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PubMed2006

Determination of lipid phase transition temperatures in hybrid bilayer membranes.

The main gel-to-liquid-crystal (LC) phase transition temperature, T(m), of the lipid monolayer in hybrid bilayer membranes (HBMs) was investigated using vibrational sum frequency spectroscopy (VSFS). In the gel phase, the acyl chains of the lipid molecules assume an ordered, all-trans configuration, whereas in the LC phase, the acyl chains exhibit a significant number of disordered gauche conformers. VSFS has unique sensitivity to the order/disorder transitions in the acyl chains and was used to determine T(m) for a series of saturated phosphatidylcholine lipids on octadecanethiolate self-assembled monolayers (SAMs). The values obtained for T(m) for all lipids studied are significantly higher than for the corresponding lipids in vesicles in solution. Additionally, the transition widths are broader for the lipids in HBMs. The underlying SAM clearly influences the phase behavior of the overlying lipid monolayer.

Journal Article↗

PubMed1996

Phase transitions of rat stratum corneum lipids by an electron paramagnetic resonance study and relationship of phase states to drug penetration.

In order to relate barrier function to stratum corneum structure and the thermal transitions of corneum lipids, samples from hairless rat skin were investigated by using ESR and drug penetration techniques. The phase transition of stratum corneum lipids was estimated using a deeper probe (16-doxyl-stearic acid) inserted in the lipid bilayers and measuring the rotational correlation time, tau(c). Results of ESR study showed that stratum corneum lipids underwent thermal transitions at 39.3 +/- 1.6 degrees C and 63.6 +/- 2.6 degrees C roughly similar to the data obtained by differential scanning calorimetry measurements. Cholesterol oxidase treatment decreased the fluidity of the lipids at lower temperatures. The treatment of stratum corneum with laurocapram (1%) and isopropyl myristate (IPM, 2%) little changed both phase transition temperatures, although the treatment highly increased the molecular motion of the lipids. The flux (J(s)) of lipophilic drugs (beta-estradiol, indomethacin and betahistine) through the skin was enhanced with increasing temperatures, with an increase in the diffusion constant within skin and a decrease in the lag time. There was a good relationship between log J(s) or log permeability coefficient (K(p)) and 1/tau(c) in the temperature range of 45 to 64 degrees C. The calculated activation energy (delta E) for diffusion of these drugs across skin was 17-40 kcal/mol. Judging from our data, stratum corneum lipids of rat probably exist as the gel, crystalline state below 39 degrees C, the mesomorphic state between 39 and 64 degrees C and the fluid, liquid-crystalline state at temperatures of 64 degrees C or above. These results are in line with the permeability of these lipophilic drugs through the intercellular lipids disordered is highly increased.

Animals↗

PubMed2005

The effects of energy sites on adsorption of Lennard-Jones fluids and phase transition in carbon slit pore of finite length a computer simulation study.

A Monte Carlo simulation method is used to study the effects of adsorption strength and topology of sites on adsorption of simple Lennard-Jones fluids in a carbon slit pore of finite length. Argon is used as a model adsorbate, while the adsorbent is modeled as a finite carbon slit pore whose two walls composed of three graphene layers with carbon atoms arranged in a hexagonal pattern. Impurities having well depth of interaction greater than that of carbon atom are assumed to be grafted onto the surface. Different topologies of the impurities; corner, centre, shell and random topologies are studied. Adsorption isotherms of argon at 87.3 K are obtained for pore having widths of 1, 1.5 and 3 nm using a Grand Canonical Monte Carlo simulation (GCMC). These results are compared with isotherms obtained for infinite pores. It is shown that the surface heterogeneity affects significantly the overall adsorption isotherm, particularly the phase transition. Basically it shifts the onset of adsorption to lower pressure and the adsorption isotherms for these four impurity models are generally greater than that for finite pore. The positions of impurities on solid surface also affect the shape of the adsorption isotherm and the phase transition. We have found that the impurities allocated at the centre of pore walls provide the greatest isotherm at low pressures. However when the pressure increases the impurities allocated along the edges of the graphene layers show the most significant effect on the adsorption isotherm. We have investigated the effect of surface heterogeneity on adsorption hysteresis loops of three models of impurity topology, it shows that the adsorption branches of these isotherms are different, while the desorption branches are quite close to each other. This suggests that the desorption branch is either the thermodynamic equilibrium branch or closer to it than the adsorption branch.

Journal Article↗

PubMed2001

Phase transitions of binary alloys with elastic inhomogeneity.

In elastically inhomogeneous alloys, in which the shear modulus depends on the composition, coarsening in phase separation can be pinned even without quenched disorder. Here networks in the soft phase enclose the domains in the hard phase. Highly asymmetric strains in the two regions create large free energy barriers that prevent further coarsening. Thus a phase transition occurs between the one-phase and the glassy two-phase states. We numerically obtain the phase diagram and show that this transition is discontinuous at any composition. Therefore there is no critical point.

Journal Article↗

PubMed1981

Characterization of a third phase transition in multilamellar dipalmitoyllecithin liposomes.

The thermotropism of dipalmitoyllecithin in fully hydrated multilamellar dispersions has been reexamined by differential scanning calorimetry, X-ray diffraction, and 31P nuclear magnetic resonance. Apart from the well-known pretransition and main transition, there exists a third transition at about 11 degrees C with a transition enthalpy of approximately 3.7 kcal/mol. Both adjoining phases are lamellar, but they differ in the lateral acyl chain packing of the lecithin molecules and in the dynamics of the polar head groups. The kinetics of this third phase transition are extremely slow in comparison with those of the other two transitions.

Calorimetry, Differential Scanning↗

PubMed2005

Spectral condensation of turbulence in plasmas and fluids and its role in low-to-high phase transitions in toroidal plasma.

Transitions from turbulence to order are studied experimentally in thin fluid layers and in magnetically confined toroidal plasma. It is shown that turbulence self-organizes through the mechanism of spectral condensation in both systems. The spectral redistribution of the turbulent energy leads to the reduction in the turbulence level, generation of coherent flow, reduction in the particle diffusion, and increase in the system's energy. The higher-order state in the plasma is sustained via the non-local spectral coupling of the linearly unstable spectral range to the large-scale mean flow. Spectral condensation of turbulence is discussed in terms of its role in the low-to-high confinement transitions in toroidal plasma which show similarity with phase transitions.

Journal Article↗

PubMed2004

Molecular ordering and phase transitions in alkanol monolayers at the water-hexane interface.

The interface between bulk water and bulk hexane solutions of n-alkanols (H(CH(2))(m)OH, where m=20, 22, 24, or 30) is studied with x-ray reflectivity, x-ray off-specular diffuse scattering, and interfacial tension measurements. The alkanols adsorb to the interface to form a monolayer. The highest density, lowest temperature monolayers contain alkanol molecules with progressive disordering of the chain from the -CH(2)OH to the -CH(3) group. In the terminal half of the chain that includes the -CH(3) group the chain density is similar to that observed in bulk liquid alkanes just above their freezing temperature. The density in the alkanol headgroup region is 10% greater than either bulk water or the ordered headgroup region found in alkanol monolayers at the water-vapor interface. We conjecture that this higher density is a result of water penetration into the headgroup region of the disordered monolayer. A ratio of 1:3 water to alkanol molecules is consistent with our data. We also place an upper limit of one hexane to five or six alkanol molecules mixed into the alkyl chain region of the monolayer. In contrast, H(CH(2))(30)OH at the water-vapor interface forms a close-packed, ordered phase of nearly rigid rods. Interfacial tension measurements as a function of temperature reveal a phase transition at the water-hexane interface with a significant change in interfacial excess entropy. This transition is between a low temperature interface that is nearly fully covered with alkanols to a higher temperature interface with a much lower density of alkanols. The transition for the shorter alkanols appears to be first order whereas the transition for the longer alkanols appears to be weakly first order or second order. The x-ray data are consistent with the presence of monolayer domains at the interface and determine the domain coverage (fraction of interface covered by alkanol domains) as a function of temperature. This temperature dependence is consistent with a theoretical model for a second order phase transition that accounts for the domain stabilization as a balance between line tension and long range dipole forces. Several aspects of our measurements indicate that the presence of domains represents the appearance of a spatially inhomogeneous phase rather than the coexistence of two homogeneous phases.

Journal Article↗

PubMed2001

Dynamic phase transition in a time-dependent Ginzburg-Landau model in an oscillating field.

The Ginzburg-Landau model below its critical temperature in a temporally oscillating external field is studied both theoretically and numerically. As the frequency or the amplitude of the external field is changed, a nonequilibrium phase transition is observed. This transition separates spatially uniform, symmetry-restoring oscillations from symmetry-breaking oscillations. Near the transition a perturbation theory is developed, and a switching phenomenon is found in the symmetry-broken phase. Our results confirm the equivalence of the present transition to that found in Monte Carlo simulations of kinetic Ising systems in oscillating fields, demonstrating that the nonequilibrium phase transition in both cases belongs to the universality class of the equilibrium Ising model in zero field. This conclusion is in agreement with symmetry arguments [G. Grinstein, C. Jayaprakash, and Y. He, Phys. Rev. Lett. 55, 2527 (1985)] and recent numerical results [G. Korniss, C. J. White, P. A. Rikvold, and M. A. Novotny, Phys. Rev. E 63, 016120 (2001)]. Furthermore, a theoretical result for the structure function of the local magnetization with thermal noise, based on the Ornstein-Zernike approximation, agrees well with numerical results in one dimension.

Journal Article↗

PubMed2005

First-order phase transition in the tethered surface model on a sphere.

We show that the tethered surface model of Helfrich and Polyakov-Kleinert undergoes a first-order phase transition separating the smooth phase from the crumpled one. The model is investigated by the canonical Monte Carlo simulations on spherical and fixed connectivity surfaces of size up to N = 15 212. The first-order transition is observed when N > 7000, which is larger than those in previous numerical studies, and a continuous transition can also be observed on the smaller surfaces. Our results are therefore consistent with those obtained in previous studies on the phase structure of the model.

Journal Article↗

PubMed2006

Activated Jak2 with the V617F point mutation promotes G1/S phase transition.

Hematopoietic stem cells in myeloproliferative diseases mostly retain the potential to differentiate but are characterized by hyper-responsiveness to growth factors, as well as partial factor-independent growth. The V617F activating point mutation in Jak2 has recently been associated with myeloproliferative disorders. Using various cell line models, mechanisms that contribute to Jak2V617-mediated signaling were investigated. Treatment of the Jak2V617F mutant-expressing erythroid leukemia cell line HEL with a small molecule Jak2 inhibitor was associated with a dose-dependent G(1) cell cycle arrest. This inhibition correlated with decreased expression of cyclin D2 and increased expression of the cell cycle inhibitor p27(Kip). Inhibition of Jak2V617F with a Jak2-targeted small interfering RNA approach resulted in a similar phenotype. Mechanisms leading to altered p27(Kip) and cyclin D2 likely involve inhibition of STAT5, a major target of Jak2 in hematopoietic cells, because a constitutively active form of STAT5 reduced p27(Kip) and increased cyclin D2 expression. Jak2V617F and constitutively active STAT5 also induced high levels of reactive oxygen species, which are sufficient to promote G(1)/S phase transition. In contrast, treatment of HEL cells with the antioxidant N-acetylcysteine decreased cell growth or expression of cyclin D2 and increased expression of p27(Kip). Similar results were obtained in BaF3 cells transfected with Jak2V617F, but these cells required coexpression of the erythropoietin receptor for optimal signaling. These results suggest that regulation of cyclin D2 and p27(Kip) in combination with redox-dependent processes promotes G(1)/S phase transition downstream of Jak2V617F/STAT5 and therefore hint at potential novel targets for drug development that may aid traditional therapy.

Apoptosis↗

PubMed1999

The events relating to lanthanide ions enhanced permeability of human erythrocyte membrane: binding, conformational change, phase transition, perforation and ion transport.

The binding and uptake of Gd3+ ions by human erythrocytes in vitro were studied by determining the Gd contents in membrane and in cytosol by means of particle-induced X-ray emission (PIXE) spectrometry. Results obtained from varied incubation time revealed that the Gd3+ ions bind to the membrane proteins and lipids at first. Gd3+ binding to the membrane lipids and proteins lasts 0 approximately 20 and 20 approximately 100 ms respectively, as shown by the stopped-flow studies. Then a fraction of Gd3+ ions diffuses through the membrane. The kinetics of Gd3+ binding indicates that the binding to phospholipids is prior to that to the membrane proteins, but a portion of the lipid-bound Gd3+ redistributed later to the proteins. PIXE studies showed that the entry of Gd3+ increased the influx of Ca2+ and Cl-. By monitoring the changes in fluorescence of proteins and that of the Ln3+, the uptake of La3+, Eu3+, Gd3+ and Tb3+ was shown to be a process comprising a series of events. Binding to the membrane molecules induces the phase transition of lipid bilayer and conformational changes and aggregation of membrane proteins. Conformational changes of the proteins were characterized by Fourier transform IR spectroscopy (FT-IR) deconvolved spectra, i.e. alpha-helix content decreases while beta-sheet increases. ESR spectra of MSL-labeled proteins reflect the aggregation state related with the conformational change. [31P]NMR spectra of membrane lipid bilayer revealed the Ln3+ ions induced hexagonal (H(II)) phase formation. Phase transition and aggregation of membrane proteins cause the formation of domain structure and perforation in the membrane. These alterations in membrane structure are responsible for the Ln3+ enhanced membrane permeability. Thus the previous Ln3+ binding will facilitate the across-membrane transport of other Ln3+ ions through the membrane.

Blood Proteins↗

PubMed2000

Determination of partition coefficient by the change of main phase transition.

The molar partition coefficients of amphiphilic additives, e.g. local anesthetics, between the aqueous phase, the liquid crystal and the gel phase of lipid membrane can be determined based on a combination of phase transition data obtained at high and low concentrations of the lipid in aqueous phase. The data obtained at high lipid concentration allow to find the phase diagram lipid-additive in the aqueous environment. The combination of this diagram with data obtained at low lipid and additive concentrations provides direct information on the concentration of anesthetics in the lipid and thus allows the calculation of the partition coefficient.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed1984

Phase transitions and critical behavior in human bimanual coordination.

Conditions that give rise to phase shifts among the limbs when an animal changes gait are poorly understood. Often a "switch mechanism" is invoked that has a neural basis which remains speculative. Abrupt phase transitions also occur between the two hands in humans when movement-cycling frequency is continuously increased. The asymmetrical out-of-phase mode shifts suddenly to a symmetrical in-phase mode involving simultaneous activation of homologous muscle groups. The boundary between the two coordinative states is indexed by a dimensionless critical number, which remains constant regardless of whether the hands move freely or are subject to resistive loading. Coordinated shifts appear to arise because of continuous scaling influences that render the existing mode unstable. Then, at a critical point, bifurcation occurs and a new stable (and perhaps energetically more efficient) mode emerges.

Computers↗

PubMed2001

Boundary induced phase transitions in driven lattice gases with metastable states.

We study the effect of metastability onto boundary induced phase transitions in a driven lattice gas. The phase diagram for open systems, parameterized by the input and output rates, consists of two regions corresponding to the free flow and jammed phase. Both have been entirely characterized. The microscopic states in the high density phase are shown to have an interesting striped structure, which undergoes a coarsening process and survives in the thermodynamic limit.

Journal Article↗

PubMed2003

Structural forces near phase transitions of liquid crystals.

The structure of the fragile liquid-crystalline phases has a strong impact on the forces between bodies immersed in a liquid crystal (LC). We have equipped an atomic force microscope with a precise temperature control and measured various liquid-crystalline structural forces at temperatures close to the phase transitions. The observed forces agree well with predictions of Landau--de Gennes phenomenological theory of LCs, even at a nanoscale length. In addition to this, we have observed a molecular layer, adsorbed on the surfactant-covered glass surface, and determined its thickness and elastic properties.

Journal Article↗

PubMed1993

Phase transitions of Acholeplasma laidlawii membranes. The involvement of Mg(2+)-ATPase in the C transition.

Highly sensitive differential scanning calorimetry has been employed to study the phase transitions of A. laidlawii membrane. The DSC curves obtained show five distinct transitions between 20 and 80 degrees C which contain a reversible lipid thermotropic transition at about 37 degrees C and four irreversible denaturation transitions of the membrane proteins occurred at about 44 degrees C, 52 degrees C, 62 degrees C, and 67 degrees C, respectively. Total enthalpy of the thermal denaturation of membrane proteins is 3.4 +/- 0.5 cal/g. Further study of A. laidlawii membrane preparations by means of thermal gel analysis and enzyme activity measurements at various temperatures provided information that the third peak (C transition) of the DSC curve involved primarily with Mg(2+)-ATPase on A. laidlawii membranes.

Acholeplasma laidlawii↗

PubMed2000

Gravitational phase transitions in a one-dimensional spherical system

The behavior of gravitational phase transitions in a system of concentric, spherical, mass shells that interact via their mutual and self gravitation is investigated. The nature of the transition in the microcanonical, canonical, and grand canonical ensembles is studied both theoretically in terms of the mean field limit and by dynamical simulation. Transitions between a quasiuniform state and a centrally concentrated state are predicted by mean field theory for the microcanonical and canonical ensembles, and this is supported by dynamical simulation. For the grand canonical ensemble, mean field theory predicts that no transition takes place, and that the thermodynamically stable state is always the uniform one. Again, this is supported by simulations under various initial distributions of mass, even when the system is initialized in a collapsed state. In addition to testing the predictions of the mean field theory and studying the effects of finite size scaling, dynamical simulation allowed us to examine the behavior of temporal and positional correlations which are predicted to vanish in the mean field limit.

Journal Article↗

PubMed2000

Dynamic approach to weak first-order phase transitions

A short-time dynamic approach to weak first-order phase transitions is proposed. Taking the two-dimensional Potts models as examples, from short-time behavior of nonequilibrium relaxational processes starting from high temperature and zero temperature states, pseudo-critical-points K* and K** are determined. A clear difference of the values for K* and K** distinguishes a weak first-order transition from a second-order one.

Journal Article↗