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A macroscopic description of lipid bilayer phase transitions of mixed-chain phosphatidylcholines: chain-length and chain-asymmetry dependence.

A macroscopic model is presented to quantitatively describe lipid bilayer gel to fluid phase transitions. In this model, the Gibbs potential of the lipid bilayer is expressed in terms of a single order parameter q, the average chain orientational order parameter. The Gibbs potential is based on molecular mean-field and statistical mechanical calculations of inter and intrachain interactions. Chain-length and chain-asymmetry are incorporated into the Gibbs potential so that one equation provides an accurate description of mixed-chain phosphatidylcholines of a single class. Two general classes of lipids are studied in this work: lipid bilayers of partially or noninterdigitated gel phases, and bilayers of mixed interdigitated gel phases. The model parameters are obtained by fitting the transition temperature and enthalpy data of phosphatidylcholines to the model. The proposed model provides estimates for the transition temperature and enthalpy, van der Waals energy, number of gauche bonds, chain orientational order parameter, and bond rotational and excluded volume entropies, achieving excellent agreement with existing data obtained with various techniques.

Biophysical Phenomena↗

Field-induced behaviors near the smectic-A-smectic-C * alpha phase transition of an antiferroelectric liquid crystal.

We have experimentally and theoretically investigated the electric-field effect on the smectic-A-smectic-C(*)(alpha) phase transition of an antiferroelectric liquid crystal4-(1-methyl-heptyloxycarbonyl)phenyl 4(')-octylcarbonyloxybiphenil-4-carboxylate. From the microscopic observations under electric fields and the measurements of the D-E hysteresis loop and apparent tilt angle, the E (electric field)-T (temperature) phase diagram was established, in which a tricritical point was found. From the dielectric measurements under dc electric fields, a soft mode inducing the transition was observed. Furthermore, we have developed a phenomenological theory under dc fields to analyze the experimental results. The origin of the soft mode observed under fields was clarified and the temperature dependence of the relaxation frequency was obtained by the analyses.

Journal Article↗

Continuous phase transitions with a convex dip in the microcanonical entropy.

The appearance of a convex dip in the microcanonical entropy of finite systems usually signals a first order transition. However, a convex dip also shows up in some systems with a continuous transition as, for example, in the Baxter-Wu model and in the four-state Potts model in two dimensions. We demonstrate that the appearance of a convex dip in those cases can be traced back to a finite-size effect. The properties of the dip are markedly different from those associated with a first order transition and can be understood within a microcanonical finite-size scaling theory for continuous phase transitions. Results obtained from numerical simulations corroborate the predictions of the scaling theory.

Journal Article↗

Phase transition of triclinic hen egg-white lysozyme crystal associated with sodium binding.

A triclinic crystal of hen egg-white lysozyme obtained from a D2O solution at 313 K was transformed into a new triclinic crystal by slow release of solvent under a temperature-regulated nitrogen-gas stream. The progress of the transition was monitored by X-ray diffraction. The transition started with the appearance of strong diffuse streaks. The diffraction spots gradually fused and faded with the emergence of diffraction from the new lattice; the scattering power of the crystal fell to a resolution of 1.5 A from the initial 0.9 A resolution. At the end of the transition, the diffuse streaks disappeared and the scattering power recovered to 1.1 A resolution. The transformed crystal contained two independent molecules and the solvent content had decreased to 18% from the 32% solvent content of the native crystal. The structure was determined at 1.1 A resolution and compared with the native structure refined at the same resolution. The backbone structures of the two molecules in the transformed crystal were superimposed on the native structure with root-mean-square deviations of 0.71 and 0.96 A. A prominent structural difference was observed in the loop region of residues Ser60-Leu75. In the native crystal, a water molecule located at the centre of this helical loop forms hydrogen bonds to main-chain peptide groups. In the transformed crystal, this water molecule is replaced by a sodium ion with octahedral coordination that involves water molecules and a nitrate ion. The peptide group connecting Arg73 and Asn74 is rotated by 180 degrees so that the CO group of Arg73 can coordinate to the sodium ion. The change in the X-ray diffraction pattern during the phase transition suggests that the transition proceeds at the microcrystal level. A mechanism is proposed for the crystal transformation.

Animals↗

Characterization by infrared spectroscopy of the bilayer to nonbilayer phase transition of phosphatidylethanolamines.

A Fourier-transform infrared spectroscopic study of the thermotropic behavior of egg yolk phosphatidylethanolamines is reported. Two phase changes were monitored, the gel to liquid-crystalline acyl chain melting transition, centered at 12 degrees C, and a transition from the liquid-crystalline to be inverted hexagonal phase, centered at 28 degrees C. It is demonstrated that the gel to liquid-crystalline phase transition results in a large increase in the conformational disorder of the acyl chains in the bilayer and that the nonbilayer phase contains a still higher degree of conformational disorder. It is shown that the transition to the inverted hexagonal phase is promoted by highly unsaturated acyl chains. A model is developed for the bilayer to nonbilayer phase transition in which it is proposed that the driving force which triggers this phase transition is the introduction of a degree of conformational disorder so high that the integrity of the bilayer surface can no longer be maintained, due to the volume requirements of the acyl chains. A number of previously reported data are rationalized in terms of this hypothesis.

Egg Yolk↗

Phase transitions and permeability changes in dry membranes during rehydration.

Dry phospholipid bilayers are known to undergo transient changes in permeability during rehydration. In this review, we present evidence from which we suggest that this permeability change is due to a gel to liquid-crystalline phase transition accompanying rehydration. If the transition is avoided, as in lipids that remain in gel phase whether dry or rehydrated, the problem of leakage during rehydration is obviated, at least in part. Further, the evidence that the transition temperature for dry bilayers can be depressed by certain sugars is discussed. Finally, we show that these principles can be extended to intact cells. Using pollen grains as a model, we have measured the transition temperature for membrane phospholipids and show that the transition is correlated with physiological measurements including permeability changes and subsequent germination. From the Tm values taken from pollen grains at different water contents, we have constructed a phase diagram for the intact pollen that has high predictive value for physiological properties.

Cell Membrane Permeability↗

On the lamellar compounds CuBiP(2)Se(6), AgBiP(2)Se(6) and AgBiP(2)S(6). Antiferroelectric phase transitions due to cooperative Cu(+) and Bi(3+) ion motion.

CuBiP(2)Se(6), AgBiP(2)Se(6), and AgBiP(2)S(6) were prepared from the corresponding elements. CuBiP(2)Se(6) and AgBiP(2)Se(6) crystallize in the space group R with a = 6.5532(16) A and c = 39.762(13) A for CuBiP(2)Se(6) and a = 6.6524(13) A and c = 39.615(15) A for AgBiP(2)Se(6). AgBiP(2)S(6) crystallizes in the triclinic space group P with a = 6.3833(13) A, b = 7.1439(14) A, c = 9.5366(19) A, alpha = 91.89(3) degrees , beta = 91.45(3) degrees , gamma = 94.05(3) degrees . CuBiP(2)Se(6) was found to exhibit a temperature-dependent antiferroelectric ordering of the Cu(+) and Bi(3+) ions in the lattice. An intermediate and a fully ordered structure were refined at 173 and 97 K, respectively. Electronic band and total energy calculations at the DFT level clearly suggest that the antiferroelectric model is energetically favored over the paraelectric and hypothetical ferrielectric models. This phase transition can be classified as a second-order Jahn-Teller distortion. The antiferroelectric state of CuBiP(2)Se(6) is an indirect gap semiconductor. The compounds were characterized with differential thermal analysis and solid-state UV/vis diffuse reflectance spectroscopy. Generalized implications regarding the expected ferroelectric behavior of compounds in the CuMP(2)Se(6) system (M = trivalent metal) are discussed.

Bismuth↗

Surface phase transitions in athermal mixtures of hard rods and excluded volume polymers investigated using a density functional approach.

Using fundamental measures' density functional framework based on Wertheim's first order perturbation theory [J. Chem. Phys. 87, 7323 (1987)] we study the surface phase transitions in athermal polymer-needle mixtures, which demix in bulk into the isotropic polymer-rich (rod-poor) and polymer-poor (rod-rich) phases. We find that the polymer-rich (rod-poor) phase wets the hard wall at coexistence and the wetting transition is of first order. In the partial wetting regime we find a sequence of layerings but these transitions are gradually suppressed as the chain length increases. For long enough chains we detect the prewetting line. Rods exhibit pronounced ordering at the wall in the polymer-rich phases. Our results imply that experiments on the (isotropic) wetting transition for colloidal rod-polymer mixtures should be easier to carry out than those for the colloidal rod-sphere mixtures because the wetting transition occurs at lower rod densities. On the other hand, layerings in sphere-needle mixtures may turn out to be difficult to observe experimentally because some of them will be metastable with respect to the freezing transition, whereas the remaining ones are located very close to the binodal.

Journal Article↗

Interaction of spherical particles dispersed in a liquid crystal above the nematic-isotropic phase transition.

The effective interaction of micron-size particles immersed in a nematic liquid crystal at temperatures above the nematic-isotropic phase transition is examined. Using the Landau-de Gennes theory we describe the surface-induced ordering of the liquid crystal. Modeling a spherical particle by a sequence of conical surfaces enables us to draw an analogy with the partial ordering in a thin nematic film and to obtain an analytical expression for the two-particle interaction. Special attention is paid to the dependence of the effective interaction on temperature and on the interfacial coupling parameters, which are chosen in agreement with recent experiments. We show that the interaction as a function of the interparticle distance exhibits a potential barrier of the order of kT. The height of the barrier decreases exponentially with increasing temperature while it grows linearly with the interfacial coupling parameters.

Journal Article↗

Absorbing state phase transitions with quenched disorder.

Quenched disorder--in the sense of the Harris criterion--is generally a relevant perturbation at an absorbing state phase transition point. Here using a strong disorder renormalization group framework and effective numerical methods we study the properties of random fixed points for systems in the directed percolation universality class. For strong enough disorder the critical behavior is found to be controlled by a strong disorder fixed point, which is isomorph with the fixed point of random quantum Ising systems. In this fixed point dynamical correlations are logarithmically slow and the static critical exponents are conjecturedly exact for one-dimensional systems. The renormalization group scenario is confronted with numerical results on the random contact process in one and two dimensions and satisfactory agreement is found. For weaker disorder the numerical results indicate static critical exponents which vary with the strength of disorder, whereas the dynamical correlations are compatible with two possible scenarios. Either they follow a power-law decay with a varying dynamical exponent, like in random quantum systems, or the dynamical correlations are logarithmically slow even for a weak disorder. For models in the parity conserving universality class there is no strong disorder fixed point according to our renormalization group analysis.

Journal Article↗

Quantum chaos triggered by precursors of a quantum phase transition: the dicke model.

We consider the Dicke Hamiltonian, a simple quantum-optical model which exhibits a zero-temperature quantum phase transition. We present numerical results demonstrating that at this transition the system changes from being quasi-integrable to quantum chaotic. By deriving an exact solution in the thermodynamic limit we relate this phenomenon to a localization-delocalization transition in which a macroscopic superposition is generated. We also describe the classical analogs of this behavior.

Journal Article↗

Exotic axion cosmology in theories with phase transitions below the QCD scale.

We show that axion phenomenology may be significantly different than conventionally assumed in theories which exhibit late phase transitions (below the QCD scale). In such theories, one can find multiple pseudoscalars with axionlike couplings to matter, including a string scale axion, whose decay constant far exceeds the conventional cosmological bound. Such theories have several dark matter candidates.

Journal Article↗

EXAFS study of phase transitions in KIO3.

The iodine K-edge EXAFS study of KIO3 was performed to clarify local structural changes on the successive phase transitions. The pair-distribution function of three oxygen atoms in an oxygen octahedron is almost independent on temperature like a covalent bond, whereas that of the other three is gradually reduced with increasing temperature like an ionic bond. The result indicates that iodine and oxygen atoms exist as an IO3- molecule in a pseudo-perovskite-type structure. The anomalous behavior in the Debye-Waller factor for the latter pair-distribution function appears around 50 K, which is associated with the orientational glass transition.

Journal Article↗

Electrostatically driven granular media: phase transitions and coarsening

We report the experimental and theoretical study of electrostatically driven granular material. We show that the charged granular medium undergoes a hysteretic phase transition from the immobile condensed state (granular solid) to a fluidized dilated state (granular gas) with a changing applied electric field. In addition we observe a spontaneous precipitation of dense clusters from the gas phase and subsequent coarsening-coagulation of these clusters. Molecular dynamics simulations show qualitative agreement with experimental results.

Journal Article↗

Protein geranylgeranylation, not farnesylation, is required for the G1 to S phase transition in mouse fibroblasts.

In order to assess the relative contributions of farnesylated and/or geranylgeranylated proteins on cell cycle progression from G1 to S phase we designed potent and selective farnesyltransferase (FTI-277) and geranylgeranyltransferase-I (GGTI-298) inhibitors. Flow cytometry studies showed that treatment of NIH3T3 cells with GGTI-298 or lovastatin, which inhibits both protein farnesylation and geranylgeranylation, arrested cells in G0/G1 whereas cells treated with FTI-277 progressed normally through the cell cycle. [3H]thymidine incorporation studies showed that mevalonate and geranylgeraniol, but not farnesol, released the lovastatin G1 block. Furthermore, mevalonate release of the lovastatin G1 block was inhibited by GGTI-298 but not by FTI-277. These results demonstrate that geranylgeranylated proteins are required for cells to proceed from G1 to S phase, and that farnesylated proteins do not play an essential role in the G1 to S phase transition

Actins↗

Refractive index measurements in a reentrant isotropic-calamitic nematic phase transition.

In this work the temperature dependence of the extraordinary/ordinary refractive indices and optical birefringence are determined near the reentrant isotropic (I(RE))-calamitic nematic (N(C)) and N(C)-isotropic (I) phase transitions in a lyotropic mixture of potassium laurate, decanol, and water. This reentrant isotropic phase is verified by our experimental data and discussed in terms of thermal variation of the micellar shape anisotropy. The results showed also, with basis in the Vuks's equation, that near the maximum optical birefringence in the range of N(C) phase the extraordinary coefficient of electronic polarizability (phi(parallel)) is equal to the ordinary coefficient (phi( perpendicular)).

Journal Article↗

Genistein induces p21(Cip1/WAF1) expression and blocks the G1 to S phase transition in mouse fibroblast and melanoma cells.

Genistein, the principal isoflavonoid in soybeans, is reported to inhibit cell cycle progression, but the molecular basis for this event is unknown. Here we show that genistein inhibits DNA synthesis and suppresses cyclin E-associated cyclin-dependent kinase-2 (CDK2) activity when quiescent BALB/c 3T3 fibroblasts are stimulated with serum. In these cells, a CDK2 inhibitor, p21(Cip1/WAF1), is markedly increased by genistein, but another CDK2 inhibitor, p27(Kip1), is not increased. In exponentially growing BALB/c 3T3 cells, genistein inhibits proliferation of the cells in a dose-dependent manner. Flow cytometric analysis and measurement of DNA synthesis indicate that genistein blocks the G1 to S phase transition of these cells, which is concomitant with G2-M arrest. In mouse B16-F1 melanoma cells, genistein also blocks the transition of G1 to S phase without arresting at G2-M at low doses. In both cell lines, genistein suppresses cyclin E/CDK2 activity and induces p21(Cip1/WAF1) expression. These results suggest that genistein affects the restriction point control of the cell cycle by inducing p21(Cip1/WAF1) expression in mouse fibroblast and melanoma cells.

3T3 Cells↗

Phase transitions in phosphatidylcholine dispersion observed with an interference refractometer.

An interferometer is used to measure the refractive index change accompanying the crystal-to-liquid-crystal phase transition in the dispersion of phosphatidylcholines. Two separate methods of obtaining the refractive index change are employed: the first method analyzes the intensity transmitted through a spatial filter and the second method utilizes a piezoeletric crystal-based electronic compensator. The results of the two methods agree well. The accuracy of the apparatus (6 X 10(-6)) permitted us to use a very dilute sample to detect the phase change. Only a fraction of a milligram of dry lecithin is needed to observe the change. The result confirms conclusively that the major reason for the turbidity change at the transition temperature is the alteration in the refractive index of the lipid membranes. The fractional change in the refractive index does not agree well with the fractional change in the density of lipid molecules in vesicles.

Chemical Phenomena↗