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Micromagnetic imaging to determine the nature of the ferromagnetic phase transition in La(0.7)Ca(0.3)MnO3.

There is considerable controversy surrounding the nature of the paramagnetic to ferromagnetic phase transition in La(0.7)Ca(0.3)MnO3. We have used transmission electron microscopy to determine whether the phase transition is first or second order. On warming through the transition point, the ferromagnetic phase retreats from the sample surface as it is replaced by the paramagnetic phase. This coexistence of ferromagnetic and paramagnetic phases indicates a primarily first order transition. However, there is also continuous loss of magnetization which precedes the phase transition. We compare this with the phase transition in nickel, an archetypal second order ferromagnet.

Journal Article↗

Landau model of the direct isotropic to smectic-C*A phase transition in antiferroelectric liquid crystals.

An orientational order parameter is proposed for the isotropic to smectic C*A phase transition in antiferroelectric liquid crystals. A phenomenological theory is developed to describe the direct isotropic to smectic-C*A phase transition on the basis of a free energy expansion. The free energy is written in terms of the coupled order parameters including the antipolar correlations. We present a detailed analysis of the different phases that can occur and analyze the question: under which conditions a direct isotropic to smectic-C*A phase transition is possible when compared to other phase transitions? The theoretical results are compared with experimental results.

Journal Article↗

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↗

Relationship between phase transitions and topological changes in one-dimensional models.

We address the question of the quantitative relationship between thermodynamic phase transitions and topological changes in the potential energy manifold analyzing two classes of one dimensional models, the Burkhardt solid-on-solid model and the Peyrard-Bishop model for DNA thermal denaturation, both in the confining and nonconfining version. These models, apparently, do not fit [M. Kastner, Phys. Rev. Lett. 93, 150601 (2004)] in the general idea that the phase transition is signaled by a topological discontinuity. We show that in both models the phase transition energy v(c) is actually noncoincident with, and always higher than, the energy v(theta) at which a topological change appears. However, applying a procedure already successfully employed in other cases as the mean field phi4 model, i.e., introducing a map M:v-->v(s) from levels of the energy hypersurface V to the level of the stationary points "visited" at temperature T, we find that M (v(c))=v(theta). This result enhances the relevance of the underlying stationary points in determining the thermodynamics of a system, and extends the validity of the topological approach to the study of phase transition to the elusive one-dimensional systems considered here.

Biophysics↗

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↗

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↗

Regulation of synthesis of the Bacillus subtilis transition-phase, spore-associated antibacterial protein TasA.

Previously, we identified a novel component of Bacillus subtilis spores, called TasA, which possesses antibacterial activity. TasA is made early in spore formation, as cells enter stationary phase, and is secreted into the medium as well as deposited into the spore. Here, we show that tasA expression can occur as cells enter stationary phase even under sporulation-repressing conditions, indicating that TasA is a transition-phase protein. tasA and two upstream genes, yqxM and sipW, likely form an operon, transcription of which is under positive control by the transition-phase regulatory genes spo0A and spo0H and negative control by the transition phase regulatory gene abrB. These results are consistent with the suggestion that yqxM, sipW, and tasA constitute a transition phase operon that could play a protective role in a variety of cellular responses to stress during late-exponential-phase and early-stationary-phase growth in B. subtilis.

Bacillus subtilis↗

Coherent light generation from a Nd:SBN nonlinear laser crystal through its ferroelectric phase transition.

In this Letter we have used the optical pump induced thermal loading to drive Nd(3+) a doped Sr(0,47)Ba(0.53)(Nb)(3))(2) laser crystal during laser operation through its ferroelectric phase transition. We demonstrate that lasing is possible below, at, and above phase transition. For temperatures close to (approximately 105 degrees C) the spatial distribution of laser radiation is remarkably affected. This feature, which leads to a laser gain depression, can be explained in terms of the strong temperature dependence of the thermo-optic coefficient during phase transition. Additionally, the visible radiation generated by intracavity self-frequency doubling disappears when the phase transition is undergone, showing a bistable behavior. The results provide fundamental information on physical parameters along the phase transition and will stimulate further work in the fields of nonlinear optics, optical switching, and data storage.

Journal Article↗

Characterization of glucose dependent gel-sol phase transition of the polymeric glucose-concanavalin A hydrogel system.

PURPOSE: The main goal of this study was to synthesize and characterize hydrogels which undergo reversible gel-sol phase transformation in response to changes in glucose concentration in the surrounding environment. METHODS: The glucose-sensitive hydrogels were made by mixing the appropriate concentrations of acrylamide-allyl glucose copolymer and concanavalin A (Con A). To examine their phase reversibility, hydrogels in dialysis membranes were cycled between glucose-free and glucose-containing buffers. The binding affinity of allyl glucose (AG) to Con A was examined by using an equilibrium dialysis technique. RESULTS: The synthesized hydrogels underwent phase transition to sol in the presence of free glucose in the environment. The concentration of external free glucose (Cf) had to be at least 4 times that of polymer-bound glucose (Cp) to induce phase transition from gel to sol. The binding affinity study showed that binding of AG to Con A was four times stronger than that of free glucose. When Cp in the gel was 0.42 mg/ml or higher, Cf had to be much higher than 4 times Cp to induce phase transition. CONCLUSIONS: The synthesized hydrogels underwent phase transition in the presence of free glucose in the environment, but the phase transition was not linearly dependent on the concentration of free glucose. This non-linear dependence was explained by the increased binding affinity of AG over native glucose to Con A, and the cooperative interactions between polymer-bound glucose and Con A.

Binding Sites↗

Direct Raman evidence for a weak continuous phase transition in liquid water.

This paper presents the Raman depolarization ratio of degassed ultrapure water as a function of temperature, in the range 303.4-314.4 K (30.2-41.2 degrees C). The pressure of the sample was the vapor pressure of water at the measurement temperature. The data provide a direct indication of the existence of a phase transition in the liquid at 307.7 K, 5.8 kPa (34.6 degrees C, 0.057 atm). The minimum in the heat capacity, C(p)(), of water occurs at 34.5 degrees C, 1.0 atm (J. Res. Natl. Bur. Stand. 1939, 23, 197(1)). The minimum in C(p)() is shallow, and the transition is a weak-continuous phase transition. The pressure coefficient of the viscosity of water changes sign as pressure increases for temperatures below 35 degrees C (Nature 1965, 207, 620(2)). The viscosity minimum tracks the liquid phase transition in the P, T plane where it connects with the minimum in the freezing point of pure water in the same plane (Proc. Am. Acad. Arts Sci. 1911-12, 47, 441(3)). Previously we argued (J. Chem. Phys. 1998, 109, 7379(4)) that the minimum in the pressure coefficient of viscosity signaled the elimination of three-dimensional connectivity in liquid water. These observations coupled with recent measurements of the coordination shell of water near 300 K (Science 2004, 304, 995(5)) suggest that the structural component that changes during the phase transition is tetrahedrally coordinated water. At temperatures above the transition, there is no tetrahedrally coordinated water in the liquid and locally planar water structures dominate the liquid structure. Water is a structured liquid with distinct local structures that vary with temperature. Furthermore, liquid water has a liquid-liquid phase transition near the middle of the normal liquid range.

Journal Article↗

Weakly first-order character of the nematic-isotropic phase transition in liquid crystals.

The classification of phase transitions in first-order and second-order (or continuous) ones is widely used. The nematic-to-isotropic (NI) transition in liquid crystals is a weakly first-order transition, with only small discontinuities in enthalpy and specific volume at the transition which are not always easy to measure. On the other hand, fluctuation effects near the transition, typical for a continuous transition, are present because of the only weakly first-order character. In a recent paper [Phys. Rev. E 69, 022701 (2004)], it was concluded from the static dielectric permittivity in the isotropic phase near the NI transition that less polar mesogens (with little or no pretransitional effects) are characteristic for a first-order NI phase transition, whereas in the case of strongly polar ones (with large pretransitional effects) the NI transition is close to second order. In this paper, we address the question whether it is, indeed, possible to use these fluctuation effects in the isotropic phase to quantify the "strength" of a weakly first-order transition, i.e., how far it is from second order. Therefore, we measured the temperature dependence of the enthalpy near the NI transition of seven liquid crystals with adiabatic scanning calorimetry and compared the measured values of the latent heat with pretransitional effects in the dielectric constant and the specific heat capacity. The compounds used in the comparison are MBBA, 5CB, 8CB, 5NCS, 5CN, 8CHBT, and D7AB. From our analysis we find, contrary to the assertion in the above reference, no correlation between the strength of the NI transition of a given compound and the pretransitional effects observed, neither dielectrically, nor thermally.

Comment↗

Estrogen accelerates G1 to S phase transition and induces a G2/M phase-predominant apoptosis in synthetic vascular smooth muscle cells.

OBJECTIVE: To investigate the mechanisms underlying the vascular-protective effects of estrogen. METHODS: The synthetic (subcultured for 3-4 passages) rat vascular smooth muscle cells were exposed to gradient concentrations (10(-10)-10(-5) M) of 17beta-estradiol. The growth, cell cycle progression and apoptosis of the cells, and the related proteins including Cyclin D1, Cdk4, p38, Bax and Bcl-2 were analyzed in MTT, flow cytometry, ELISA or Western blot. RESULTS: 17beta-estradiol in the physiological concentrations (10(-10)-10(-8) M) promoted the smooth muscle cell growth in a concentration-dependent manner, accelerated transition of the cells from G1 to S phases, and up-regulated expressions of Cyclin D1 and Cdk4. Meanwhile, the hormone (10(-9)-10(-7) M) triggered a G2/M phase-predominant apoptosis of the cells in a concentration- and time-dependent manner, which was accompanied by increased phosphorylation of p38 and expression of Bax. CONCLUSIONS: The effect of estrogen on the synthetic vascular smooth muscle cell is dual. It promotes proliferation of the cells by accelerating their G1/S phase transition via up-regulating Cyclin D1 and Cdk4; and on the other hand, it induces apoptosis of the proliferating cells by up-regulating Bax through p38-MAPK pathway.

Analysis of Variance↗

Detection of bilayer packing stress and its release in lamellar-cubic phase transition by time-resolved fluorescence anisotropy.

An introduction of nonlamellar-forming lipids into planar bilayers generates packing stress, which is important for the biological functions of plasma membranes and is a driving force for the lamellar-nonlamellar phase transition. We have investigated the phase behavior of a binary system consisting of egg yolk phosphatidylcholine and monoolein (MO) and the changes in the local orientation order of lipids in a lamellar-bicontinuous cubic phase transition. Small-angle X-ray scattering has revealed that the lamellar-bicontinuous cubic phase transition occurs at an MO molar fraction (X(MO)) between 0.6 and 0.7. These phases were dispersed to form liposomes and cubosomes to monitor the anisotropy of the incorporated fluorescence probe, in which Pluronic F127, used as a dispersion stabilizer of the cubic phase, has been proven not to alter the cubic structure and the location of the probes. Time-resolved fluorescence anisotropy measurements on these dispersions have revealed that the order parameter of the probe in the lamellar phase increases with increasing X(MO), and that it decreases during the transition to the cubic phase. This observation suggests that packing stress generated by the addition of the nonlamellar-forming lipid is released by the phase transition.

Algorithms↗

Phase transition temperature and chilling sensitivity of bovine oocytes.

A limiting factor for achieving cryopreservation of oocytes is direct chilling injury (DCI), which occurs during cooling. DCI, or cold shock, is defined as an irreversible damage expressed shortly after exposure to low, but not freezing, temperatures. The primary target of DCI is thought to be the plasma membrane. Recently, an association between DCI in sperm and the thermotropic phase transition of their membrane lipids was demonstrated. In the present study, we examined the phase transition of the membrane lipids of immature and in vitro-matured bovine oocytes during cooling, using Fourier transform infrared spectroscopy (FTIR). The phase transition of the membrane lipids of oocytes at the germinal vesicle (GV) stage occurred between 13 and 20 degrees C, while a very broad phase transition, which centered around 10 degrees C, was observed for mature oocytes (MII) stage. Thermotropic phase transitions were demonstrated to be related to the temperature at which DCI affected the integrity of the oocyte membranes. When immature oocytes were cooled to 13 degrees C, fewer oocytes (40%) retained their membrane integrity than after exposure to 4 degrees C (51%) or holding them at 38 degrees C (78%), (as determined by the Fluorescein Diacetate-FDA test). This finding might suggest that holding immature oocytes at the phase transition temperature is more damaging to their membranes than exposure to lower temperatures. By contrast, no significant differences in membrane integrity were observed when in vitro-matured oocytes were cooled to the same temperatures. Subsequently, GV oocytes were cooled to 4 degrees C, and 26% underwent maturation and 19% underwent fertilization in vitro. In vitromatured oocytes that were cooled to 4 degrees C displayed a slightly decreased rate of fertilization; the overall fertilization was 60% with 24% polyspermy, rather than the 76% fertilization rate with 12% polyspermy obtained with those not subjected to cooling. The high rate of polyspermy indicates that a site(s) other than the plasma membrane is affected during cooling of bovine oocytes. Nucleated bovine GV oocytes were electrofused with in vitro-matured and enucleated oocytes, and then cooled to 4 degrees C. Evaluation of the membrane integrity of the fused oocytes showed that these oocytes are chilling resistant, which strongly suggests that alteration of the membrane composition of an oocyte can change the cell's susceptibility to low temperatures. This finding led to an improvement in the survival of oocytes after cryopreservation.

Animals↗

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↗

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↗

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↗

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↗