Interface-mediation of lipid bilayer organization and dynamics.

We report on the morphology and dynamics of planar supported lipid bilayer structures as a function of pH and ionic strength of the aqueous overlayer. Supported lipid bilayers composed of three components (phosphocholine, sphingomyelin and cholesterol) are known to exhibit phase segregation, with the characteristic domain sizes dependent on the amount and identity of each constituent, and the composition of the aqueous overlayer in contact with the bilayer. We report on fluorescence anisotropy decay imaging measurements of a rhodamine chromophore tethered to the headgroup of a phosphoethanolamine, where anisotropy decay images were acquired as a function of solution overlayer pH and ionic strength. The data reveal a two-component anisotropy decay under all conditions, with the faster time constant being largely independent of pH and ionic strength and the slower component depending on pH and ionic strength in different manners. For liposomes of the same composition, a single exponential anisotropy decay was seen. We interpret this difference in terms of bilayer curvature and support surface-bilayer interactions, and the pH and ionic strength dependencies in terms of ionic screening and protonation in the bilayer headgroup region.

State-dependent rotational diffusion of tetracene in n-alkanes. Evidence for a dominant energy relaxation pathway.

We have investigated the rotational diffusion of tetracene in the n-alkanes octane through hexadecane. Emission from the S1 state was monitored following excitation to the S1 state or the S2 state. Our data show that fast, non-radiative relaxation from S2 to S1 gives rise to local heating in the immediate vicinity of the chromophore. This local heating effect exhibits a solvent aliphatic chain length dependence for solvents C11 and longer, where solvents with an even number of carbons behave differently than those with an odd number of carbons. These data shed light on the possible origin(s) of odd-even effects in n-alkanes and suggest that a dominant intermolecular relaxation pathway for excess vibrational energy involves the S1 chromophore ring breathing mode (ca. 1383 cm(-1)) and the solvent terminal methyl group rocking mode (1375 cm(-1)).

Emulsions of crude glycerin from biodiesel processing with fuel oil for industrial heating.

There is considerable interest in using crude glycerin from biodiesel production as a heating fuel. In this work crude glycerin was emulsified into fuel oil to address difficulties with ignition and sustained combustion. Emulsions were prepared with several grades of glycerin and two grades of fuel oil using direct and phase inversion emulsification. Our findings reveal unique surfactant requirements for emulsifying glycerin into oil; these depend on the levels of several contaminants, including water, ash, and components in MONG (matter organic non-glycerin). A higher hydrophile-lipophile balance was required for a stable emulsion of crude glycerin in fuel oil compared to water in fuel oil. The high concentration of salts from biodiesel catalysts generally hindered emulsion stability. Geometric close-packing of micelles was carefully balanced to mechanically stabilize emulsions while also enabling low viscosity for pumping and fuel injection. Phase inversion emulsification produced more stable emulsions than direct emulsification. Emulsions were tested successfully as fuel for a waste oil burner.