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At least 73 records · Page 4Linked to original sources

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↗

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↗

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↗

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↗

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↗

PubMed1993

Cold shock damage is due to lipid phase transitions in cell membranes: a demonstration using sperm as a model.

When cells are cooled to temperatures above the freezing point of water at rates greater than a few degrees per minute, they sustain irreversible injury. Reduction of this "cold shock" damage could increase the survival of animals and plants at low environmental temperatures and improve the cryopreservation of plant and animal cells. Leakage of solutes across membranes, associated with thermotropic phase transitions in membrane lipids, is thought to be responsible, but this hypothesis has not been tested directly. Using Fourier transform infrared spectroscopy (FTIR), we measured the lipid phase transitions in intact, living sperm, the animal cell in which cold shock has been studied most extensively. A shift in the CH2 absorbance peaks indicates the transition from liquid-crystalline to gel phase. The phase transition in sperm membranes occurred at a lower temperature for a marine shrimp than for the pig. In each case, potassium leakage, which is a hallmark of cold shock damage, increased abruptly near the end of the phase transition. Human sperm are quite resistant to cold shock, and an abrupt lipid phase transition was not detected. This phase behavior is typical of membranes containing a high proportion of cholesterol, and human sperm have an unusually high sterol content. High cholesterol levels are known to stabilize membranes during cooling. Overall, the lipid phase behavior was consistent with the temperature range over which cooling was damaging for pig and shrimp sperm, and the with the extent of damage produced in pig and human sperm. This is the first direct evidence that cold shock results from lipid phase transitions in cell membranes.

Animals↗

PubMed1993

Attempted improvement in mammography by inducing a phase transition in silicone gel.

An attempt was made to achieve a temporary alteration of the molecular structure (a "phase transition") of silicone gel, the end result of which would be to improve mammography. It was hoped that a phase transition of this type would result in either a reduction in gel volume or increased radiopenetration. Unfortunately, an electrically induced phase transition of silicone gel was not seen. In fact, a temporarily altered molecular orientation (phase transition) was not even possible under the extremes of voltage confirming the fact that silicone is extremely inert.

Electricity↗

PubMed1982

Optical detection of phase transitions in simple and mixed lipid-water phases.

A simple method for the detection of phase transitions in lipid-water systems by recording the intensity of the transmitted light through a sample placed between crossed polarizers as a function of the temperature was developed. A very small amount of lipid material is sufficient for its effective application. Two zwitterionic lipids in water, dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine (DPPE) as well as their mixtures were studied by means of this method. The results were compared with differential scanning calorimetry (DSC) data and a good correspondence was established. A phase diagram of the DPPC-DPPE mixture is constructed. This study also throws additional light on the nature of the 'pretransition' of DPPC.

Birefringence↗

PubMed1988

Modulation of the bilayer to hexagonal phase transition and solvation of phosphatidylethanolamines in aqueous salt solutions.

Several salts affect the temperature of the bilayer to hexagonal phase transition of phosphatidylethanolamines. Their effects are dependent on the anion as well as the cation of the salt. Salt effects on this transition can be explained by preferential hydration and ion binding. Those salts which are excluded from the solvation sphere of the membrane promote hexagonal phase formation. For example, Na2SO4 promotes preferential hydration and is a hexagonal phase promoter while NaSCN does not do this and is a bilayer stabilizer. Unlike amphiphiles and hydrocarbons, salts can shift the bilayer to hexagonal phase transition temperature without altering the cooperativity of the transition. The effect of these salts on the gel to liquid-crystal transition is opposite to their effect on the bilayer to hexagonal phase transition. We also find that MnCl2 markedly raises the gel to liquid-crystal transition temperature. This effect is due to binding of the cation to the membrane surface. The effect is reduced with MnSO4 because of preferential hydration. Our results demonstrate that the nature of the anion as well as the cation can alter the effect of salts on lipid phase transition properties. The observed effects can be explained as resulting from preferential hydration and ion binding.

Lipid Bilayers↗

PubMed1976

Detection of lipid phase transitions by surface tensiometry.

A technique for the detection of lipid phase transitions is described, which involves measurement of the surface tension as a function of temperature. In the case of insoluble lipids, such as dipalmitoylphosphatidylcholine (DPPC) the lipid is spread as a multibilayer film on an aqueous substrate, while in the case of water-soluble lipids such as lysophosphatidylcholine (LPC) the surface tension of aqueous sols is measured. Surface tension at the interface, is monitored using a Wilhelmy plate while the temperature is continuously varied. Discontinuities or changes in slope in the surface tension-temperature (gamma-T) curve reflect phase transitions in the lipid. In the case of DPPC, the technique has been used to demonstrate the well-known gel-liquid crystalline thermal transition. This occurs at 36-38 degrees C in the multibilayer films; in bulk DPPC-water dispersions the transition is at 41 degrees. Cholesterol has the effect of lowering the thermal transition and broadening the temperature range. In films containing DPPC-cholesterol at a molar ratio of 2:1 or less, the transition is not present. These results are in agreement with a large number of previous studies of this system. In the case of LPC sols, a phase transition at about 70 degrees was detected when the concentration of SPC was close to the critical micelle concentration (CMC) at 70 degrees. This transition appears to reflect an increase in the equilibrium constant for micelle formation at this temperature. At higher concentrations of LPC a transition at 30 degrees, corresponding to a gel-liquid crystalline transition, was also detected. A complete description of gamma as a function of concentration and temperature in the range 10(-7) to 10(-3) g cm-3 and 20 degrees to 80 degrees has been obtained for LPC sols. The CMC varies from 6 X 10(-6) g cm-3 at 20 degrees to 10(-5) g cm-3 at 80 degrees.

Binding Sites↗

PubMed1983

Lateral lipid distribution and phase transition in phosphatidylethanolamine/phosphatidylserine vesicles. A cross-linking study.

To determine the nonideal mixing of two lipid components within the membrane, lipid cross-linking experiments were carried out on dipalmitoylphosphatidylethanolamine (DPPE) vesicles and on dipalmitoylphosphatidylethanolamine/dipalmitoylphosphatidylserine (DPPE/DPPS) vesicles. By comparison of the cross-linking reactions on both types of vesicle the mean neighbourhood relations within the binary lipid mixture can be obtained. To elucidate the relationship between cluster formation and phase transition, the temperature dependences of the lipid arrangement within the vesicle membrane and of the lipid order parameter describing the fluidity of the membrane were measured. Cluster size and phase transition correlate: during the phase transition of the lipid species with the lower phase-transition temperature (DPPS) the nonideality of the mixture increases by phase separation. Above the phase transition temperature of the second lipid species (DPPE) the clusters disappear and a slight alternating lipid arrangement is characteristic of the fluid phase.

Chemical Phenomena↗

PubMed1977

Redetermination of the pressure dependence of the lipid bilayer phase transition.

The effect of pressure on the phase transition temperature for the dipalmitoyllecithin bilayer was redetermined by following the volume change accompanying the transition. These measurements were carried out isothermally with the transition from the ordered to the disordered phase induced by decreasing the pressure. This contrasts with our previous measurements which were carried out at constant pressure and increasing temperature. The transition at every temperature was sharp and confirmed our previous observation that the volume change associated with the transition (0.033 mL g-1) is invariant with pressure. However, our present measurements, in contrast to our previous results, indicate that dP m/dTm at all pressures is in agreement with the 1 atm value of delta H/Tm delta V within experimental error where Tm and Pm are the temperature and pressure of the phase transition, respectively. These results, which are now in agreement with all other known pressure data, indicate that the entropy change associated with the transition is invariant with pressure.

Electron Spin Resonance Spectroscopy↗

PubMed1986

Dimyristoylphosphatidic acid/cholesterol bilayers. Thermodynamic properties and kinetics of the phase transition as studied by the pressure jump relaxation technique.

Lipid bilayers and monolayers composed of dimyristoylphosphatidic acid (DMPA) and cholesterol were characterized by differential scanning calorimetry and film balance measurements. Increasing cholesterol content decreases the bilayer phase transition temperature and enthalpy in a manner similar to that observed before for other lipid/cholesterol systems. In monomolecular films at the air-water interface cholesterol exhibits the well known condensing effect in the liquid-expanded phase, while the liquid-condensed phase is less affected. As with the bilayer phase transition, the transition temperature and change in area at the liquid-condensed to liquid-expanded phase transition, as measured from isobars at 25 dynes/cm, decreases with increasing cholesterol content. The kinetics of the phase transition of DMPA/cholesterol bilayers were measured using the pressure jump relaxation technique with optical detection. Three relaxation times were observed. The relaxation times and amplitudes pass through maximum values at the transition midpoint. With increasing cholesterol content the maximum values of the relaxation times decrease but not in a linear fashion. The time constants display an intermediate maximum at ca. 10% to 12 mol% cholesterol. This observation is discussed in terms of a possible change in the nature of the phase transition from first-order with phase separation to a continuous second-order transition. The dependence of the relaxation amplitudes on cholesterol content gave evidence for nucleation being the rate limiting step for the transition in this particular system.

Calorimetry, Differential Scanning↗

PubMed1982

Delivery of antitumor drug to bladder cancer by use of phase transition liposomes and hyperthermia.

It has been proposed that liposomes (phospholipid bilayer vesicles) could be used to entrap enzymes or drugs and then be administered intravenously to patients as a natural molecule to be metabolized. After liposome degradation, the entrapped molecules would be released at higher concentrations in target tissues. In 1979, it was shown that liposomes containing a chemotherapeutic agent could preferentially release the agent at the transition temperature of the lipids. In an effort to deliver high dose methotrexate (MTX) to animal transitional cell carcinomas (TCC), we used liposomes with phase transition temperature a few degrees above 37 C. Experimentally induced bladder TCC tumors (induced with N-(4-(5-nitro-2-furyl)-2 thiazolyl) formamide) were transplanted into hind legs of C3H/Bi mice. These animals received tritiated MTX encapsulated in phase transition liposomes. Tumors were heated to 42 +/- 0.5 C (by ultrasound) before receiving the liposomes containing tritiated molecules of MTX. After an appropriate time sequence the tumors were removed and MTX uptake of each tumor was noted and compared to the controls having unheated tumors. Heated TCC tumors accumulated 11.9-fold more MTX than nonheated tumors receiving the same dose. Animals receiving free MTX did not exhibit a temperature dependent difference. This indicates that the phase transition temperature of specifically engineered liposome may be used to increase delivery of high dose methotrexate to transitional cell carcinomas.

Animals↗