bilayers
composed of lipids having a reactive group
at the hydrophobic terminus of the lipid tail(s). The
possible explanations for the inefficient nature of
the lipid bilayer cross-linking are discussed with regard to the
preferred conformation of monomeric lipids
in the bilayer, the motions of the lipid tails, and competing side
reactions. These studies provide a new
insight into the behavior of polymerizations in organized assemblies,
which will aid in the design of new
materials based on bilayers or other types of assemblies, e.g. inverted
hexagonal or bicontinuous cubic
phases.
The concept of gelation of step or chain polymerizations has been fruitfully employed for more than a half century.1•2 In three-dimensional polymerizations the gel point occurs when the polymer molecules have been cross-linked to one another to form an infinite network or macroscopic molecule. The physical properties of the polymer are dramatically altered at this point. The application of this concept to two-dimensional polymerizations is addressed here. By two-dimensional polymerizations we refer to the polymerization of supramolecular arrays of hydrated amphiphiles, e.g., monolayers, LB films, vesicles (liposomes), extended bilayers, cast multilayers, and tubules. The last decade has seen the introduction of several methods to polymerize these supramolecular assemblies (see ref 3-5 for reviews). Other approaches to twodimensional polymeric networks have been described for
Static and dynamic light scattering measurements with nitrobenzene/isooctane mixtures of critical composition in combination with measurements of temperature dependence of specific heat and density are used to obtain values of parameters appearing in the Ferrell‐Bhattacharjee theory of ultrasound absorption of binary critical mixtures (σ0: characteristic temperature independent relaxation rate, ω0 = (43.8 ± 0.7) GHz; g: coupling constant, g = – (0.56 ± 0.01). Recent ultrasound absorption data of that system are reanalysed on the basis of Ferrell‐Bhattacharjee theory. The analysis of data measured at seven frequencies of ultrasound in the range 9 MHz to 45 MHz gives values of the parameters ω0 and g which are in satisfactory agreement with those obtained from light scattering and thermodynamic measurements (ω0 = (37 σ 3) GHz; lgl = 0.5).
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