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PubMed1990

A solid-solution theory of anesthetic interaction with lipid membranes: temperature span of the main phase transition.

Anesthetics (or any other small additives) depress the temperature of the main phase transition of phospholipid bilayers. Certain anesthetics widen the temperature span of the transition, whereas others do not. The widening in a first-order phase transition is intriguing. In this report, the effects of additive molecules on the temperature and its span were explained by the solid-solution theory. By assuming coexistence of the liquid-crystal and solid-gel phases of lipid membranes at phase transition, the phase boundary is determined from the distribution of anesthetic molecules between the liquid-crystal membrane versus water and between the solid-gel membrane versus water. The theory shows that when the lipid concentration is large or when the lipid solubility of the drug is large, the width of the transition temperature increases, and vice versa. Highly lipid-soluble molecules, such as long-chain alkanols and volatile anesthetics, increase the width of the transition temperature when the lipid:water ratio is large, whereas highly water-soluble molecules, such as methanol and ethanol, do not. The aqueous phase serves as the reservoir for anesthetics. Depletion of the additive molecules from the aqueous phase is the cause of the widening. When the reservoir capacity is large, the temperature width does not increase. The theory also predicts asymmetry of the specific heat profile at the transition.

Anesthetics↗

PubMed1981

Influence of dicarboxylic phosphatidylcholines on the stability and phase transition of phosphatidylcholine liposomes.

The effect of dicarboxylic phosphatidylcholines (glutaryl phosphatidylcholine) on the stability and phase transition of phosphatidylcholine liposomes is examined by using liposomes prepared with egg phosphatidylcholine or dipalmitoyl phosphatidylcholine and by varying the surface charge by addition of dicetyl phosphate. Light-scattering and osmotic behaviour studies showed that the stability of liposomes containing dicarboxylic phosphatidylcholine is influenced by the charge and the fatty acid saturation of the liposomes. Increasing the glutaryl phosphatidylcholine-to-phosphatidylcholine molar ratio in liposomes caused the formation of mixed glutaryl phosphatidylcholine/phosphatidylcholine micelles. The sensitivity of the lipid bilayers towards glutaryl phosphatidylcholine action increases with the fatty acid saturation of liposomes. Dipalmitoyl phosphatidylcholine liposomes are most sensitive to the dicarboxylic phosphatidylcholine effect. Dicetyl phosphate addition enhances the solubilization of liposomes prepared from saturated phospholipids. The effect of increasing concentrations of glutaryl phosphatidylcholine on the gel-to-liquid crystal thermal transition of dipalmitoyl phosphatidylcholine was observed. Glutaryl phosphatidylcholine modifies the thermal phase transition of the constituents of the liposome. The presence of dicetyl phosphate in liposomes affects the phase transition temperature of these liposomes. It is suggested that the formation of the mixed micelles is responsible for the phase transition modifications. These data show that the solubilization of liposomes by dicarboxylic phosphatidylcholines depends on the fatty acid composition of phosphatidylcholine and on the presence of dicetyl phosphate.

Liposomes↗

PubMed2001

Quantum phase transition for gamma-soft nuclei.

We examine a quantum phase transition in gamma-soft nuclei, where the O(6) limit is simultaneously a dynamical symmetry of the U(6) group of the interacting boson model and a critical point of a prolate-oblate phase transition. This is the only example of phase transitional behavior that can be described analytically for a finite s,d boson system.

Journal Article↗

PubMed1979

Antagonism between high pressure and anesthetics in the thermal phase-transition of dipalmitoyl phosphatidylcholine bilayer.

The antagonizing action of hydrostatic pressure against anesthesia is well known. The present study was undertaken to quantitate the effects of hydrostatic pressure and anesthetics upon the phase-transition temperature of dipalmitoyl phosphatidylcholine vesicles. The drugs used to anesthetize the phospholipid vesicles included an inhalation anesthetic, halothane, a dissociable local anesthetic, lidocaine and an undissociable local anesthetic, benzyl alcohol. All anesthetics decreased the phase-transition temperature dose-dependently. In the case of lidocaine, the depression was pH dependent and only uncharged molecules were effective. The application of hydrostatic pressure increased the phase-transition temperature both in the presence and the absence of anesthetics. The temperature-pressure relationship was linear over the entire pressure range studied up to 340 bars. Through the use of Clapeyron-Clausius equation, the volume change accompanying the phase-transition of the membrane was calculated to be 27.0 cm3/mol. Although the anesthetics decreased the phase-transition temperature, the molar volume change accompanying the phase-transition was not altered. The anesthetics displaced the temperature-pressure lines parallel to each other. The mole fraction of the anesthetics in the liquid crystalline membrane, calculated from the van't Hoff equation, was independent of pressure. This implies that pressure does not displace the anesthetics from the liquid membrane, and the partition of these agents remains constant. The volume change of the anesthetized phospholipid membranes is entirely dependent upon the phase-transition and not on the space occupied by the anesthetics.

Anesthetics↗

PubMedDate not supplied

Chilling sensitivity in zebrafish (Brachydanio rerio) oocytes is related to lipid phase transition.

Oocytes of zebrafish were used to study chilling sensitivity and membrane lipid phase transitions in tropical fish. The oocytes were divided into two groups: small (without yolk, <0.1mm) and large (with yolk, >0.1mm). After exposure of the oocytes to different temperatures (25, 22, 19, 16, 12, 8, 0, -8+0.5 degree C) for 15 minutes, the integrity of their membranes was determined by carboxyfluorescein diacetate (CFDA) staining. At 16 and 12 degree C, damage was maximum (membrane integrity decreased by 50%) for small and large sizes, respectively. Lipid phase transition (LPT), which was evaluated using Fourier transform infrared (FTIR) microscopy, indicated phase transitions at the same temperatures at which damage was maximal (between 22 and 12 degree C).In another series of experiments, the chilling sensitivity of oocytes taken from zebrafish which had been held at 16 degree C for different periods of time (0, 15, 30, 60 minutes) was determined as described above. In small oocytes membrane integrity decreased after 15 minutes, and in large oocytes integrity decreased after 30 minutes. Chilling sensitivity was also measured in oocytes from zebrafish that had been held at 16 degree C for 30 minutes and then rewarmed to 28 degree C for 2 hours. Despite this recovery period, the integrity of the oocytes remained low. We suggest that chilling sensitivity in zebrafish oocytes is related to lipid phase transition of their membranes and starts at 10 degree C below the physiological temperature

Journal Article↗

PubMed2002

A theoretical framework of ecological phase transitions for characterizing tree-grass dynamics.

This paper describes a theoretical framework of ecological phase transitions for modeling tree-grass dynamics and analyzing the shifts or phase transitions from one vegetation structure to another in the southern Texas landscape. This framework implements the integration of percolation theory, fractal geometry and phase transition theory as a method for modeling the spatial patterns of tree-grass dynamics, and nonlinear Markov non-equilibrium thermodynamic stability theory as a method for characterizing temporal tree-grass dynamics and phase transition. An historical sequence of aerial photographs at a Prosopis-thornscrub savanna parkland site in southern Texas was used to determine the parameters of the models. The preliminary analytical result accords well with current understanding and field survey of vegetation dynamics in the southern Texas landscape. The potential of such approaches and other relevant theories such as self-organized criticality and synergetics to vegetation dynamics is also discussed.

Ecosystem↗

PubMed2002

Coupling-reentrant phase transition, complex hysteretic behavior, and efficiency optimization in coupled phase oscillators submitted to colored flashing potentials.

A recent mean-field analysis of a model consisting of N nonlinear phase oscillators-under the joint influence of global periodic coupling with strength K0 and of local multiplicative and additive noises-has shown a nonequilibrium phase transition towards a broken-symmetry phase exhibiting noise-induced transport, or "ratchet" behavior. In a previous paper we focused on the relationship between the character of the (mean velocity vs load force F) hysteresis loop, the number of "homogeneous" mean-field solutions, and the shape of the stationary mean-field probability distribution function (PDF). Here we assume that the multiplicative noises of the model are Ornstein-Uhlenbeck with common strength Q and self-correlation time tau. By resorting to an effective Markovian approximation, we study the tau dependence of the phase boundary, and that of the line signaling the transition from the "interaction-driven regime" to the "noise-driven regime." We also study-for selected representative points of the K0 vs Q phase diagram-the tau dependence of the transport properties induced by coupling and colored multiplicative noise (including the efficiency epsilon of the mechanical rectification process) and that of the above-mentioned PDF.

Journal Article↗

PubMed1999

Two-photon fluorescence microscopy observation of shape changes at the phase transition in phospholipid giant unilamellar vesicles.

Using the sectioning effect of the two-photon fluorescence microscope, we studied the behavior of phospholipid giant unilamellar vesicles (GUVs) composed of pure diacylphosphatidylcholine phospholipids during the gel-to-liquid crystalline phase transition. We used the well-characterized excitation generalized polarization function (GP(ex)) of 6-dodecanoyl-2-dimethylamine-naphthalene (LAURDAN), which is sensitive to the changes in water content in the lipid vesicles, to monitor the phase transition in the GUVs. Even though the vesicles do not show temperature hysteresis at the main phase transition, we observed different behaviors of the vesicle shape, depending on how the GUV sample reaches the main phase transition. During the cooling cycles, we observed an increase in the vesicle diameter at the phase transition ( approximately 0.5-1%), followed by a decrease in the diameter when the vesicle reached the gel phase. During the heating cycles and close to the phase transition temperature, a surprising behavior is observed, showing a sequence of different vesicle shapes as follows: spherical-polygonal-ellipsoidal. We attribute these changes to the effect of lipid domain coexistence on the macroscopic structure of the GUVs. The "shape hysteresis" in the GUVs is reversible and largely independent of the temperature scan rate. In the presence of 30 mol% of cholesterol the events observed at the phase transition in the GUVs formed by pure phospholipids were absent.

2-Naphthylamine↗

PubMed2003

Disorder-induced rounding of certain quantum phase transitions.

We study the influence of quenched disorder on quantum phase transitions in systems with overdamped dynamics. For Ising order-parameter symmetry disorder destroys the sharp phase transition by rounding because a static order parameter can develop on rare spatial regions. This leads to an exponential dependence of the order parameter on the coupling constant. At finite temperatures the static order on the rare regions is destroyed. This restores the phase transition and leads to a double-exponential relation between critical temperature and coupling strength. We discuss the behavior based on Lifshitz-tail arguments and illustrate the results by simulations of a model system.

Journal Article↗

PubMed1998

Investigation of phase transitions in bilayer membranes.

This article described three techniques used to study phase transitions in phospholipid bilayers. The complementarity of the three techniques in characterizing the thermotropic and structural properties of phospholipid bilayers has been demonstrated by describing their use to characterize a series of mixed-chain-length PCs. It has been shown that an understanding of the energetics that govern the packing of phospholipid chains in the gel phase can be used to construct a model to interpret thermodynamic data of the PCs. This model, in turn, provided a framework for designing and interpreting the Raman spectroscopic and X-ray diffraction experiments on this series of phospholipids. The result was a complete description of the phase transitions and gel phase packing properties of the mixed-chain-length PCs. The phase diagram of Fig. 5B has been expanded to include the mixed-chain-length PC series C18C18PC through C18C0PC. Furthermore, the phase diagram and the chain inequivalence parameter have been shown to describe the behavior of any mixed-chain-length PC, irrespective of the lengths of the hydrocarbon chains or the position of the chains on the glycerol backbone. This is demonstrated by the additional mixed-chain-length PCs plotted in Fig. 5B. With minor modifications, the phase diagram also accurately describes the behavior of mixed-chain-length phosphatidylethanolamines, sphingomyelins, and unsaturated PCs. Finally, it has been demonstrated that a correlation exists between the thermodynamic and the Raman spectroscopic parameters determined for the phase transition of phospholipid bilayers. This correlation is based on the common chain energetics being measured by these two techniques.

Calorimetry, Differential Scanning↗

PubMed1979

Studies on human finger tapping neural networks by phase transition curves.

The human finger tapping was studied psychologically by the phase transition curves. We assumed that some oscillatory neural network controls the tapping. One of our future works on the human finger tapping is to devise a method to change the magnitude of perturbation continuously in phase resetting experiments of a constant tapping interval with a same kind of task. If this is achieved, we can obtain a phase transition surface (i.e. the new phase as a function of the old phase and the magnitude of perturbation). From the shape of a phase transition surface, the intrinsic properties of the oscillatory network which controls the tapping can be studied (Kawato et al., 1978).

Conditioning, Psychological↗

PubMed1986

Interaction of surfactants with vesicle membrane of dipalmitoylphosphatidylcholine. Effect on gel-to-liquid-crystalline phase transition of lipid bilayer.

The gel-to-liquid-crystalline phase transition of dipalmitoylphosphatidylcholine (DPPC) vesicle membrane was observed in the presence of various types of surfactants; sodium alkylsulfates, alkyltrimethylammonium bromides, alkanoyl-N-methylglucamides, and hexaethyleneglycol mono n-dodecyl ether. The phase transition was monitored by a change in scattered light intensity of the lipid suspension. For all the surfactants examined, the phase transition temperature was depressed linearly with the surfactant concentration in the measured concentration range, from which the partition coefficient, K, of the surfactant between bulk solution and lipid membrane was estimated. Except alkyltrimethylammonium bromides, log K and log CMC showed a linear relationship, which indicates that the driving force to transfer the surfactant from bulk solution to lipid membrane is a hydrophobic interaction. The addition of surfactants increased the transition width. The extent of widening the transition width was in the order of sodium alkylsulfate greater than alkyltrimethylammonium bromides greater than hexaethyleneglycol mono n-dodecyl ether; in the case of alkanoyl-N-methylglucamides, the transition width was not affected by the addition. These effects on the transition width was interpreted qualitatively in terms of the cooperativity of the transition.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed1983

Order-disorder phase transition and lipid dynamics in rabbit small intestinal brush border membranes. Effect of proteins.

The total lipids extracted from brush border membranes form smectic lamellar phases when dispersed in water. 31P broad-band nuclear magnetic resonance (NMR) shows that between body temperature (37 degrees C) and freezing of the solvent, the extracted lipids form bilayers with the lipid molecules undergoing fast anisotropic motion. This is also true for the lipids present in the brush border membrane. The electron spin resonance (ESR) results obtained with various hydrophobic spin probes incorporated in either brush border vesicle membranes or their extracted lipids are consistent with this interpretation. By use of a variety of chemically different spin-labels, the temperature dependence of brush border membranes and their extracted lipids was probed. The temperature dependence of various ESR spectral parameters shows discontinuities that, by comparison with differential scanning calorimetry, are assigned to a lipid thermotropic phase transition. Differential scanning calorimetry shows that the lipid in brush border membranes undergoes a broad, reversible phase transition of low enthalpy between 10 and 30 degrees C, with a peak temperature of about 25 degrees C. Hence, the brush border membrane of rabbit small intestine functions in the liquid-crystalline state, well above the peak temperature and also above the upper limit of the lipid phase transition. Therefore, in itself, the thermotropic lipid phase transition is unlikely to play a physiological role. The low enthalpy of the lipid phase transition, indicative of a lack of cooperativity, is primarily attributed to the relatively high cholesterol content and to heterogeneity in the lipid composition of this membrane [Hauser, H., Howell, K., Dawson, R. M. C., & Bowyer, D. E. (1980) Biochim. Biophys. Acta 602, 567-577].(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

PubMed2000

Classification of phase transitions in small systems

We present a classification scheme for phase transitions in finite systems like atomic and molecular clusters based on the Lee-Yang zeros in the complex temperature plane. In the limit of infinite particle numbers the scheme reduces to the Ehrenfest definition of phase transitions and gives the right critical indices. We apply this classification scheme to Bose-Einstein condensates in a harmonic trap as an example of a higher order phase transition in a finite system and to small Ar clusters.

Journal Article↗

PubMed1992

Energetics of a hexagonal-lamellar-hexagonal-phase transition sequence in dioleoylphosphatidylethanolamine membranes.

The phase diagram of DOPE/water dispersions was investigated by NMR and X-ray diffraction in the water concentration range from 2 to 20 water molecules per lipid and in the temperature range from -5 to +50 degrees C. At temperatures above 22 degrees C, the dispersions form an inverse (HII) phase at all water concentrations. Below 25 degrees C, an HII phase occurs at high water concentrations, an L alpha phase is formed at intermediate water concentrations, and finally the system switches back to an HII phase at low water concentrations. The enthalpy of the L alpha-HII-phase transition is +0.3 kcal/mol as measured by differential scanning calorimetry. Using 31P and 2H NMR and X-ray diffraction, we measured the trapped water volumes in HII and L alpha phases as a function of osmotic pressure. The change of the HII-phase free energy as a function of hydration was calculated by integrating the osmotic pressure vs trapped water volume curve. The phase diagram calculated on the basis of the known enthalpy of transition and the osmotic pressure vs water volume curves is in good agreement with the measured one. The HII-L alpha-HII double-phase transition at temperatures below 22 degrees C can be shown to be a consequence of (i) the greater degree of hydration of the HII phase in excess water and (ii) the relative sensitivities with which the lamellar and hexagonal phases dehydrate with increasing osmotic pressure. These results demonstrate the usefulness of osmotic stress measurements to understand lipid-phase diagrams.

Calorimetry, Differential Scanning↗

PubMed1998

Proton induced vesicle fusion and the isothermal lalpha-->HII phase transition of lipid bilayers: a 31P-NMR and titration calorimetry study.

The proton-induced isothermal fusion of unilamellar lipid vesicles (Duzgunes et al., Biochemistry 24 (1985) 3091-3098) is compared with the lamellar (Lalpha)-->hexagonal (HII) phase transition of multilamellar lipid dispersions. Both lipid systems are composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) and oleic acid (OA) at a 7:3 molar ratio. Using solid-state phosphorus-31 nuclear magnetic resonance (31P-NMR) it is demonstrated that the multilamellar lipid dispersions are in the bilayer state at physiological pH and undergo a Lalpha-->HII phase transition between pH 6.3 and 5.7. This phase transition can also be induced at constant pH by increasing the temperature. The midpoint of the temperature-induced Lalpha-->HII transition is Th=56 degrees C (at pH 7.4) and the corresponding transition enthalpy is DeltaH=0. 7+/-0.1 kcal/mol as determined with differential scanning calorimetry. Both the proton-induced and the temperature-induced phase transition can be completely inhibited by addition of 30 mol% of 1-palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine (LPC). In a second set of experiments unilamellar vesicles are prepared either by sonication or by extrusion through polycarbonate filters at pH 7. 4 and are titrated into buffer at pH 5.7. The proton-induced fusion of the lipid vesicles is monitored with isothermal titration calorimetry, light scattering and fluorescence spectroscopy. The fusion reaction is characterized by an endothermic enthalpy of DeltaH=0.5+/-0.2 kcal/mol (at 28 degrees C). The fusion enthalpy is independent of the vesicle diameter and is only slightly reduced by an increase in temperature to 50 degrees C. Vesicle fusion is accompanied by an increase in light scattering, indicating the formation of larger lipid structures. The transition from unilamellar vesicles to fused lipid structures occurs in the same narrow pH range of 6.3-5.7 as observed for the Lalpha-->HII transition of multilamellar dispersions. Vesicle fusion can be inhibited with 30% LPC. The virtually identical set of parameters found for the Lalpha-->HII phase transition and the vesicle fusion reaction suggests that vesicle fusion also entails a Lalpha-->HII phase transition.

Calorimetry↗

PubMed1984

Changes in thermal phase transition of various membranes during temperature acclimation in Tetrahymena.

Changes in the thermal phase transition temperature of membrane lipids were studied by X-ray wide-angle diffraction during adaptation of Tetrahymena pyriformis to a lower growth temperature. After a shift in growth temperature from 39 to 15 degrees C, the phase transition temperature was lowered gradually in microsomal and pellicular phospholipids, whereas that in mitochondrial phospholipids was unchanged for 10 h after the temperature shift. Only a small decrease in the transition temperature of mitochondrial phospholipids was observed, even after 24 h following the shift. Transition temperatures of microsomal, pellicular and mitochondrial phospholipids reached the growth temperature (15 degrees C) about 6, 10 and 24 h after the temperature shift. The temperature dependence of the solid phase in membrane phospholipids was estimated from the 4.2 A peak of the X-ray diffraction pattern. In the case of the phospholipids extracted from cells grown at 39 degrees C, the solid phase was increased upon lowering temperature in a similar manner in all three membrane fractions: mitochondria, pellicles and microsomes. However, in the case of the phospholipids from cells exposed to a lower growth temperature (15 degrees C) for 10 h, the increase in the solid phase was significantly smaller in mitochondrial phospholipids than in two other membrane fractions. The difference in the thermal behaviour of mitochondrial lipid from pellicular and microsomal lipids is discussed in terms of phase transition and phase separation.

Adaptation, Physiological↗

PubMed1992

Effect of the chirality of the glycerol backbone on the bilayer and nonbilayer phase transitions in the diastereomers of di-dodecyl-beta-D-glucopyranosyl glycerol.

We have studied the physical properties of aqueous dispersions of 1,2-sn- and 2,3-sn-didodecyl-beta-D-glucopyranosyl glycerols, as well as their diastereomeric mixture, using differential scanning calorimetry and low angle x-ray diffraction. Upon heating, both the chiral lipids and the diastereomeric mixture exhibit characteristically energetic L beta/L alpha phase transitions at 31.7-32.8 degrees C and two or three weakly energetic thermal events between 49 degrees C and 89 degrees C. In the diastereomeric mixture and the 1,2-sn glycerol derivative, these higher temperature endotherms correspond to the formation of, and interconversions between, several nonlamellar structures and have been assigned to L alpha/QIIa, QIIa/QIIb, and QIIb/HII phase transitions, respectively. The cubic phases QIIa and QIIb, whose cell lattice parameters are strongly temperature dependent, can be identified as belonging to space groups Ia3d and Pn3m/Pn3, respectively. In the equivalent 2,3-sn glucolipid, the QIIa phase is not observed and only two transitions are seen at 49 degrees C and 77 degrees C, which are identified as L alpha/QIIb and QIIb/HII phase transitions, respectively. These phase transitions temperatures are some 10 degrees C lower than those of the corresponding phase transitions observed in the diastereomeric mixture and the 1,2-sn glycerol derivative. On cooling, all three lipids exhibit a minor higher temperature exothermic event, which can be assigned to a HII/QIIb phase transition. An exothermic L alpha/L beta phase transition is observed at 30-31 degrees C. A shoulder is sometimes discernible on the high temperature side of the L alpha/L beta event, which may originate from a QIIb/L alpha phase transition prior to the freezing of the hydrocarbon chains. None of the lipids show evidence of a QIIa phase on cooling. No additional exothermic transitions are observed on further cooling to -3 degrees C. However, after nucleation at 0 degrees C followed by a short period of annealing at 22 degrees C, the 1,2-sn glucolipid forms an Lc phase that converts to an L alpha phase at 39.5 degrees C on heating. Neither the diastereomeric mixture nor the 2,3-sn glycerol derivative shows such behavior even after extended periods of annealing. Our results suggest that the differences in the phase behavior of these glycolipid isomers may not be attributable to headgroup size per se, but rather to differences in the stereochemistry of the lipid polar/apolar interfacial region, which consequently effects hydrogen-bonding, hydration, and the hydrophilic/hydrophobic balance.

Biophysical Phenomena↗