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At least 433 records · Page 24Linked to original sources
PubMed1982

On the phase transition kinetics of phospholipid bilayers. Relaxation experiments with detection of fluorescent anisotropy.

Relaxation experiments were performed on vesicles of dimyristoylphosphatidylcholine in the lipid phase transition region by means of a Joule heating temperature jump technique. The time course of fluorescence anisotropy of the dye 1,6-diphenyl-1,3,5-hexatriene (DPH), incorporated in the bilayer, was observed. Since the dye always exhibits stationary anisotropy in the time range of observation, its anisotropy represents the order of the bilayer during the entire course of the experiment. Two relaxation processes were detected within the 1-100 ms range with maximal time constants at the midpoint of transition. At least one process was faster than the temperature jump dead time. The relaxation times, especially the maximal relaxation times, depend strongly on the bilayer curvature: larger vesicles imply larger time constants. This observation can explain differences between kinetic results of different laboratories. A comparison between the kinetic findings by means of three different dyes located at different sites along the lipid molecules suggests that the slower steps of the lipid phase transition mechanism involve the entire lipid molecule rather than individual parts of the molecule. The results of this present contribution reconfirm the recently published phase transition mechanism which postulates a series of steps of which the first, the kink formation, is fast and noncooperative and the following ones, representing the expansion of the aggregates, are slower and cooperative.

Dimyristoylphosphatidylcholine↗
PubMed2006

Anomalous latent heat in nonequilibrium phase transitions.

We study first-order phase transitions in a two-temperature system, where due to the time-scale separation all the basic thermodynamical quantities (free energy, entropy, etc.) are well defined. The sign of the latent heat is found to be counterintuitive: it is positive when going from the phase where the temperatures and the entropy are higher to the one where these quantities are lower. The effect exists only out of equilibrium and requires conflicting interactions. It is displayed on a lattice gas model of ferromagnetically interacting spin-1/2 particles.

Journal Article↗
PubMed1994

Differential scanning calorimetry of thermotropic phase transitions in vitaminylated lipids: aqueous dispersions of N-biotinyl phosphatidylethanolamines.

The thermotropic phase behavior of a homologous series of saturated diacyl phosphatidylethanolamines in which the headgroup is N-derivatized with biotin has been investigated by differential scanning calorimetry. In 1 M NaCl, derivatives with acyl chainlengths from C(12:0) to C(20:0) all exhibit sharp chain-melting phase transitions, which are reversible with a hysteresis of 1.5 degrees or less, except for the C(12:0) lipid which has a transition temperature below 0 degree C. The transition enthalpy and the transition entropy depend approximately linearly on the lipid chainlength, with incremental values per CH2 group that are very similar to those obtained for the corresponding underivatized phosphatidylethanolamines in aqueous dispersion. The chainlength-independent contribution to the transition enthalpy is significantly smaller than that for the underivatized phosphatidylethanolamines, and that for the transition entropy is much smaller; the latter suggesting that the N-biotinylated phosphatidylethanolamine headgroups are differently hydrated from those of the underivatized lipids. The gel-to-fluid phase transition temperatures of the N-biotinylated lipids are lower than those of the parent phosphatidylethanolamines, and their chainlength dependence conforms well with that predicted by assuming that the transition enthalpy and entropy are linearly dependent on chainlength. Although the chain-melting phase behavior is generally similar to that of the parent phosphatidylethanolamines, the gel phases (and the fluid phases in the case of chainlengths C(12:0) to C(16:0)) have a different lyotropic structure in the two cases, and this is reflected in the chainlength-independent contributions to the thermodynamic parameters. In the absence of salt, the thermotropic phase behavior of aqueous dispersions of the N-biotinyl phosphatidylethanolamines is considerably more complex. The transition temperatures are consistently lower than those in 1 M NaCI, but the transitions are broader, contain multiple peaks and exhibit a much larger hysteresis between heating and cooling scans. Additionally, the lipids with shorterchainlengths exhibit metastability in the absence of salt, converting from a micellar solution to a lamellar gel phase only after incubation at low temperature with freeze-thaw cycling.

Biotin↗
PubMed2002

London theory for superconducting phase transitions in external magnetic fields: application to UPt3.

For multicomponent superconductors, it is known that the presence of symmetry breaking fields can lead to multiple superconducting phase transitions. Motivated by recent small angle neutron scattering experiments on the vortex state of UPt3, the London theory in the vicinity of such phase transitions is determined. It is found that the form of this London theory is in general quite different than that for conventional superconductors. This is due to the existence of a diverging correlation length associated with these phase transitions. One striking consequence is that nontrivial vortex lattices exist arbitrarily close to H(c1). Applications to UPt3, CeIn3, U(1-x)Th(x)Be(13), electron doped cuprate superconductors, Sr(2)RuO(4), and MgCNi(3) are discussed.

Journal Article↗
PubMed2004

Investigation of temperature-induced phase transitions in DOPC and DPPC phospholipid bilayers using temperature-controlled scanning force microscopy.

Under physiological conditions, multicomponent biological membranes undergo structural changes which help define how the membrane functions. An understanding of biomembrane structure-function relations can be based on knowledge of the physical and chemical properties of pure phospholipid bilayers. Here, we have investigated phase transitions in dipalmitoylphosphatidylcholine (DPPC) and dioleoylphosphatidylcholine (DOPC) bilayers. We demonstrated the existence of several phase transitions in DPPC and DOPC mica-supported bilayers by both atomic force microscopy imaging and force measurements. Supported DPPC bilayers show a broad L(beta)-L(alpha) transition. In addition to the main transition we observed structural changes both above and below main transition temperature, which include increase in bilayer coverage and changes in bilayer height. Force measurements provide valuable information on bilayer thickness and phase transitions and are in good agreement with atomic force microscopy imaging data. A De Gennes model was used to characterize the repulsive steric forces as the origin of supported bilayer elastic properties. Both electrostatic and steric forces contribute to the repulsive part of the force plot.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1981

Phase transitions in lipid bilayers. A theoretical model for phosphatidylethanolamine and phosphatidic acid bilayers.

We present an application of an earlier model to the description of phase transitions in phosphatidylethanolamine and phosphatidic acid bilayers. For the former system we modify the model to allow for very slightly closer chain packing. This small modification alone is sufficient to shift the main phase transition temperature to higher values, and to eliminate the lower transition. For the charged bilayers we incorporate electrostatic contributions into the free energy using double layer theory and we consider the excluded volume of counterions at the bilayer/water interface. Phase transition temperatures and the presence of absence of a lower transition are determined for various pH values, and the results are compared with experiment.

Hydrogen-Ion Concentration↗
PubMed2004

Nonequilibrium phase transitions in models of adsorption and desorption.

The nonequilibrium phase transition in a system of diffusing, coagulating particles in the presence of a steady input and evaporation of particles is studied. The system undergoes a transition from a phase in which the average number of particles is finite to one in which it grows linearly in time. The exponents characterizing the mass distribution near the critical point are calculated in all dimensions.

Journal Article↗
PubMed1980

Lipid and protein composition and thermotropic lipid phase transitions in fatty acid-homogeneous membranes of Acholeplasma laidlawii B.

The membrane composition and lipid physical properties have been systematically investigated as a function of fatty acid composition for a series of Acholeplasma laidlawii B membrane preparations made homogeneous in various fatty acids by growing cells on single fatty acids and avidin, a potent fatty acid synthetic inhibitor. The membrane protein molecular weight distribution is essentially constant as a function of fatty acid composition, but the lipid/protein ratio varies over a 2-fold range when different fatty acid growth supplements are used. The membrane lipid head-group composition varies somewhat under these conditions, particularly in the ratio of the two major neutral glycolipids. Differential thermal analytical investigations of the thermotropic phase transitions of various combinations of membrane components suggest that these compositional changes are unlikely to result in qualitative changes in the nature of lipid-protein or lipid-lipid interactions, although lesser changes of a quantitative nature probably do occur. The total lipids of membranes made homogeneous in their lipid fatty acyl chain composition exhibit sharper than normal gel-to-liquid-crystalline phase transitions of which midpoint temperatures correlate very well with the phase transition temperatures of synthetic hydrated phosphatidylcholines with like acyl chains. Our results indicate that using avidin and suitable fatty acids to grow A. laidlawii B, it is possible to manipulate the position and the sharpness of the membrane lipid phase transition widely and independently without causing major modifications in other aspects of the membrane composition. This fact makes the fatty acid-homogeneous A. laidlawii B membrane a very useful biological membrane preparation in which to study lipid physical properties and their functional consequences.

Acholeplasma laidlawii↗
PubMed1976

Fluorescence depolarization studies of phase transitions and fluidity in phospholipid bilayers. 2 Two-component phosphatidylcholine liposomes.

The fluorescence deplorarization associated with the hydrophobic fluorescent probe 1,6-diphenyl-1,3,5-hexatriene is used to monitor changes in fluidity accompanying the gel-liquid crystalline phase transition in phosphatidylcholine dispersions. In this way, the parameters of the phase transition are determined for both large, multilamellar liposomes and small, single-lamellar vesicles composed of three mixtures of phosphatidycholines: dimyristoyl-dipalmitoyl, dimyristoyl-distearoyl, and dioleyl-dipalmitoyl. Phase diagrams for these mixed-lipid vesicles are constructed by plotting the delimiting temperatures of the phase transition vs. the lipid compostion of the vesicle. The phase diagrams are interpreted to suggest that the miscibilities of the lipids studied are markedly different in small, single-lamellar vesicles and large multilamellar liposomes. These results are discussed in terms of the effects of high curvature on the structure of biological membranes.

Binding Sites↗
PubMed1980

Fluorescence depolarization studies of phase transition and fluidity in lecithin liposomes containing alpha-tocopherol.

The effects of alpha-tocopherol and related compounds on the membrane fluidity of liposomes composed of dipalmitoyl-lecithin or egg lecithin were studied by measuring the fluorescence polarization of DPH(1,6-diphenyl-1,3,5-hexatriene), a hydrophobic fluorescent probe distributed in the hydrocarbon region of lipid bilayers. The transition temperature of dipalmitoyl-lecithin liposomes was lowered on incorporation of alpha-tocopherol into the membranes. A similar effect was observed on incorporation of phytol or phytanic acid into liposomes, but not on incorporation of 2,2,5,7,8-pentamethyl-1-hydroxychroman as an alpha-tocopherol model compound (TMC) which lacks an isoprenoid side chain. Above the phase-transition temperatures, incorporation of alpha-tocopherol or TMC dose-dependently increased the polarization values of DPH in dipalmitoyl-lecithin and egg lecithin liposomes, while incorporation of phytol or phytanic acid had little effect or slightly lowered the polarization. These results suggest that the effect of alpha-tocopherol in lowering the phase-transition temperature depends on its hydrophobic side chain, and that its effect in decreasing the membrane fluidity above the phase-transition temperature depends on its hydrophylic chroman ring portion. Cholesterol had an effect similar to alpha-tocopherol on membrane fluidity. alpha-Tocopherol and cholesterol had independent effects in increasing the polarization of DPH above the phase-transition temperature when the two compounds were incorporated together into liposomes.

Cholesterol↗
PubMed2005

Liquid-liquid phase transition for an attractive isotropic potential with wide repulsive range.

We investigate how the phase diagram of a repulsive soft-core attractive potential, with a liquid-liquid phase transition in addition to the standard gas-liquid phase transition, changes by varying the parameters of the potential. We extend our previous work on short soft-core ranges to the case of large soft-core ranges, by using an integral equation approach in the hypernetted-chain approximation. We show, using a modified van der Waals equation we recently introduced, that if there is a balance between the attractive and repulsive part of the potential this potential has two fluid-fluid critical points well separated in temperature and in density. This implies that for the repulsive (attractive) energy U(R)(U(A)) and the repulsive (attractive) range w(R)(w(A)) the relation U(R)/U(A) proportional to w(R)/w(A) holds for short soft-core ranges, while U(R)/U(A) proportional to 3w(R)/w(A) holds for large soft-core ranges.

Journal Article↗
PubMed1979

Thermotropic phase transitions of phosphatidylcholines with odd-numbered n-acyl chains.

Diacyl phosphatidylcholines with n-C13, -C15, -C17 and -C19 saturated acyl chains have been synthesized and their phase transitions in the presence of excess water monitored by differential thermal analysis. The C15-, C17- and C19-diacyl species show gel to liquid-crystalline transitions and pretransitions like those of the even-chain phosphatidylcholines. A plot of the main phase transition temperature, Tc, vs. acyl chain length is a smooth curve on which the Tc values of both odd- and even-chain species fall, while a similar plot for the pretransition temperature, Tp, shows significant alternation of Tp between odd- and even-chain species. Consideration of these results in terms of the physical basis of the odd-even alternation of phase transition temperatures in homologous series of paraffinic compounds suggests that the acyl chains of disaturated phosphatidylcholines are tilted with respect to the bilayer normal below Tp but become perpendicular to the bilayer surface above the pretransition temperature.

Crystallization↗
PubMed2005

Multiphysics modelling of volume phase transition of ionic hydrogels responsive to thermal stimulus.

This paper presents the analysis of the volume phase transition of ionic thermo-sensitive hydrogels to thermal stimulus through mathematical modelling. The model is termed the multi-effect-coupling thermal-stimulus (MECtherm) model and it considers the effects of multi-phases and multi-physics. Its application to steady-state analysis of the hydrogels in swelling equilibrium is validated against available experimental data for the relation between volume swelling ratio and temperature, in which very good agreement is achieved. The phenomenon of volume phase transition is studied for the thermal-stimulus responsive hydrogel. The numerical studies predict well the influences of initially fixed charge density and initial volume fraction of polymeric network on the swelling equilibrium of the hydrogels.

Algorithms↗
PubMed1980

Gel to liquid-crystalline phase transitions of lipids and membranes isolated from Escherichia coli cells.

Differential scanning calorimetry (DSC) was used to examine the relationship of the gel to liquid-crystalline phase transition of lipids to fatty acid composition with membrane lipids and spheroplast membranes isolated from cells of a wild strain and an unsaturated fatty acid auxotroph of Escherichia coli grown under various conditions. These lipids and membranes underwent thermotropic phase transitions at different temperatures depending on the thermal properties of their constituent fatty acids. The lipid phase transition occurred at higher temperatures in biomembranes than in extracted lipids. DSC thermograms of lipids synthesized by bacterial cells which were observed at a temperature scanning rate as slow as 0.3 K min-1 were characterized by a distinctly plain peak summit. Endothermic peaks given by samples derived from elaidic acid-enriched cells were relatively narrow and asymmetric. The discrepancy between the transition temperatures measured with extracted lipids and with membraneous fractions, and the shape of the endothermic peaks, are discussed.

Calorimetry, Differential Scanning↗
PubMed1990

Effect of high electrolyte concentration on the phase transition behaviour of DPPC vesicles: a spin label study.

We have investigated by Electron Spin Resonance spectroscopy, the effects of high electrolyte concentration on the phase transitions of unilamellar vesicles of dipalmitoylphosphatidylcholine at the pH values of 5.0 and 9.0. Using the 5-nitroxide stearic acid as spin probe we have found that, at both pH values, the lipid main phase transition is not quite affected by variations of the electrolyte concentration up to the value of 3 M. Instead, the pretransition at pH 5.0 disappears in the presence of 1 M electrolyte, and at pH 9.0, the pretransition temperature shifts upward from 25.5 to 31.0 degrees C when the electrolyte concentration reaches the value of 3 M. The observed results on the pre- and main phase transition widths, transition temperatures and their cooperativity indicate that the presence of salt in the bulk solution leads to structural changes of the lipid bilayer which essentially concern either the polar zone or the hydrogen belt region of the DPPC vesicles. The extent of observed perturbation depends on salt concentration.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2006

First order phase transition in the frustrated triangular antiferromagnet CsNiCl3.

By means of high-resolution ultrasonic velocity measurements, as a function of temperature and magnetic field, the nature of the different low temperatures magnetic phase transitions observed for the quasi-one-dimensional compound CsNiCl3 is established. Special attention has been devoted to the field-induced 120 degrees phase transition above the multicritical point in the H-T phase diagram where the elastic constant C44 reveals a steplike variation and hysteresis effects. These results represent the first experimental evidence that the 120 degrees phase transition is weakly first order and contradict the popular notion of new universality classes for chiral systems.

Journal Article↗
PubMed2006

Ferroelectric phase transition in individual single-crystalline BaTiO3 nanowires.

We report scanned probe characterizations of the ferroelectric phase transition in individual barium titanate (BaTiO3) nanowires. Variable-temperature electrostatic force microscopy is used to manipulate, image, and evaluate the diameter-dependent stability of ferroelectric polarizations. These measurements show that the ferroelectric phase transition temperature (TC) is depressed as the nanowire diameter (dnw) decreases, following a 1/dnw scaling. The diameter at which TC falls below room temperature is determined to be approximately 3 nm, and extrapolation of the data indicates that nanowires with dnw as small as 0.8 nm can support ferroelectricity at lower temperatures. We also present density functional theory (DFT) calculations of bare and molecule-covered BaTiO3 surfaces. These calculations indicate that ferroelectricity in nanowires is stabilized by molecular adsorbates such as OH and carboxylates. These adsorbates are found to passivate polarization charge more effectively than metallic electrodes, explaining the observed stability of ferroelectricity in small-diameter BaTiO3 nanowires.

Anisotropy↗
PubMed2001

Nature of the liquid crystalline phase transitions in the cesium pentadecafluorooctanoate (CsPFO)-water system: the nematic-to-isotropic transition.

Deuterium NMR spectroscopy of 2H2O has been used to monitor the magnetic-field-induced order on approaching a transition to a nematic phase in isotropic solutions of disklike micelles of cesium pentadecafluorooctanoate. Highly accurate data on the phase boundaries and spinodals have been obtained for solutions with volume fraction concentration straight phi between 0.078 and 0.201. The quantity TIN-T*, where T* is the spinodal limit of the isotropic phase and TIN is the temperature at which the nematic phase first appears on cooling, decreases linearly with decreasing concentration, extrapolating to zero only at zero concentration. Thus, there is no evidence to support the presence of a Landau point along the transition line as has previously been conjectured. The values for (TIN-T*)/TIN are in the range 10(-5)-10(-4), up to two orders of magnitude smaller than corresponding values reported for calamitic thermotropic nematics. The transition gap (phiNI-phiIN)/phiIN approximately 0.33% for phi<0.20 is also very small, although finite as required for a first-order phase transition. These data, when combined with previously measured properties, present an intriguing picture of the isotropic-to-nematic phase transition in a paradigmatic system of self-assembled diskotic particles. However, it is not completely clear, within the context of current theoretical understanding, whether the behavior of this system is explicable by hard-particle models, or if the self-assembly plays a crucial role in weakening the phase transition.

Journal Article↗