New ordered metastable phases between the gel and subgel phases in hydrated phospholipids.

Formation of low-temperature ordered gel phases in several fully hydrated phosphatidylethanolamines (PEs) and phosphatidylcholines (PCs) with saturated chains as well as in dipalmitoylphosphatidylglycerol (DPPG) was observed by synchrotron x-ray diffraction, microcalorimetry, and densitometry. The diffraction patterns recorded during slow cooling show that the gel-phase chain reflection cooperatively splits into two reflections, signaling a transformation of the usual gel phase into a more ordered phase, with an orthorhombic chain packing (the Y-transition). This transition is associated with a small decrease (2-4 microl/g) or inflection of the partial specific volume. It is fully reversible with the temperature and displays in heating direction as a small (0.1-0.7 kcal/mol) endothermic event. We recorded a Y-transition in distearoyl PE, dipalmitoyl PE (DPPE), mono and dimethylated DPPE, distearoyl PC, dipalmitoyl PC, diC(15)PC, and DPPG. No such transition exists in dimyristoyl PE and dilauroyl PE where the gel L(beta) phase transforms directly into subgel L(c) phase, as well as in the unsaturated dielaidoyl PE. The PE and PC low-temperature phases denoted L(R1) and SGII, respectively, have different hydrocarbon chain packing. The SGII phase is with tilted chains, arranged in an orthorhombic lattice of two-nearest-neighbor type. Except for the PCs, it was also registered in ionized DPPG. In the L(R1) phase, the chains are perpendicular to the bilayer plane and arranged in an orthorhombic lattice of four-nearest-neighbor type. It was observed in PEs and in protonated DPPG. The L(R1) and SGII phases are metastable phases, which may only be formed by cooling the respective gel L(beta) and L(beta') phases, and not by heating the subgel L(c) phase. Whenever present, they appear to represent an indispensable intermediate step in the formation of the latter phase.

Detection of the metastable rippled gel phase in hydrated phosphatidylcholine by fluorescence spectroscopy.

Steady-state and time-resolved emission spectroscopy of 1-anilinonaphthalene-8-sulfonic acid (ANS) have been used for characterization of the metastable rippled gel phase, Pbeta'(mst), formed in fully-hydrated dipalmitoylphosphatidylcholine (DPPC) upon cooling from the liquid crystalline phase Lalpha [Tenchov et al., Biophys. J. 56 (1989) 757]. The Pbeta'(mst) phase of DPPC clearly differs from the stable Pbeta' phase by increased (approximately 27%) ANS emission intensity, by enhanced (approximately 23%) average radiative rate constant, and by reduced (approximately 18%) non-radiative quenching rate constant. The fluorescence intensity peak at the Pbeta'-->Lalpha transition temperature is replaced by a large, reversible stepwise intensity drop at the Pbeta'(mst)-->Lalpha transition. No such effects have been found for dimiristoylphosphatidylcholine (DMPC) dispersions confirming previous results that DMPC does not form a Pbeta'(mst) phase. Since ANS is known to predominantly reside in the interfacial region, the observed effects indicate differences between the stable and metastable rippled phases in the organization and dynamics of their lipid/water interfaces. The data demonstrate that the metastable rippled phase manifests its appearance also through interactions with small molecules (ANS size approximately 8 A).

Discrete reduction of type I collagen thermal stability upon oxidation.

The oxidation of acid-soluble calf skin collagen type I caused by metal-dependent free radical generating systems, Fe(II)/H2O2 and Cu(II)/H2O2, was found to bring down in a specific, discrete way the collagen thermal stability, as determined by microcalorimetry and scanning densitometry. Initial oxidation results in splitting of the collagen denaturational transition into two components. Along with the endotherm at 41 degrees C typical for non-oxidized collagen, a second, similarly cooperative endotherm appears at 35 degrees C and increases in enthalpy with the oxidant concentration and exposure time, while the first peak correspondingly decreases. The two transitions at 35 and 41 degrees C were registered by densitometry as stepwise increases of the collagen-specific volume. Further oxidation results in massive collagen destruction manifested as abolishment of both denaturational transitions. The two oxidative systems used produce identical effects on the collagen stability but at higher concentrations of Cu(II) in comparison to Fe(II). The discrete reduction of the protein thermal stability is accompanied by a decrease of the free amino groups, suggestive of an oxidation attack of the side chains of lysine residues. Since the denaturation temperature of collagen shifts from above to below body temperature (41 degrees C-35 degrees C) upon oxidation, it appears important to account for this effect in a context of the possible physiological implications of collagen oxidation.

An ordered metastable phase in hydrated phosphatidylethanolamine: the Y-transition.

By using time-resolved X-ray diffraction, differential scanning calorimetry and scanning densitometry, we observed rapid formation at low temperature of a metastable ordered phase, termed LR1 phase, in fully hydrated dihexadecylphosphatidylethanolamine (DHPE). The LR1 phase has the same lamellar repeat period as the gel Lbeta phase but differs from the latter in its more ordered, orthorhombic hydrocarbon chain arrangement. It forms at about 12 degrees C upon cooling and manifests itself as splitting of the sharp, symmetric wide-angle X-ray peak of the DHPE gel phase into two reflections. This transition, designated the 'Y-transition', is readily reversible and proceeds with almost no hysteresis between cooling and heating scans. Calorimetrically, the LR1-->Lbeta transition is recorded as a low-enthalpy (0.2 kcal/mol) endothermic event. The formation of the LR1 phase from the gel phase is associated with a small, about 2 microl/g, decrease of the lipid partial specific volume recorded by scanning densitometry, in agreement with a volume calculation based on the X-ray data. The formation of the equilibrium Lc phase was found to take place from within the LR1 phase. This appears to be the only observable pathway for crystallisation of DHPE upon low-temperature incubation. Once formed, the Lc phase of this lipid converts directly into Lbeta phase at 50 degrees C, skipping the LR1 phase. Thus, the LR1 phase of DHPE can only be entered by cooling of the gel Lbeta phase. The data disclose certain similarities between the low-temperature polymorphism of DHPE and that of long-chain normal alkanes.

Phases and phase transitions of the phosphatidylcholines.

LIPIDAT (http://www.lipidat.chemistry.ohio-state.edu) is an Internet accessible, computerized relational database providing access to the wealth of information scattered throughout the literature concerning synthetic and biologically derived polar lipid polymorphic and mesomorphic phase behavior and molecular structures. Here, a review of the data subset referring to phosphatidylcholines is presented together with an analysis of these data. This subset represents ca. 60% of all LIPIDAT records. It includes data collected over a 43-year period and consists of 12,208 records obtained from 1573 articles in 106 different journals. An analysis of the data in the subset identifies trends in phosphatidylcholine phase behavior reflecting changes in lipid chain length, unsaturation (number, isomeric type and position of double bonds), asymmetry and branching, type of chain-glycerol linkage (ester, ether, amide), position of chain attachment to the glycerol backbone (1,2- vs. 1,3-) and head group modification. Also included is a summary of the data concerning the effect of pressure, pH, stereochemical purity, and different additives such as salts, saccharides, amino acids and alcohols, on phosphatidylcholine phase behavior. Information on the phase behavior of biologically derived phosphatidylcholines is also presented. This review includes 651 references.

Accelerated formation of cubic phases in phosphatidylethanolamine dispersions.

By means of x-ray diffraction we show that several sodium salts and the disaccharides sucrose and trehalose strongly accelerate the formation of cubic phases in phosphatidylethanolamine (PE) dispersions upon temperature cycling through the lamellar liquid crystalline-inverted hexagonal (Lalpha-HII) phase transition. Ethylene glycol does not have such an effect. The degree of acceleration increases with the solute concentration. Such an acceleration has been observed for dielaidoyl PE (DEPE), dihexadecyl PE, and dipalmitoyl PE. It was investigated in detail for DEPE dispersions. For DEPE (10 wt% of lipid) aqueous dispersions at 1 M solute concentration, 10-50 temperature cycles typically result in complete conversion of the Lalpha phase into cubic phase. Most efficient is temperature cycling executed by laser flash T-jumps. In that case the conversion completes within 10-15 cycles. However, the cubic phases produced by laser T-jumps are less ordered in comparison to the rather regular cubic structures produced by linear, uniform temperature cycling at 10 degrees C/min. Temperature cycles at scan rates of 1-3 degrees C/min also induce the rapid formation of cubic phases. All solutes used induce the formation of Im3m (Q229) cubic phase in 10 wt% DEPE dispersions. The initial Im3m phases appearing during the first temperature cycles have larger lattice parameters that relax to smaller values with continuation of the cycling after the disappearance of the Lalpha phase. A cooperative Im3m --> Pn3m transition takes place at approximately 85 degrees C and transforms the Im3m phase into a mixture of coexisting Pn3m (Q224) and Im3m phases. The Im3m/Pn3m lattice parameter ratio is 1. 28, as could be expected from a representation of the Im3m and Pn3m phases with the primitive and diamond infinite periodic minimal surfaces, respectively. At higher DEPE contents ( approximately 30 wt%), cubic phase formation is hindered after 20-30 temperature cycles. The conversion does not go through, but reaches a stage with coexisting Ia3d (Q230) and Lalpha phases. Upon heating, the Ia3d phase cooperatively transforms into a mixture of, presumably, Im3m and Pn3m phases at about the temperature of the Lalpha-HII transition. This transformation is readily reversible with the temperature. The lattice parameters of the DEPE cubic phases are temperature-insensitive in the Lalpha temperature range and decrease with the temperature in the range of the HII phase.

Low amounts of PEG-lipid induce cubic phase in phosphatidylethanolamine dispersions.

By using time-resolved X-ray diffraction we demonstrate that low amounts (5-10 mol%) of a phospholipid with two saturated hydrocarbon acyl chains 14 carbon atoms long and PEG550 chain covalently attached to its phosphoethanolamine polar head group, DMPE(PEG550), induce spontaneous formation of a cubic phase with lattice constant 20.5 nm (cubic aspect #8, space group Im3m) in aqueous dispersions of dielaidoylphosphatidylethanolamine (DEPE). This phase displays a highly resolved X-ray diffraction pattern with 17 low-angle reflections. The cubic phase was found to intrude in the temperature range between the lamellar liquid crystalline (L(alpha)) phase and the inverted hexagonal phase (H(II)) known to form in pure DEPE/water dispersions. A higher DMPE(PEG550) amount of 20 mol% was found to eliminate the non-lamellar phases in the temperature scale up to 100 degrees C. DMPE grafted with PEG5000 only shifts the L(alpha)-H(II) transition of DEPE to higher temperatures but does not promote formation of cubic phase. These findings indicate that, consistent with their bulky head groups, the PEG-lipids decrease the tendency for negative interfacial mean curvature of the DEPE bilayers.

Modulation of lipid phase behavior by kosmotropic and chaotropic solutes : Experiment and thermodynamic theory.

By means of differential scanning calorimetry and from a review of published data we demonstrate in this work that low-molecular weight kosmotropic substances (water-structure makers) of different chemical structure such as disaccharides, proline, and glycerol have identical effects on the phase behavior of several kinds of phospholipids and glycolipids. These substances favor formation of the high-temperature inverted hexagonal phase (H(II)) and the low-temperature lamellar crystalline (L(c)) and gel (L( ß )) phases at the expense of the intermediate lamellar liquid-crystalline phase (L( α )). The latter phase may completely disappear from the phase diagram at high enough solute concentration. By contrast, chaotropic substances (water-structure breakers) such as sodium thiocyanate and guanidine hydrochloride expand the existence range of L( α ) at the expense of the adjacent L( ß ) and H(II) phases. Moreover, chaotropes are able to induce the appearance of missing intermediate liquid-crystalline phases in lipids displaying direct L( ß )→H(II) transitions in pure water. In previous publications we have considered the influence of chaotropic and kosmotropic substances on the lipid phase behavior as a manifestation of their indirect (Hofmeister) interactions with the lipid aggregates. For a quantitative characterization of this effect, here we derive a general thermodynamic equation between lipid phase transition temperature and solute concentration, analogous to the Clapeyron-Clausius equation between transition temperature and pressure. It provides a clear description in physical quantities of the disparate effects of kosmotropic and chaotropic substances on the relative stability of the lipid-water phases. According to this equation, the magnitude of the solute effect is proportional to the hydration difference of the adjacent lipid phases and inversely proportional to the transition latent heat. The sign and magnitude of the transition shifts depend also on the degree of solute depletion (for kosmotropes) or enrichment (for chaotropes) at the interfaces, in comparison to the solute concentration in bulk water.

Metastable rippled gel phase in saturated phosphatidylcholines: calorimetric and densitometric characterization.

A long-living metastable rippled phase P beta' mst has been earlier reported to form in aqueous dispersions of dipalmitoylphosphatidylcholine (DPPC) upon cooling from the lamellar liquid crystalline phase L alpha (Tenchov et al. (1989) Biophys. J. 56, 757-768). Here we demonstrate that similar metastable phases form also in distearoylphosphatidylcholine (DSPC) and dihexadecylphosphatidylcholine (DHPC) but not in dimyristoylphosphatidylcholine (DMPC). The thermodynamic parameters of P beta' mst in DPPC, DSPC and DHPC have been characterized in detail by means of differential scanning calorimetry and scanning densitometry. It is shown that the P beta' mst phase in these three lipids has higher specific heat capacity by 0.1-0.4 kcal K-1 mol-1 and higher specific volume by 1-2 microliters/g than the equilibrium P beta' phase formed upon heating from the L beta' phase. The P beta' mst-->L alpha transition in these three lipids takes place at 0.06-0.14 degree C lower temperature than the P beta'-->L alpha transition. Its enthalpy is lower by 5-11% and the apparent maximum specific heat Cp max is lower by 11-14%. The P beta' mst phase is a long-living phase-it does not relax into the equilibrium P beta' for at least several hours. The replacement of the ester glycerol-hydrocarbon chain linkages in DPPC with ether bonds in DHPC does not influence the formation of P beta' mst.

New phases induced by sucrose in saturated phosphatidylethanolamines: an expanded lamellar gel phase and a cubic phase.

A new lamellar gel phase (L beta *) with expanded lamellar period was found at low temperatures in dihexadecylphosphatidylethanolamine (DHPE) and dipalmitoylphosphatidylethanolamine (DPPE) dispersions in concentrated sucrose solutions (1-2.4 M). It forms via a cooperative, relatively broad transition upon cooling of the L beta gel phase of these lipids. According to the X-ray data, the transformation between L beta and L beta * is reversible, with a temperature hysteresis of 6-10 degrees C and a transition width of about 10 degrees C. No specific volume changes and a very small heat absorption of about 0.05 kcal/mol accompany this transition. The L beta *-L beta transition temperature strongly depends on the disaccharide concentration. From a value of about 10 degrees C below the melting transition of DHPE, it drops by 25 degrees C with decrease of sucrose concentration from 2.4 M to 1 M. The low-temperature gel phase L beta * has a repeat spacing by 8-10 A larger than that of the L beta gel phase and a single symmetric 4.2 A wide-angle peak. It has been observed in 1, 1.25, 1.5 and 2.4 M solutions of sucrose, but not in 0.5 M of sucrose. The data clearly indicate that the expanded lamellar period of the L beta * phase results from a cooperative, reversible with the temperature, increase of the interlamellar space of the L beta gel phase. Other sugars (trehalose, maltose, fructose, glucose) induce similar expanded low-temperature gel phases in DHPE and DPPE. The L beta * phase is osmotically insensitive. Its lamellar period does not depend on the sucrose concentration, while the lattice spacings of the L alpha, L beta and HII phases decrease linearly with increase of sucrose concentration. Another notable sugar effect is the induction of a cubic phase in these lipids. It forms during the reverse HII-L alpha transition and coexists with the L alpha phase in the whole temperature range between the HII and L beta phases. The cubic phase has only been observed at sucrose concentrations of I M and above. In accordance with previous data, sucrose suppresses the L alpha phase in both lipids and brings about a direct L beta-HII phase transition in DHPE. A raid, reversible gel-subgel transformation takes place at 17 degrees C in both DPPE and DHPE. Its properties do not depend on the sucrose concentration. The observed new effects of disaccharides on the properties of lipid dispersions might be relevant to their action as natural protectants.

Thermal stability of calf skin collagen type I in salt solutions.

The thermal stability of acid-soluble collagen type I from calf skin in salt solutions is studied by high-sensitivity differential scanning calorimetry. Three concentration ranges have been clearly distinguished in the dependence of collagen thermal stability on ion concentration. At concentrations below 20 mM, all studied salts reduce the temperature of collagen denaturation with a factor of about 0.2 degree C per 1 mM. This effect is attributed to screening of electrostatic interactions leading to collagen stabilisation. At higher concentrations, roughly in the range 20-500 mM, the different salts either slightly stabilise or further destabilise the collagen molecule in salt-specific way that correlates with their position in the lyotropic series. The effect of anions is dominating and follows the order H2PO4- > or = SO4(2-) > Cl- > SCN-, with sign inversion at about SO4(2-). This effect, generally known as the Hofmeister effect, is associated with indirect protein-salt interactions exerted via competition for water molecules between ions and the protein surface. At still higher salt concentrations (onset concentrations between 200 and 800 mM for the different salts), the temperature of collagen denaturation and solution opacity markedly increase for all studied salts due to protein salting out and aggregation. The ability of salts to salt out collagen also correlates with their position in the lyotropic series and increases for chaotropic ions. The SO4(2-) anions interact specifically with collagen - they induce splitting of the protein denaturation peak into two components in the range 100-150 mM Na2SO4 and 300-750 mM Li2SO4. The variations of the collagen denaturation enthalpy at low and intermediate salt concentrations are consistent with a weak linear increase of the enthalpy with denaturation temperature. Its derivative, d(delta H)/dT, is approximately equal to the independently measured difference in the heat capacities of the denatured and native states, delta Cp = Cp(D) - Cp(N) approximately 0.1 cal.g-1 K-1.

Rapid reversible formation of a metastable subgel phase in saturated diacylphosphatidylcholines.

Formation of well ordered lamellar subgel (SGII) phase in aqueous dispersions of L-dipalmitoylphosphatidylcholine upon cooling from the lamellar gel phase, without low-temperature equilibration, is observed in real time using synchrotron x-ray diffraction. It has the same lamellar repeat period as the gel phase from which it was formed but differs in its wide-angle diffraction pattern. The SGII phase forms at about 7 degrees C upon cooling at 2 degrees C/min. In temperature jump experiments at 1 degree C/s from 50 to -5 degrees C, the relaxation time of the lamellar gel-SGII transition is found to be approximately 15 s. The conversion between the lamellar gel and SGII phase is cooperative and rapidly reversible. Upon heating, it coincides in temperature with an endothermic event with a calorimetric enthalpy of 0.35 kcal/mol, the so-called sub-subtransition. Similar sub-subtransitions are also observed calorimetrically at temperatures approximately 10 degrees C below the subtransition, without low-temperature storage, in aqueous dispersions of L-dimyristoylphosphatidylcholine and L-distearoylphosphatidylcholine, but not in racemic DL-dipalmitoylphosphatidylcholine. The formation of the equilibrium lamellar crystalline Lc phase appears to take place only from within the SGII phase.

Phases and phase transitions of the sphingolipids.

LIPIDAT is a computerized database providing access to the wealth of information scattered throughout the literature concerning synthetic and biologically derived polar lipid polymorphic and mesomorphic phase behavior. Herein, we present a review of the LIPIDAT data subset referring to sphingolipids together with an analysis of these data. It includes data collected over a 40-year period and consists of 867 records obtained from 112 articles in 25 different journals. An analysis of these data has allowed us to identify trends in hydrated sphingolipid phase behavior reflecting differences in fatty acyl chain length, saturation and hydroxylation, head group type, and sphingoid base identity. Information on the mesomorphism of biologically-derived and dry sphingolipids is also presented. This review includes 161 references.

Thermal stability of lipid-depleted purple membranes at neutral and low pH values.

Differential scanning calorimetry was used to compare the thermal behavior of native and delipidated purple membrane fragments at pH values corresponding to purple, blue and acid-purple forms. At neutral pH, delipidation results in a 2.5- to 3-times increase in the cooperativity of the denaturational transition, accompanied by a minor increase in its temperature. At pH values below 5 the delipidated membranes exhibit considerably higher thermal stability than the native membranes. The reversible predenaturational transition observed in the native state is not detectable upon delipidation. There is no strict correlation between color changes upon acidification and deionization of either native or delipidated purple membranes and their thermal stability.

Phases and phase transitions of the glycoglycerolipids.

LIPIDAT is a computerized database providing access to the wealth of information scattered throughout the literature concerning synthetic and biologically derived polar lipid polymorphic and mesomorphic phase behavior. The database is considered comprehensive for glycerophospholipids, glycoglycerolipids, sphingolipids and natural membrane extracts. Here, a review of the LIPIDAT data subset referring to glycoglycerolipids is presented together with an analysis of these data. The glycoglycerolipids subset represents 4% of all LIPIDAT records. It includes data collected over a 20-year period and consists of 419 records obtained from 37 articles in 13 journals. An analysis of the data in the subset has allowed us to identify trends in hydrated glycoglycerolipids phase behavior reflecting differences in hydrocarbon chain length, chain branching, chain-glycerol linkage type (ether vs. ester), sugar headgroup-glycerol linkage type (alpha vs. beta) and sugar headgroup identity. Included is a summary of the data concerning the effect of pH and of stereochemical purity on glycoglycerolipid phase behavior. Information on the mesomorphism of biologically derived and dry glycoglycerolipids is also presented. This review includes 92 references.

Phases and phase transitions of the hydrated phosphatidylethanolamines.

LIPIDAT is a computerized database providing access to the wealth of information scattered throughout the literature concerning synthetic and biologically derived polar lipid polymorphic and mesomorphic phase behavior. Here, a review of the LIPIDAT data subset referring to hydrated phosphatidylethanolamines (PE) is presented together with an analysis of these data. The PE subset represents 14% of all LIPIDAT records. It includes data collected over a 38-year period and consists of 1511 records obtained from 203 articles in 35 different journals. An analysis of the data in the subset has allowed us to identify trends in synthetic PE phase behavior reflecting changes in lipid chain length, chain unsaturation (number, isomeric type and position of double bonds), chain asymmetry and branching, type of chain-glycerol linkage (ether vs. ester) and headgroup modification. Also included is a summary of the data concerning the effect of pH, stereochemical purity, and different additives such as salts, saccharides, alcohols, amino adds and alkanes on PE phase behavior. Information on the phase behavior of biologically derived PE is also presented. This review includes 236 references.

Different phase behaviour of the sn-1 and sn-3 stereoisomers of the glycolipid di-tetradecyl-beta-D-galactosylglycerol.

The phase behaviour of a synthetic, stereochemically pure glycolipid 2,3-di-O-tetradecyl-1-O-beta-D-galactosyl-sn-glycerol (14-2,3-Gal) in excess water has been characterized by differential scanning calorimetry and time-resolved X-ray diffraction and compared with that of the previously studied sn-3 stereoisomer, 1,2-di-O-tetradecyl-3-O-beta-D-galactosyl-sn-glycerol (14-1,2-Gal), and 1,2-di-O-tetradecyl-3-O-beta-D-glucosyl-sn-glycerol (14-1,2-Glc). The properties of 14-1,2-Gal and 14-2,3-Gal are completely different with respect to phase sequences, metastable behaviour, transition temperatures and enthalpies, but there is a rather close similarity between the phase patterns of 14-2,3-Gal and 14-1,2-Glc. The sn-3 stereoisomer, 14-1,2-Gal, exhibits a direct lamellar crystalline to inverted hexagonal phase transition (Lc-->HII) on heating and a HII-->L alpha (metastable)-->L beta(metastable)-->Lc phase sequence in subsequent cooling, while both 14-2,3-Gal and 14-1,2-Glc are characterized by an Lc-->L alpha-->HII sequence in first heating, and reversible L beta<-->L alpha<-->HII phase sequences in subsequent heating and cooling scans. The peak areas and temperatures of the L beta-->L alpha transitions are practically identical, while the Lc-->L alpha and L alpha-->HII temperatures for 14-2,3-Gal are about 5 degrees C higher than the corresponding temperatures for 14-1,2-Glc. These data are interpreted in terms of a significantly greater stability and faster formation kinetics of the lamellar crystalline Lc phase of 14-1,2-Gal.(ABSTRACT TRUNCATED AT 250 WORDS)

Structure and phase behavior of a charged glycolipid (1,2-O-dialkyl-3-O-beta-D-glucuronosyl-sn-glycerol).

In order to investigate the effects of a net surface charge on the properties of glycolipid membranes, we have synthesized a glyceroglycolipid, 1,2-O-dialkyl-3-O-beta-D-glucuronosyl- sn-glycerol (GlcUA lipid), with saturated alkyl chains of varying length (14, 16, and 18 carbon atoms; 14-, 16-, and 18-GlcUA, respectively) and glucuronic acid with an ionizable 6-carboxyl group as polar residue. Aqueous dispersions of GlcUA lipids have been characterized by differential scanning calorimetry, densitometry, and X-ray diffraction methods as a function of pH. The carboxyl group deprotonation of apparent pK about 5.5 leads to a decrease of the melting temperatures by about 7 degrees C for all three compounds and to a chain-length-dependent reduction of the transition enthalpies by 0, 7, and 14% for 14-, 16-, and 18-GlcUA, respectively. The decrease of the transition temperature is consistent with current electrostatic concepts and models of charged membrane interfaces, but the chain-length-specific dependence of the enthalpy decrease with an increase of pH shows that the pH effects in GlcUA lipids are not of purely electrostatic origin. However, these effects appear to be simpler in some instances than corresponding effects in phospholipids with multiply ionizable head groups. For this reason, the lipids with the glucuronic acid head group appear to represent an appropriate model system for studies of net electric charge effects on the membrane properties.(ABSTRACT TRUNCATED AT 250 WORDS)