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Electrostatically stabilized aqueous dispersions of nm-sized free lipid A particles at low volume fractions (1.0×10-4 ρTEM=8.0±0.6%) yield similar values for the particle size and particle size distribution ( ρQELS=10.9±0.75 %), whereas conductivity and acid-base titrations estimate surface chemical parameters (dissociation constant, ionizable sites, and Stern capacitance). Effective particle charges were determined by fits of the integral equation calculations of the polydisperse static structure factor, S(Q), to the light scattering data. Using the particle properties as determined from these experiments, the polydisperse structure factor, S(Q), was calculated as a function of volume fraction, θ, which was found to be consistent with a S(Q) dependence on the number particle density. It can be concluded that, at low volume fractions and low ionic strength, the light scattering data are well represented by a Poisson-Boltzmann model (PBC) of fluid-like ordering of free lipid A in aqueous solution. We find that the light scattering data of this dispersion are best described by a model where only a small fraction of the ionizable phosphate groups is dissociated at neutral pH. Finally, light scattering studies of lipid A dispersions of volume fractions of 3.9×10-4

The crystal structures of the hydrated cationic surfactant benzethonium (Bzth) chloride, bromide, hydroxide, and citrate have been determined by X-ray diffraction analysis and compared with their structures in solution well above their critical micelle concentration. The differences in the nature of the various anions of the four Bzth-X materials lead to unique anion environments and 3-D molecular arrangements. The water molecule in the monoclinic Bzth-Cl or Bzth-Br forms is hydrogen bonded to the halides and particularly to the hydrogens of the methoxy groups of the Bzth moiety notwithstanding the weak Brønsted acidity of the methoxy hydrogens. The citrate strongly interacts with the hydrogens of the methoxy group forming an embedded anionic spherical cluster of a radius of 2.6 Å. The Bzth-OH crystallizes in a hexagonal lattice with two water molecules and reveals free water molecules forming hydrogen bonded channels through the Bzth-OH crystal along the c-axis. The distances between the cationic nitrogen and the halides are 4.04 Å and 4.20 Å, significantly longer than expected for typical van der Waals distances of 3.30 Å. The structures show weakly interacting, alternating apolar and polar layers, which run parallel to the crystallographic a-b planes or a-c planes. The Bzth-X salts were also examined in aqueous solution containing 20% (v/v) ethanol and 1.0 % (v/v) glycerol well above their critical micelle concentration by small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The [1,1,1] planes for the Bzth Cl or Br, the [0,0,2] and [1,1,0] planes for the Bzth-citrate, the [2,-1,0] planes and the [0,0,1] planes for the Bzth-OH found in the crystalline phase were also present in the solution phase, accordingly, the preservation of these phases are a strong indication of periodicity in the solution phase.

Single crystalline clusters of lipid A-monophosphate were grown from organic dispersions containing 5-15% (v/v) water at various volume fractions, φ, and temperatures. The morphology of the single lipid A-monophosphate crystals was either rhombohedral or hexagonal. The hexagonal crystals were needlelike or cylindrical in shape, with the long dimension parallel to the c axis of the unit cell. The crystalline clusters were studied using electron microscopy and x-ray powder diffraction. Employing molecular location methods following a Rietveld refinement and whole-pattern refinement revealed two monoclinic crystal structures in the space groups P2(1) and C2, both converged with R(F) = 0.179. The two monoclinic crystal structures were packing (hydrocarbon chains) and conformational (sugar) polymorphs. Neither of these two structures had been encountered previously. Only intramolecular hydrogen bonding was observed for the polymorphs, which were located between the amide and the carboxyl groups. Another crystalline structure was found in the volume-fraction range 2.00 × 10(-3) ≤ φ ≤ 2.50 × 10(-3), which displayed hexagonal symmetry. The hexagonal symmetry of the self-assembled lipid A-monophosphate crystalline phase might be reconciled with the monoclinic symmetry found at low-volume-fractions. Therefore, lowering the symmetry from cubic, i.e., Ia 3d, to rhombohedral R 3 m, and finally to the monoclinic space group C2 was acceptable if the lipid A-monophosphate anion was completely orientationally ordered.