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Molecular dynamics simulation of POPC at low hydration near the liquid crystal phase transition.

We report results of a preliminary molecular dynamics study of a 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) bilayer at low hydration (5% in weight). Our results suggest a gel phase structure where the oleic chain is bent recalling the crystalline oleic acid structure. We have also found a discontinuity in the volume/temperature curve which might be related to the gel to liquid crystal phase transition in POPC.

1,2-Dipalmitoylphosphatidylcholine↗

Photoinduced nematic-isotropic phase transition: a case for the random-field Ising model.

Experiments have been carried out on a photoactive guest-nonphotoactive host system exhibiting a photoinduced nematic-isotropic phase transition. It is shown that the phenomenon of photoinduced shift in the transition temperature is similar to the induction of cooperative chiral order in "sergeant-soldier" copolymer systems. An expression resembling the one given by the random-field model proposed for the latter system is seen to quantitatively describe the shift in the transition temperature as a function of the magnitude of the radiation.

Journal Article↗

[Manifestation of the structural phase transitions of lipid bilayers in the ESR spectrum of s-ions in the electron state].

The mechanism of S-ion line width for the tetrahonal cubic complex which was formed by lipids of the lipid bilayer at phase transition is considered. Within the framework of the one-dimensional model of domain walls or kinks created in the phase separation regions of the bilayer the spectral density of crystal field fluctuation of S-ion by radial distortion of the paramagnetic complex is calculated. If the modulation frequencies of an axial component of the crystal field are near the two-fold frequency of ESR, it is possible to reveal the characteristic band of narrowing and broadening of ESR line width for binding S-ions in the bilayer. The proposed theoretical model can be useful in the explanation of experimental values of ESR line width of S-ions binding in plankton. Characteristic parameters of kinks are estimated.

Electron Spin Resonance Spectroscopy↗

Probing the liquid-to-gas phase transition in a cluster via a caloric curve.

High-energy collisions ( 60 keV/amu) of hydrogen cluster ions with a helium target have been completely analyzed on an event-by-event basis. By selecting specific decay reactions we can start after the energizing collision with a microcanonical cluster ion ensemble of fixed excitation energy and we derive corresponding temperatures of the decaying cluster ions. The relation between the temperature and the excitation energy (caloric curve) exhibits the typical prerequisites of a first-order phase transition in a finite system, in the present case signaling the transition from a bound cluster to the gas phase.

Journal Article↗

A new method for membrane reconstitution: fusion of protein-containing vesicles with planar bilayer membranes below lipid phase transition temperature.

A new method of membrane reconstitution was developed by fusion of channel protein containing vesicles with planar bilayer membranes. The fusion process only occurred below and near the phase transition temperature of the lipid used. We obtained the following results: 1. Our system is solvent-free and vesicles do not come into contact with the air/water interface. This obviates a possible denaturation of hydrophobic proteins. 2. Channel forming proteins and protein complexes, respectively, are active in a frozen lipid matrix. 3. We detected an unknown channel in cilia fragments. 4. Purified acetylcholine receptors form fluctuating channels in a membrane consisting of a pure synthetic lecithin (two component system).

Animals↗

Relationship between local structure and phase transitions of a disordered solid solution.

The Pb(Zr,Ti)O3 (PZT) disordered solid solution is widely used in piezoelectric applications owing to its excellent electromechanical properties. Six different structural phases have been observed for PZT at ambient pressure, each with different lattice parameters and average electric polarization. It is of significant interest to understand the microscopic origin of the complicated phase diagram and local structure of PZT. Here, using density functional theory calculations, we show that the distortions of the material away from the parent perovskite structure can be predicted from the local arrangement of the Zr and Ti cations. We use the chemical rules obtained from density functional theory to create a phenomenological model to simulate PZT structures. We demonstrate how changes in the Zr/Ti composition give rise to phase transitions in PZT through changes in the populations of various local Pb atom environments.

Journal Article↗

The molecular organization of lipids in the membrane of Escherichia coli: phase transitions.

X-ray diffraction techniques have been used to investigate the physical state of the lipids in the membrane of an unsaturated fatty acid auxotroph of Escherichia coli. Thermotropic phase transitions have been detected in membranes prepared from cells grown on various fatty acid supplements. Below the transition temperature, the X-ray diffraction pattern features a sharp ring at 420 pm (4.2 A) due to the close hexagonal packing of the apolar groups of the lipids; above the transition temperature the lipids are in a less organized liquid-crystalline state that gives rise to a diffuse band centered at a Bragg spacing of 460 pm (4.6 A). This transition occurs at or below the temperature at which the cells were grown. Disparities between this transition temperature and the temperature of discontinuities in the Arrhenius plots for proline transport and succinic dehydrogenase activity lead us to conclude that the distribution of lipids within the membrane is heterogeneous.

Cell Membrane↗

Nonequilibrium kinetic phase transition of a monomer-dimer reaction model with sequential dimer adsorption in two dimensions.

We study a monomer-dimer reaction model in two dimensions in which the adsorption process of a dimer on the surface sites is separated into two steps (i.e., B2+*-->B2 *, and B2 * +*-->2B*, where * is an empty site), as first introduced by Evans and co-workers. It is clear that the dissociation of a dimer is dependent on the complicated configuration of the adsorbate. We show that the continuous transition from the reactive state to the O-passivated state and the discontinuous transition to the CO-passivated state both shift toward higher values of the fraction p of the monomer in gas phase but the reaction window decreases compared to the Ziff-Gulari-Barshad model. For the model studied here, the critical exponents of the continuous phase transition still exhibit a directed percolation character as expected.

Journal Article↗

Superfluid-superfluid phase transitions in a two-component Bose-Einstein condensate.

Depending on the Hamiltonian parameters, two-component bosons in an optical lattice can form at least three different superfluid phases in which both components participate in the superflow: a (strongly interacting) mixture of two miscible superfluids (2SF), a paired superfluid (PSF) vacuum, and (at a commensurate total filling factor) the super-counter-fluid (SCF) state. We study the universal properties of the 2SF-PSF and 2SF-SCF quantum phase transitions and show that (i) they can be mapped onto each other and (ii) their universality class is identical to the (d+1)-dimensional normal-superfluid transition in a single-component liquid. The finite-temperature 2SF-PSF(SCF) transitions and the topological properties of 2SF-PSF(SCF) interfaces are also discussed.

Journal Article↗

The low-temperature phase transition of 9-methylfluoren-9-ol: comparison of the crystal structures at 100 and 200 K.

Crystals of 9-methylfluoren-9-ol, C(14)H(12)O, undergo a reversible phase transition at 176 (2) K. The structure of the high-temperature alpha form at 200 K is compared with that of the low-temperature beta form at 100 K. Both polymorphs crystallize in space group P1 with Z = 4 and contain discrete hydrogen-bonded R(4)(4)(8) ring tetramers arranged around crystallographic inversion centres. The most obvious changes observed on cooling the crystals to below 176 K are an abrupt increase of ca 0.5 A in the shortest lattice translation, and a thermal transition with deltaH = 1 kJ mol(-1).

Journal Article↗

Effect of a Decapeptide (VPDLLADLLK) on the Phase Transition of Dimyristoylphosphatidylcholine Lipid Bilayer.

VPDLLADLLK is a synthetic decapeptide, which shows a difference in conformation in various environments. Circular dichroism spectral studies show that it exists in an unordered conformation in the aqueous phase, and in dimyristoylphosphatidylcholine (DMPC) lipid bilayer, it exhibits an alpha-helical structure. The membrane property modification due to the peptide incorporation has been studied by using differential scanning calorimetry and fluorescence spectroscopy. With incorporation of the peptide the average steady-state anisotropy of DPH in the membrane decreases slightly in the gel state but remains more or less the same in the liquid crystalline state. The peptide incorporation causes a shift in the phase-transition temperature from 23 to 26 degrees C for 15 mol% and 29 degrees C for 30 mol% of the peptide, which is accompanied by a decrease in the sharpness and a broadening of the DSC thermogram. This preferential stabilization of the more ordered gel phase by the peptide could be due to the hydrophobic mismatch between the length of the peptide and the length of the hydrophobic segment of the DMPC bilayer. Copyright 2001 Academic Press.

Journal Article↗

Phase transition theory for abnormal ocular dominance column formation.

A thermodynamic theory has previously been introduced for explaining the formation of ocular dominance columns in the visual cortex. This paper extends the theory to account for the variation in patterns of ocular dominance columns as a phase transition phenomenon. For this purpose, an "Order parameter" is calculated by Monte Carlo simulation. On a phase diagram representing a two-dimensional parameter space, the conditions in which abnormal ocular dominance columns arise are visualized, and several visual deprivation experiments are successfully explained.

Computer Simulation↗

Dissipation-driven quantum phase transitions in a Tomonaga-Luttinger liquid electrostatically coupled to a metallic gate.

The dissipation induced by a metallic gate on the low-energy properties of interacting 1D electron liquids is studied. As a function of the distance to the gate, or the electron density in the wire, the system can undergo a quantum phase transition from a Tomonaga-Luttinger liquid to two kinds of dissipative phases, one of them with a finite spatial correlation length. We also define a dual model, which describes an attractive one-dimensional metal with a Josephson coupling to a dirty metallic lead.

Journal Article↗

An ionotropic phase transition in phosphatidylcholine: cation and anion cooperativity.

Evidence is presented for cooperative interaction between cations and anions specifically bound to dimyristoylphosphatidylcholine (DMPC). The cooperativity is with regard to an ion-induced (ionotropic) phase transition for the lipid and is signalled by a change in the luminescence from bound Tb3+. The intrinsic binding of Tb3+ to DMPC was determined from equilibrium dialysis experiments, using conventional methods to correct for electrostatic contributions. Preliminary results demonstrate great potential for infrared spectroscopy as a means to relate these Tb3+ luminescence studies to experiments involving less tractable cations. This work provides insight into the role of bound ions in modifying lateral phase behavior in phospholipid membranes.

Cations↗

Peculiarities of first-order phase transitions in the presence of an electric field.

In this study, we developed a variational approach for thermodynamic systems with nondistributed parameters in the presence of the external electrostatic field. Using the obtained general relations, we analyzed some characteristic features of the first-order phase transitions in the presence of electric field. We determined the range of the thermodynamic parameters where both phases are stable (hysteresis), and the range of the parameters whereby both phases are metastable. In the range where both phases are metastable, we considered kinetics of formation of a new phase and determined the dependencies of the concentrations of phases in the region of their metastability on the amplitude of the external electric field. The obtained results imply the feasibility to control phase composition in the system by varying the amplitude of the external electrostatic field.

Journal Article↗

Dependence of the bilayer to hexagonal phase transition on amphiphile chain length.

Several series of amphiphiles of increasing chain length were tested for their abilities to modify the L alpha-HII transition of dielaidoylphosphatidylethanolamine using differential scanning calorimetry. Acylcarnitines, alkyl sulfates, alkylsulfobetaines, and phosphatidylcholines, with chain lengths between about 6 and 12 carbon atoms, show an increasing capacity to raise the L alpha-HII phase transition temperature of phosphatidylethanolamine. This is ascribed to increased partitioning of the added amphiphile from water into the membrane as the chain length increases. Alkyl sulfates and alkyltrimethylammonium bromides have diminished capacities to raise the L alpha-HII transition temperature as the chain length is increased from 12 to 16. This is caused by an increase in the hydrophobic portion of the amphiphile leading to a change in the intrinsic radius of curvature and a decrease in the hydrocarbon packing constraints in the HII phase relative to the shorter chain amphiphiles. The L alpha-HII transition temperature of phosphatidylethanolamine with acylcarnitines of chain length 14-20 carbon atoms, alkylsulfobetaines above 14 carbon atoms, and phosphatidylcholines with acyl groups having above 10 carbon atoms is relatively insensitive to chain length. We suggest that this is caused by a balance between increasing hydrocarbon volume promoting the HII phase through decreased intrinsic radius of curvature and greater relief of hydrocarbon packing constraints vs greater intermolecular interactions favoring the more condensed L alpha phase. This latter effect is more important for amphiphiles with large headgroups which can pack more efficiently in the L alpha phase. The phosphatidylcholines show a gradual decrease in bilayer stabilization between 10 and 22 carbon atoms.(ABSTRACT TRUNCATED AT 250 WORDS)

Calorimetry, Differential Scanning↗

Electrostatic interactions at charged lipid membranes. Kinetics of the electrostatically triggered phase transition.

Charged lipid membranes of dimyristoylmethylphosphatidic acid were mixed rapidly in a stopped-flow cell with protons or Ca2+ to compensate the charges and thereby trigger the ordered-fluid phase transition. The kinetics of the transition was studied by following the time development of the fluorescence anisotropy of diphenylhexatriene. A relaxation process was observed with a characteristic time in the range 10-200 ms. By comparison with existing theories of non-equilibrium relaxation it was concluded that the relaxation process is governed by a nucleation step.

Calcium↗

On the role of the macromolecular phase transitions in biology in response to change in solution volume or macromolecular composition: action as an entropy buffer.

We have used numerical simulation to demonstrate the potential for macromolecular precipitate solution phase transitions existing within the cell, to play a role in the minimization of changes in location or quaternary state of other macromolecular components, predicted to accompany changes in cell volume. For our modeling we have employed thermodynamic relations that take into account the large effects upon the thermodynamic activity coefficient produced by a solution environment that is highly volume occupied due to the presence of high concentrations of soluble macromolecule. The theoretical approach adopted, along with the simulated results, provide a framework for the interpretation of certain proteins' behavior (e.g. cytoskeletal elements such as tubulin and actin and possibly some prion structures) in response to cell volume change.

Buffers↗