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L J Lis

Publications and source records attributed to L J Lis.

At least 37 records · Page 2Linked to original sources
PubMed1988

Lamellar gel-lamellar liquid crystal phase transition of dipalmitoylphosphatidylcholine multilayers freeze-dried from aqueous trehalose solutions. A real-time X-ray diffraction study.

The mechanism of the phase transition of dipalmitoylphosphatidylcholine multilayers freeze-dried from fully hydrated gel phase (L beta') in the presence of trehalose has been investigated by real-time X-ray diffraction methods. Sequential diffraction patterns were recorded with an accumulation time of 3 s during heating and 1.2 s during cooling between about 20 and 80 degrees C. A transition is observed in the range 47-53 degrees C that involves structural events typical of a lamellar gel-lamellar liquid-crystal (L beta--L alpha) transformation. This transition is completely reversible with a temperature hysteresis of 2-3 degrees C and thereby resembles the main phase transition of fully hydrated dipalmitoylphosphatidylcholine multilayers. The mechanism of the transition from L beta to L alpha as seen in the wide-angle scattering profiles show that the sharp peak at about 0.41 nm, characteristic of the gel phase, broadens and shifts progressively to about 0.44 nm towards the end of the transition. A temperature jump of 6C degrees/s through the phase transition region of a freeze-dried dipalmitoylphosphatidylcholine: trehalose mixture (molar ratio 1:1) showed that the phase transition had a relaxation time of about 2 s which is similar to that of the main transition in the fully hydrated lipid. X-ray diffraction studies of the melting of dipalmitoylphosphatidylcholine freeze-dried from the lamellar-gel phase in the absence of trehalose showed a transition at above 70 degrees C. The low-angle diffraction data of phospholipid/trehalose mixtures are consistent with an arrangement of trehalose molecules in a loosely packed 'monolayer' separating bilayers of phospholipid. Trehalose appears to reduce the direct interbilayer hydrogen bond coupling thereby modifying the thermal stability and the phase transition mechanism of the bilayers.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1988

Monovalent ion-phosphatidylcholine interactions: an electron paramagnetic resonance study.

The apparent Mn2+ binding constant for L-alpha-dipalmitoylphosphatidylcholine (DPPC) bilayers dispersed in monovalent salt and MnCl2 dispersions was determined as a function temperature using electron paramagnetic resonance (ERP). Reproducibility in the data sets requires the use of a standard salt solution and dual cavity techniques. Changes in the binding constant at different phase states and temperatures were observed and correlated to the influence of monovalent salts on the thermal properties of DPPC. The turning points (i.e. changes in slope) in the curves of the apparent Mn2+ binding constant versus temperature can be understood in terms of differences in ion binding to headgroups with different bilayer surface areas. The influence of Li+ and SCN- on Mn2+ binding is viewed as a function of their presence in the ionic media in contact with the bilayer rather than as a competitive event. Other monovalent ions studied appear to have little effect on the measured apparent Mn2+ binding constants for DPPC headgroups.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1988

Structures and mechanisms of lipid phase transitions in nonaqueous media. Dipalmitoylphosphatidylethanolamine in fused salt.

The phase transitions for dipalmitoylphosphatidylethanolamine (DPPE) dispersed in water and in N-ethylammonium nitrate (EAN) were examined using differential scanning calorimetry and time-resolved x-ray diffraction. Subgel, pre-, and main-phase transitions were observed for DPPE in water, whereas only the pre- and main transitions were observed for DPPE in EAN. Hysteresis was observed for both dispersions upon cooling. In addition, the lamellar (L alpha) to hexagonal (H alpha) phase transition was observed for DPPE dispersed in EAN when using time-resolved x-ray diffraction but not when using calorimetry. This low enthalpy process occurred at 73-77 degrees C, which is significantly lower than that observed for DPPE in water. The presence of EAN stabilizes the existence of the H alpha phase in DPPE by its influence on the bilayer interfacial properties, primarily on the area per lipid head group.

Calorimetry, Differential Scanning↗
PubMed1987

Mechanism and kinetics of the subtransition in hydrated L-dipalmitoylphosphatidylcholine.

The mechanism of the subtransitions (Lc to L beta') in L-dipalmitoylphosphatidylcholine bilayers in excess water has been investigated by time-resolved X-ray diffraction using synchrotron radiation. The temperature dependence of the diffraction patterns closely correlate with the asymmetric excess specific heat variation recorded by differential scanning calorimetry. During the subtransition two prominent wide-angle reflections, characteristic of the low-temperature crystalline phase, Lc, gradually change such that a sharp peak at a spacing of 0.430 nm decreases in intensity and ultimately disappears while a broader peak initially located at 0.375 nm progressively shifts to an eventual spacing of 0.410 nm. This behaviour is interpreted as a lateral deformation of the acyl chain packing subcell as the chains begin to rotate until a state is reached where the chains pack on a regular hexagonal array characteristic of the L beta phase. An increase in lamellar repeat distance from 6.0 to 6.4 nm takes place simultaneously with the acyl chain rearrangement at relatively low (5 K/min) as well as high (6 K/s) heating rates. As judged from the shape of the wide-angle peak, transformation to L beta' phase occurs some minutes after transition to the L beta phase. The X-ray data characterise the subtransition as a continuous (second order) phase transition in which a presumably orthorhombic subcell is transformed into a hexagonal subcell in a gradual process. In temperature jump experiments at 6 K/s between 0 degree C and 80 degrees C the relaxation time of the subtransition was found to be about 5 s while the relaxation time of the main gel to liquid-crystalline transition was about 2 s.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1986

Thiocyanate and bromide ions influence the bilayer structural parameters of phosphatidylcholine bilayers.

The influence of monovalent cations and anions on the structural parameters of dipalmitoylphosphatidylcholine (DPPC) bilayers was examined at 25 degrees C using X-ray diffraction. It was shown that monovalent salts, in general, have little effect on lipid packing within the bilayer. However, fully hydrated DPPC bilayers in 1 M KSCN pack in an interdigitated acyl chain phase. This is the first observation of an ion-induced interdigitated bilayer phase in a zwitterionic lipid. In addition, gel state DPPC bilayers in 1 M KBr imbibe approx. 10 A more solvent than bilayers in water. The influence of these same salts on the phase transitions of DPPC bilayers was also examined using high-resolution differential scanning calorimetry. These results are discussed in terms of ion-induced changes in solvent and solvent/bilayer structure.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1986

Ca2+ induced phase separations in phospholipid mixtures.

We have probed the character of the observed phase separation in mixtures of phosphatidylcholines (PC) and/or phosphatidylethanolamines (PE) in the presence of CaCl2 solutions. Egg yolk phosphatidylethanolamine (EYPE) and a 1:1 molar ratio of dioleoylphosphatidylcholine/dioleoylphosphatidylethanolamine (DOPC/DOPE) were observed to undergo phase separation in CaCl2 solutions, as was previously observed for egg yolk phosphatidylcholine (EYPC) (L.J. Lis et al. Biochemistry, 20 (1981) 1771-1777). However, the mixed chain lipid, palmitoyloleoyl-PC, yielded only a single phase in water or CaCl2 solution. We hypothesize that two lipid species are necessary for the observed phase separation to occur, but that the separation itself is not a function of the individual lipid species, but of the mixture.

Calcium↗
PubMed1986

The influence of ion species on phosphatidylcholine bilayer structure and packing.

The effects of various monovalent cations and anions on the bilayer packing and structure of dipalmitoylphosphatidylcholine were studied using X-ray diffraction and differential scanning calorimetry. It was observed from the X-ray diffraction studies that monovalent salts, in general, have no effect on bilayer packing. The results of DSC studies on metal chloride systems are consistent with the interpretation that cations in general and Li+ in particular bind to DPPC bilayers. The effect of potassium salts on pre- and main-transition temperatures suggest that anions, such as Acetate-, also significantly bind to DPPC head groups.

Anions↗
PubMed1986

The influence of oxygenated sterol compounds on dipalmitoylphosphatidylcholine bilayer structure and packing.

Fourier Transform Infra-red and Raman Spectroscopies indicate that 7 alpha-hydroxycholesterol and 7-ketocholesterol have a diminished capacity to condense (increase the packing order of) fluid-state dipalmitoylphosphatidylcholine (DPPC) acyl chains when compared with the effects of cholesterol and the other oxidized sterols studied. DPPC head groups were also more ordered by 7-ketocholesterol over the temperature range 10 degrees - 70 degrees C. Primary effects of these sterols appear to be associated with the hydrophillic regions of the DPPC bilayer, although packing arrangements with acyl chains are also involved. Phosphate and acyl chain ester groups were observed to possess a packing order which was invariant which indicates that these may be the target groups in the interaction with 7-ketocholesterol. A surprising observation was the synergistic amplification of the effects of 7-ketocholesterol by the presence of cholesterol in the DPPC bilayer.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1985

Oxygenated cholesterols synergistically immobilize acyl chains and enhance protein helical structure in human erythrocyte membranes.

Fourier transform infrared spectroscopy revealed that insertion of 20 alpha-hydroxycholesterol into human erythrocyte membranes (10% of total membrane sterol) immobilized the lipid acyl chains to a degree equivalent to enriching total membrane cholesterol by 50% (Rooney, M.W., Lange, Y. and Kauffman, J.W. (1984) J. Biol. Chem. 259, 8281-8285). Raman spectroscopy showed that the amount of acyl chain rotamers was not significantly altered by the presence of 20 alpha-hydroxycholesterol, indicating that acyl chain immobilization was limited to an inhibition of lateral motion. The presence of 20 alpha-hydroxycholesterol may synergistically enhance the acyl-chain-immobilizing behavior of membrane cholesterol. In addition, protein helical structure was not altered by 20 alpha-hydroxycholesterol. The insertion of 7 alpha-hydroxycholesterol into erythrocyte membranes resulted in an increase in protein helical structure which was comparable to that observed for erythrocyte membranes enriched with pure cholesterol by 50%. However, both acyl chain mobility and conformation were unchanged. These results suggest a synergistic behavior between oxysterols and cholesterol in modifying erythrocyte membrane packing.

Cholesterol↗
PubMed1983

Anion influence on the binding of divalent cations to phosphatidylcholine.

We have used the osmotic pressure technique of Rand, Parsegian and co-workers (Nature 259 (1976) 601-603) to investigate the effect of anion species on the binding of M2+ to dipalmitoylphosphatidylcholine bilayers. Calcium and magnesium salts show a complex behavior which is consistent with both anion binding and screening. We observe virtually no change, within the accuracy of our experiment, in the decay of repulsive pressure with inter-bilayer separation for the acetate and nitrate salts of magnesium and calcium; however, the chloride salt does show a different pressure decay. At any given bilayer separation, 35 A less than dw less than 75 A, with calcium and magnesium salts present, the anions produce a decrease in the repulsive pressure in the order acetate- greater than Cl- greater than NO-3.

Anions↗
PubMed1983

Raman spectroscopic and X-ray diffraction studies of the effect of temperature and Ca2+ on phosphatidylethanolamine dispersions.

Raman spectroscopy and X-ray diffraction are used to study the effect of heat and Ca2+ on dimyristoylphosphatidylethanolamine dispersions. Unlike phosphatidylcholine dispersions, dimyristoylphosphatidylethanolamine bilayers (at pH 8) require heating above Tm in order for hydration to occur and apparently bind Ca2+ at very low levels. These results are related to models for membrane fusion.

Calcium↗
PubMed1982

Changes in the plasma membrane of yeast observed by spin label electron spin resonance and caused by photodynamic attack.

Spin label electron spin resonance (ESR) was used to characterize the response of lipid regions of the plasma membrane of yeast to photodynamic attack. Following photodynamic attack, the structure of these lipid regions changed resulting in the disappearance of an apparent order-disorder phase transition as well as impeding the diffusion of the steric acid based spin label 12NS into and across the plasma membrane. We propose that singlet molecular oxygen reacting with unsaturated carbon bonds in the fatty acyl chains of lipid surrounding channel proteins leads to an increase in the order of the lipid array and/or a change in the channel protein's conformation and is the cause of the lethal effect of externally sensitized photodynamic action.

Cell Membrane↗
PubMed1982

Interactions between neutral phospholipid bilayer membranes.

We have obtained force vs. separation relations between bilayers in 10 different phospholipid preparations: dilauroyl-dimyristoyl-, dipalmitoyl-, distearoyl-, or dioleoylphosphatidylcholine (PC); egg phosphatidylethanolamine; cholesterol-containing bilayers of dipalmitoyl PC and of egg PC. The chemical potential of water in the multilamellar lattice is determined at all water contents and changes continuously with bilayer separation; no discrete classes of water are observed. The interbilayer van der Waals force is estimated from the balance of forces at the bilayer separation where the multilayer lattice is in equilibrium with pure water. Although quantitative differences are evident for different phospholipids, all force curves but one show a clear, exponentially decaying "hydration "repulsion" whose decay distance is 2-3 A . Estimates of forces between bilayer vesicles show great sensitivity to the identity of the phospholipid polar group and to the packing of the hydrocarbon acyl chains. On major implication of this is the likelihood of local structural changes and lipid segregation in the area of closest approach of interacting vesicles of mixed phospholipids.

Chemical Phenomena↗
PubMed1982

Measurement of the lateral compressibility of several phospholipid bilayers.

Lateral compressibilities of bilayers in multilayer lattices are given for 10 phospholipid preparation:dilauryl-, dimyristoyl-, dipalmitoyl-, distearoyl-, and dioleoylphosphatidylcholine (PC); egg phosphatidylethanolamine (PE); as well as cholesterol-containing bilayers of dipalmitoyl PC or of egg PC. Bilayer deformability is highly nonlinear and does not permit description in terms of a simple modulus. The presence of cholesterol or C=C bonds (dioleoyl PC) increases deformability, but freezing of acyl chains does not cause dramatic stiffening of the bilayer. Lateral compression of dilauryl PC an dimyristoyl PC causes a transition from "melted" to "frozen" acyl chains above the normal transition temperatures. Our measurements do not correspond in any obvious way to lateral compressibilities in monolayers at the air-water interface.

Cholesterol↗
PubMed1981

Binding of divalent cations of dipalmitoylphosphatidylcholine bilayers and its effect on bilayer interaction.

We have confirmed that CaCl2 swells the multilayer lattice formed by dipalmitolyphosphatidylcholine (DPPC) in an aqueous solution. Specifically, at room temperature 1 mM CaCl2 causes these lipid bilayers to increase their separation, dw, from 19 A in pure water to greater than 90 A. CaCl2 concentrations greater than 4 mM cause less swelling. We have measured the net repulsive force between the bilayers in 30 mM CaCl2 at T = 25 degrees C (below the acyl chain freezing temperature). For interbilayer separations between 30 and 90 A, the dominant repulsion between bilayers is probably electrostatic; Ca2+ binds to DPPc lecithin bilayers, imparting a charge to them. The addition of NaCl to CaCl2 solutions decreases this repulsion. For dw less than 20 A, the bilayer repulsion appears to be dominated by the "hydration forces" observed previously between both neutral and charged phospholipids. From the electrostatic repulsive force, we estimate the extent of Ca2+ binding to the bilayer surface. The desorption and bound Ca2+, apparent when bilayers are pushed together, is more rapid than one would expect if an association constant governed Ca2+ binding. The association affinity does not appear to be a fixed quantity but rather a sensitive function of ionic strength and bilayer separation.

Calcium↗
PubMed1981

Adsorption of divalent cations to a variety of phosphatidylcholine bilayers.

We have determined the degree of binding of divalent cations to several kinds of phosphatidylcholine (PC) bilayers. This has been done by measuring the electrostatic interbilayer repuslive force that results when multilamellar lattices are exposed to Me2+Cl2 solutions. Divalent cations bind to dipalmitoylphosphatidylcholine in the sequence Ca2+ approximately equal to Cd2+ approximately equal to Mn2+ greater than Ca2+ approximately equal to Mg2+ greater than Ba2+. Among the different synthetic lipids, preference for Ca2+ is in the sequence DOPC less than DLPC less than DMPC approximately equal to DPPC approximately equal to DSPC. The density of bound charge is proportional to the density of polar groups on the bilayer surface. Phosphatidylcholines with mixed hydrocarbon chains, such as egg PC or 1:1 mixtures of synthetic PC's, form two distinct lamellar phases in CaCl2 solutions. In all cases the electrostatic force between bilayers decays exponentially with their separation but more slowly than expected from ionic double-layer theory. We suggest that the electric fields from opposing surfaces perturb the zwitterionic charge-binding polar groups and continuously modify their ion binding affinities as the bilayers approach.

Calcium↗
PubMed1980

The effect of cholesterol on measured interaction and compressibility of dipalmitoylphosphatidylcholine bilayers.

We have examined the phase diagram of dipalmitoylphosphatidylcholine (DPPC)--cholesterol-water mixtures at low cholesterol content, and report phase separation between 3 and 10 mol% cholesterol. The two lamellar phases at equilibrium in this region appear to be pure DPPC and 11 mol% cholesterol in DPPC. For these two lamellar phases, which are made up of alternating layers of water and bimolecular lipid leaflets, we have measured the forces of interaction between leaflets and the lateral pressure and compressibility of the leaflets. Both bilayers experience a strong repulsive force when forced together only a few ångströms (1 A = 0.1 nm) closer than their maximum separation in excess water. However, the presence of 11 mol% cholesterol causes the bilayers to move apart of 35-A separation from the 19-A characteristic of pure DPPC in excess water. This swelling may result from a decrease in van der Waals attraction between bilayers or from an increase in bilayer repulsion. Differences in bilayer interaction can be a cause for phase separation. More importantly these differences can cause changes in the composition of regions of membranes approaching contact. At 11 mol%, cholesterol substantially increases the lateral compressibility of DPPC bilayers leading to higher lateral density fluctuations and potentially higher bilayer permeability.

Chemical Phenomena↗