Effect of hydroxyl group position and system parameters on the features of hydroxystearic Acid monolayers.

The characteristic features of hydroxystearic acid monolayers OH-substituted in the mid position of the alkyl chain deviate considerably from those of the usual nonsubstituted stearic acid. The phase behavior, domain morphology, and two-dimensional lattice structure of 9-, 11-, and 12-hydroxystearic acids are studied, using pi-A isotherms, Brewster angle microscopy (BAM), and grazing incidence X-ray diffraction (GIXD), to obtain detailed information on the effect of the exact position of the OH-substitution. The pi-A isotherms of all three hydroxyoctadecanoic acids have an extended flat plateau region, the extension of which only slightly decreases with the increase of temperature. At the same temperature, the extension of the plateau region increases and the plateau pressure decreases from 9-hydroxyoctadecanoic acid to 12-hydroxyoctadecanoic acid. The absolute -DeltaH and -DeltaS values for the phase transition increase slightly from 9-hydroxyoctadecanoic acid to 12- hydroxyoctadecanoic acid and indicate differences in the ordering of the condensed phase under consideration of the special reorientation mechanism of these bipolar amphiphiles at the fluid/condensed phase transition. The morphology of the condensed phase domains formed in the fluid/condensed coexistence region is specific for the position of the OH-substitution of the alkyl chain, just as the lattice structures of the condensed monolayer phase. 11-hydroxyoctadecanoic acid monolayers form centered rectangular lattices with the chain tilt toward the NNN (next nearest neighbor) direction, and 12-hydroxyoctadecanoic acid monolayers have an oblique lattice over the entire pressure range. A special feature of 9-hydroxystearic acid monolayers is the phase transition between two condensed phases observed in the pi-A isotherm of 5 degrees C at approximately 18 mN/m, where the centered rectangular lattice shows a NNN/NN transition. The morphology of the condensed phase domains formed in the fluid/condensed coexistence region, just as the lattice structures of the condensed monolayer phase, reveal the high specifity of the monolayer feature of the bipolar hydroxystearic acids OH-substituted in the mid position.

Model membrane/substrate interactions: ethanol and procaine interactions.

The ability of ethanol to lower the surface tension of water plays a major role in its ability to affect membrane lipids. Typical lipids will show little expansion on exposure to ethanol substrates and may even show condensations. At the same time, the overall stability of the lipid phase is significantly reduced. Previously, we reported experimental and theoretical studies of the stearic acid (SA)/procaine (PR) system. PR substrate concentrations were examined in the 10(-4)-10(-2) M range as Gibbs monolayers, in order to establish the surface activity of both charged and uncharged species, and to estimate the orientation of the PR species at the air/water interface. SA interactions with PR substrates were studied by compressing films of the former and recording the surface pressure/area per molecule isotherms at both pH 2 and 8, so that the SA was in an uncharged and charged state, respectively. More recently, we have carried out similar studies with L-alpha-dipalmitoyl phosphatidylcholine (DPPC), maintaining the substrate pH at between 5 and 6, at PR concentrations of 10(-6)-10(-2)M. We also carried out studies of the DPPC/PR system using fluorescence microscopy in order to examine the effects of PR on the biphasic liquid expanded/liquid condensed (LE/LC) transition region. In the absence of any lipid film, PR species appear to be horizontally oriented at the air/water interface, while the surface activity of PR species increases in the order PRH(2+)

A comparative monomolecular film study of 1,2-di-O-palmitoyl-3-O-(alpha- and beta-D-glucopyranosyl)-sn-glycerols.

The polar headgroup contribution to monolayer behavior of dipalmitoylglucosylglycerol has been examined through studies of 1,2-di-O-palmitoyl-3-O-(alpha-D-glucopyranosyl)-sn-glycerol (di-16:0-alpha GlcDG) and 1,2-di-O-palmitoyl-3-O-(beta-D-glucopyranosyl)-sn-glycerol (di-16:0-beta GlcDG) in which the sugar headgroup is linked via an alpha or beta linkage to the diacylglycerol moiety. The results indicate that the limiting areas per molecule of the resultant condensed states are smaller than those of the corresponding phosphatidylcholine (DPPC) but larger than those of dipalmitoylphosphatidylethanolmine (DPPE). In the expanded state, while the areas per molecule are similar to those of DPPC at low pressures, both glycolipids occupy smaller areas at higher pressures. The expanded-state areas of the glucolipids are also slightly greater than those of DPPE. The initial compressional phase transition pressure of the glucolipid liquid-expanded/liquid-condensed transition (pi t) is, however, less sensitive to temperature than are the pi t values of phospholipids. Both of these effects must relate to strong headgroup/water interactions, which, in turn, result in a stabilization of the liquid-expanded states. In the expanded states the alpha anomers are slightly less tightly packed than the beta anomers, as is indicated by the somewhat higher areas per molecule of the expanded states and the lower transition temperatures. These differences in chain-melting temperatures are slightly smaller than those observed in bilayers. While the areas per molecule of the dipalmitoyl glucolipids are greater than those of dipalmitoylphosphatidylethanolamine, they nevertheless exhibit a greater tendency to form nonbilayer structures. Such observations indicate that other factors besides geometric shape play a role in bilayer/nonbilayer transitions.

Electrostatically induced growth of spiral lipid domains in the presence of cholesterol.

The formation of crystalline domains of the phospholipid L-alpha-dimyristoyl-phosphatidic acid containing 1 mol% cholesterol, was studied as a function of head group charge by fluorescence microscopy with monolayers at the air/water interface. It is shown that the usual dendritic growth occurs at low pH (8), whereas spiral domains are formed at high pH (11), where the head group contains two negative charges. The findings are ascribed to an electrostatically induced chain tilt that, in conjunction with an in-plane dipole moment, causes a ferroelectric state. This allows for domain aggregation and orientation originating in elongated domains that, additionally, are bent because of the chirality of the molecules. The structure is stabilized and further elongated due to the anisotropic edge activity of cholesterol.

Mixed monolayers of straight-chain/branched-chain phospholipids. I. Mixed monolayers of distearoyl phosphatidylcholine and diisoeicosanoyl phosphatidylcholine.

The temperature dependence of the force/area isotherms of monolayer of distearoyl phosphatidylcholine (DSPC), diisoeicosanoyl phosphatidylcholine (DIEPC) and a complete mixed compositional range of these two lecithins are reported. The isotherms for DSPC closely resemble those previously reported for dipalmitoyl phosphatidylcholine but are shifted to higher temperatures by 16 degrees C. The isotherms of DIEPC, an iso-branched lecithin, show differences from these obtained for similar straight-chain lecithins in that the full condensed isotherms are more expanded, the fully expanded isotherms are more condensed and therefore the liquid expanded (LE)/liquid condensed (LC) intermediate region is significantly reduced. This means that the condensed state is more disordered and the expanded state is less disordered than the corresponding states in straight-chain lecithins. Data for the mixed films are interpreted in terms of surface pressure/mole fraction phase diagrams and both energies and entropies of compression associated with the LE/LC transition. The phase diagrams at 34.1 degrees C, 35.8 degrees C and 38.5 degrees C are all of the negative azeotropic type with the surface pressure minimum point shifting with temperature. The thermodynamic analysis indicates that from 34.1 degrees C to 38.5 degrees C the driving force for mixing changes from the entropy to the energy of the transition. It would seem that at the lower temperature the packing of the distearoyl lecithin is perturbed by the diisoeicosanoyl lecithin, while at higher temperatures the very high entropy of pure or nearly pure diisoeicosanoyl lecithin results in other mixtures having less entropy than would be expected on an ideal mixing basis.

Molecular packing in steroid-lecithin monolayers. IV. Mixed films of epicoprostanol with dipalmitoyl phosphatidylcholine.

Studies of the two-component monomolecular film system, dipalmitoyl phosphatidylcholine (DPPC) - epicoprostanol have been carried out at 21 degrees C utilizing a wide compositional range of films. The results obtained indicate that on initial mixing of the two components, epicoprostanol condensed expanded DPPC films to a greatly reduced degree and expanded condensed DPPC films to a significantly greater degree compared with cholesterol. It is thought that, even on an initial compressional procedure, partial microscopic segregation of epicoprostanol takes place. The segregation is postulated to result from an epicoprostanol-epicoprostanol overlap, leading to row packing with an accompanying reduction in the number of adjacent acyl chains. Subsequent decompression and recompression of DPPC-epicoprostanol films leads to macroscopic segregation of pure or nearly pure epicoprostanol; however, partial miscibility below 20 mol% epicoprostanol may persist. The phase diagram of the initially compressed film may be of the eutectic type, but the mixed system is unstable. The inability of epicoprostanol to substitute for cholesterol appears to be due to a combination of two effects: the tilting of the sterol at the air-water interface, to satisfy the immersion requirements of the 3 alpha-OH group, and the bent alpha-face of the sterol. The alpha-OH group of epicoprostanol is postulated to play an indirect role in the weak condensation capabilities of this sterol by inducing a tilt in the molecule and reducing epicoprostanol - acyl chain hydrophobic interactions.

Fluorescent probes in model membranes. II. Monolayer studies of 2,2'-(vinylenedi-p-phenylene)bisbenzoxazole, d-3-aminodesoxyequilenin and N-octadecylnaphthyl-2-amino-6-sulfonic acid with host-lipid tetradecanoic acid.

Film studies at the air-water interface have been carried out for pure films of 2,2'-(vinylenedi-p-phenylene)bisbenzoxazole (VPBO), d-3-aminodesoxyequilenin (EQ) and N-octadecylnapthyl-2-amino-6-sulfonic acid (ONS), and for mixed films with tetradecanoic acid for the first two fluorescent probes. Pure film isotherms indicate highly rigid non-monomolecular films for both VPBO and EQ, revealing the presence of strong intermolecular forces. In mixed films with tetradecanoic acid VPBO rapidly segregates with resultant film loss over a wide concentration range. EQ, however, can be stabilized by the host-lipid at low concentrations. This, coupled with an ability to only slightly affect the host-lipid liquid-condensed/liquid-expanded phase change, suggests that EQ can be regarded as "non-perturbing" and should be retained in condensed lipid phases. ONS, because of its unusual polar headgroup, resembled hexadecanoic acid more than octadecanoic acid. While difficulties in spreading ONS precluded the study of mixed films, the indications are that it would be a satisfactory expanded lipid state probe if mixing can be brought about.

Fluorescent probes in model membranes I: anthroyl fatty acid derivatives in monolayers and liposomes of dipalmitoylphosphatidylcholine.

A study of three fluorescent anthroyl probes has been carried out using pure and mixed monomolecular films with dipalmitoylphosphatidylcholine. In addition, fluorescence depolarization and differential scanning calorimetry data were obtained from dipalmitoylphosphatidylcholine vesicles with incorporated anthroyl probes. The three probes used were 2-(9-anthroyl)palmitic acid. 12-(9-anthroyl)stearic acid, and 16-(9-anthroyl)palmitic acid. The latter probe was synthesized for these studies. In monolayers the probes shifted the onset of the liquid-condensed/liquid-expanded monolayer phase transition with the extent of the shift decreasing in the order: 2-(9-anthroyl)palmitic acid greater than 12-(9-anthroyl)stearic acid greater than 16-(9-anthroyl)stearic acid. A corresponding decrease in the gel-liquid crystalline bilayer transition temperature (Tc) showed the same order of perturbation in both the fluorescence depolarization and differential scanning calorimetry data. Locating the anthroyl entity in the center of the bilayer would appear to provide a minimum perturbation.

Model membrane studies of spin-label probes. Part 1. Mixed monolayers of 12-nitroxide stearic acid and myristic acid.

Pure and mixed monomolecular films of a cell membrane spin label probe, 12-nitroxide stearic acid have been studied where myristic acid was selected as the host lipid. The behavior of 12-nitroxide stearic acid at the air water interface is understood in terms of two molecular configurations: erect (with only the carboxyl group in the interface) and bent (with both the carboxyl group and the oxazolidine ring in the interface). In mixed films both of these conformations play a role at high surface pressures. At low probe concentrations, 12-nitroxide stearic acid is primarily in an erect conformation, while at high probe concentrations the reverse is true. This particular host lipid appears capable of erecting the probe molecule with only small concentrations of myristic acid. In a condensed host lipid, the probe is partially immiscible, and segregates to form a heterogeneous film from which it is readily collapsed. The probe is seen to perturb the molecular packing in this mixed system and the perturbation to be dependent on both the molecular shape and nature of the probe.

A comparison of a spin-label and a fluorescent cell membrane probe using pure and mixed monomolecular films.

Monocular films studies of 12-nitroxide stearic acid and 12-(9-anthroyl) stearic acid reveal that deviations from the behavior of the parent molecule (stearic acid) are as much dictated by the polar, or nonpolar, nature of the probe group as by its size. In mixed films under membrane-like conditions, the spin label probe, 12-nitroxide stearic acid, exhibits positive deviations from ideality and should read too high a fluidity. The picture is, however, complicated by a tendency of this probe molecule to adopt a bent conformation, a tendency apparently enhanced by specific interactions with the lecithin zwitterion. 12-(9-anthroyl) stearic acid, in contrast, shows only negative deviations from ideality in mixed dipalmitoyl lecithin films and should read too low a fluidity.

Water vapor from a lunar breccia: implications for evolving planetary atmospheres.

The exposure of a typical complex lunar breccia to hydrogen after a thorough outgassing produces a fully reduced surface state. Subsequent outgassing over a wide temperature range results in the production of water vapor formed from the chemisorbed hydrogen and oxygen from the lunar sample; the proposed mechanism has been confirmed in terms of the chemisorption of deuterium and the release of heavy water. Since the conditions of the experiments are consistent with those on the lunar surface, it is postulated that water vapor will be produced on the moon through the interaction of the solar wind with lunar soil. It is also proposed that such a process could play an important role in the early history of many planets where an oxygen-rich soil is exposed to a reducing atmosphere.