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At least 865 records · Page 48Linked to original sources
PubMed1983

The effect of a phase transition on penetration of phospholipid monolayers by melittin and glucagon.

The penetration of melittin and glucagon into phospholipid monolayers was studied by measuring compression isotherms of phospholipids in the absence and presence of various concentrations of protein in the subphase. Differences in molecular area were calculated as a function of protein concentration at constant pressure. Area change as a function of surface pressure at constant protein concentration was also calculated. Melittin showed greater affinity for penetration into phosphatidylglycerol (PG) than into phosphatidylcholine (PC) monolayers. The cutoff pressure for melittin penetration was 45 mN/m with PC and 60 mN/m (extrapolated) with PG. Dipalmitoyl PC and PG monolayers show phase transitions upon compression at 25 degrees C. Both melittin and glucagon showed increased penetration as measured by area change within the region of the phase transition with both lipids. Glucagon showed a cutoff pressure of 25 mN/m for penetration into dimyristoyl PC. The preference of glucagon for interaction with lipid bilayers in the gel phase is discussed with respect to monolayer penetration as a function of surface pressure.

Bee Venoms↗
PubMed2004

Two-dimensional infrared spectroscopy study on phase transition and structural variations of a hydrogen-bonded liquid crystal.

Infrared (IR) spectra have been measured for a liquid crystal (LC) consisting of one trans-butene diacid (BD) molecule as a proton donor and two 4-(2,3,4-tridecyloxybenzoyloxy)-4'-stilbazoles (DBS) molecules as a proton acceptor (DBS:BD:DBS) linked together with each other by inter-molecular hydrogen bonds over a temperature range from 20 to 120 degrees C to explore its phase transition and heat-induced structural variations. The temperature-dependent IR spectra have shown that the inter-molecular hydrogen bonds are stable in the liquid crystalline phase but become slightly decoupled with temperature increasing. Two kinds of two-dimensional (2D) correlation spectroscopy, variable-variable (VV) and sample-sample (SS) 2D spectroscopy, have been employed to analyze the observed temperature-dependent spectral variations more efficiently. The SS 2D correlation analysis in the spectral range of 2700-1800 cm(-1) has demonstrated that a change in hydrogen bonds in the LC starts from 40 degrees C, which is not clarified by differential scanning calorimetry (DSC) and conventional IR and Raman spectroscopic analyses. On the other hand, the phase transition of LC revealed by SS 2D spectroscopy in the specific spectral regions of 1750-1650 and 3000-2700 cm(-1) is in a good agreement with that revealed by DSC for the heating process. The VV 2D correlation spectroscopy analysis has provided information about the structural variations of inter-molecular hydrogen bonds. The different species of hydrogen-bonded and free -COOH and -COO- groups in the LC have been clarified by the VV 2D correlation analysis. It has also elucidated the specific order of the temperature-induced structural changes in the intra- and inter-molecular hydrogen bonds concerning with the -COOH and/or -COO- groups in the LC.

Alkenes↗
PubMed1982

Calorimetric evidence for phase transitions in spin-label lipid bilayers.

Dispersions of pure, spin-label phosphatidylcholines in aqueous buffer have been investigated with the Privalov high-sensitivity differential scanning calorimeter. The lipids studied are mixed-chain ones in which C-2 of glycerol bears a spin-label derivative of stearic acid and the fatty acid group at C-1 is palmitate. A well-defined phase transition is observed at 30.3-30.7 degrees C for the phosphatidylcholine labeled near the polar end of the stearate chain (label at C-5). A sharp transition (32-34 degrees C) is also observed for the lipid spin-labeled near the terminal methyl of stearate (label at C-16), but the thermodynamic parameters for this lipid depend strongly on the history of the sample. Calorimetric evidence for hysteresis in the phase transition of the C-16-labeled lipid is presented. In contrast to the above spin-label lipids, the lipid labeled at C-12 does not show a sharp transition in the region 5-35 degrees C. In general, therefore, the thermal behavior of the spin-label phosphatidylcholines resembles that of phosphatidylcholines bearing double bonds or branched methyl groups at similar locations on acyl chains. During synthesis of mixed-chain lipids, migration of acyl chains occurs. Methyl esterification procedures which are compatible with the acid-labile spin-label group are described. Gas chromatographic analysis of methyl esters shows that chain migration during synthesis gives 15-20% of the spin-label fatty acid at the glycerol C-1 position.

Calorimetry, Differential Scanning↗
PubMed2005

Phase transitions induced by noise cross-correlations.

A general approach for treating the spatially extended stochastic systems with the nonlinear damping and correlations between additive and multiplicative noises is developed. Within the modified cumulant expansion method, we derive an effective Fokker-Planck equation with stationary solutions that describe the character of the ordered state. We find that the fluctuation cross-correlations lead to a symmetry breaking of the distribution function even in the case of zero-dimensional system. In a general case, continuous, discontinuous and reentrant noise induced phase transitions take place. It appears that the cross-correlations play the role of bias field which can induce a chain of phase transitions of different nature. Within the mean field approach, we give an intuitive explanation of the system behavior by an effective potential of the thermodynamic type. This potential is written in the form of an expansion with coefficients defined by the temperature, intensity of spatial coupling, autocorrelation and cross-correlation times and intensities of both additive and multiplicative noises.

Journal Article↗
PubMed1997

On the Nature of The Liquid Expanded/Liquid Condensed Phase Transition in Monolayers of Polar Molecules.

During the liquid expanded/liquid condensed (LE/LC) phase transition, the long range repulsive interactions among fatty acid or phospholipid molecules induce the formation of a dispersion of LC islands (of almost the same size) as a superlattice in a continuous phase of LE molecules. Assuming that the transformation occurs at thermodynamic equilibrium, one demonstrates that, as the surface fraction of LC phase increases, the surface pressure pi increases. Consequently, the LE/LC transition can have characteristics different from those of the conventional first order transitions. Copyright 1997 Academic Press.

Journal Article↗
PubMed2005

Dynamic phase transition in the kinetic spin-1 Blume-Capel model under a time-dependent oscillating external field.

We study within a mean-field approach the stationary states of the kinetic spin-1 Blume-Capel model in the presence of a time-dependent oscillating external magnetic field. We use the Galuber-type stochastic dynamics to describe the time evolution of the system. We have found that the behavior of the system strongly depends on the crystal field interaction D . We have obtained two types of solutions: a symmetric one, which corresponds paramagnetic phase where the magnetization (m) of the system oscillates in time around zero, and an antisymmetric one where m oscillates in time around a finite value different from zero. There are regions of the phase space where both solutions coexist. The dynamic phase transition from one regime to the other can be a first- or a second-order depending on the region in the phase diagram. Hence, the system exhibits one or more dynamic tricritical point, which depends on the values D . We also calculate the Liapunov exponent to verify the stability of the solutions and the dynamic phase transition points.

Journal Article↗
PubMed2006

Interplay of spin conversion and structural phase transformations: re-entrant phase transitions in the 2-propanol solvate of tris(2-picolylamine)iron(II) dichloride.

Crystal structures, magnetic and thermodynamic properties of the spin-crossover compound tris(2-picolylamine)iron(II) dichloride (with 2-propanol solvent molecules) have been measured in the temperature range from 15 to 293 K. X-ray diffraction, SQUID, and calorimetric experiments all showed two first-order phase transitions with hysteresis loops, a narrow one at T(1) approximately 196 K and a broad, triangular one covering the range 153<T(2)<166 K. Crystal structures were analysed at fourteen temperatures in a cooling cycle and at seven temperatures in a heating cycle. They reveal a complex, temperature-dependent ordering behaviour of both the complex cations and the alcohol molecules. A phenomenological model accounting for spin conversion, solvent ordering and coupling between the two processes describes the observed phase transitions and ordering phenomena reasonably well. Similarities and differences in the behaviour of the corresponding ethanol solvate with the same crystal architecture are discussed. It is concluded that spin-crossover behaviour depends as much on molecular properties as it does on intermolecular interactions, both of the spin active and the spin inactive components.

Journal Article↗
PubMed1980

The appearance of single-ion channels in unmodified lipid bilayer membranes at the phase transition temperature.

Ion-specific channels in artificial membranes have been formed by the addition of gramicidin A, alamethicin, polyene antibiotics and some proteins to the solution surrounding the bilayer lipid membrane. Until now there have been no reports of single-ion channels in unmodified lipid membranes. We have now studied the electrical conductance of planar lipid bilayers membranes made of synthetic distearoylphosphorylcholine (DSPC). Current fluctuations of amplitude approximately 1pA and duration approximately 1 s have been discovered at phase transition temperature, which shows that the appearance of ionic channels may be the result of lipid domain interactions. This would explain the dramatic increase in ion permeability observed in liposomes during phase transition. We suggest that these channels could conduct the transmembrane ionic current in biological membranes without the involvement of peptides and proteins.

Electric Conductivity↗
PubMed2000

The NaCl- to CsCl-type phase transition discussed on the basis of the cP to cI deformation with the symmetry Cmcm 4(c) m2m

A structure forming a cubic primitive lattice cP may be deformed into a structure forming a cubic body-centred lattice cI in the space group Cmcm at position 4(c) m2m 0,y,1/4. If in related structures the sites are alternately occupied by unlike atoms, the NaCl and the CsCl types occur, respectively. The corresponding phase transition can be described as a deformation of a heterogeneous sphere packing in the subgroup Pmmn (a,-c,b) of Cmcm. All sphere configurations with symmetry Cmcm 4(c) m2m were derived. On the basis of this information, further possibilities for phase transitions that also correspond to sphere-packing deformations were found with this symmetry. Two of them possibly may take place in metals. The first one leads from a primitive hexagonal lattice to a hexagonal close packing, the other from a cubic body-centred lattice also to a hexagonal close packing.

Journal Article↗
PubMed2006

Effect of chemical structure on the volume-phase transition in neutral and weakly charged poly(N-alkyl(meth)acrylamide) hydrogels studied by ultrasmall-angle x-ray scattering.

Neutral poly(N-isopropylacrylamide) (PIPAAm), poly(N,N-diethylacrylamide) (PDEAAm), and poly(N-isopropylmethacrylamide) (PIPMAm) hydrogels and their weakly charged counterparts prepared by copolymerizing with sodium methacrylate (x(MNa)=0,0.025,0.05) were studied using ultrasmall-angle x-ray scattering. The volume-phase transition in hydrogels was observed as an increase in the inhomogeneity correlation length of the networks. The change in inhomogeneity correlation length was abrupt in neutral PIPAAm and PIPMAm gels with increase in temperature but was continuous in neutral PDEAAm gels. Addition of ionic comonomer to the network backbone suppressed the volume-phase transition in poly(N-alkylacrylamide)s but not in PIPMAm. The observed differences in temperature-induced volume change of these three polymers in water cannot be rationalized based on their relative hydrophobicity and are instead explained by considering the hydrogen-bonding constraints on their thermal fluctuations. Both PIPAAm and PDEAAm undergo volume collapse since their thermal fluctuations are constrained by hydrogen bonding with water to an extent that beyond a critical temperature they seek entropic compensation. Although thermal fluctuations in both PIPAAm and PIPMAm are equally constrained, thermal energy of the latter can be relaxed via the rotation of alpha-methyl groups allowing it greater flexibility. Compared to N-alkylacrylamides, N-alkylmethacrylamide can thus sustain hydrogen bonding to relatively higher temperatures before seeking entropic compensation by undergoing volume collapse.

Journal Article↗
PubMed1988

Effects of 2.45-GHz microwave and 100-MHz radiofrequency radiation on liposome permeability at the phase transition temperature.

Large unilamellar dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylglycerol (DPPG) liposomes loaded with an aqueous chemotherapeutic drug, cytosine arabinofuranoside (ARA-C), were exposed for 30 min to 60 W/kg continuous-wave (CW) 100-MHz or 2.45-GHz radiation in vitro at temperatures between 37 degrees C and 43 degrees C. Liposomes were exposed in HEPES buffer or in HEPES buffer supplemented with 44% by volume fetal calf serum (FCS). Characteristic phase transition responses were detected in the range of 39 degrees C to 40 degrees C with the presence of FCS, increasing maximum % release of 3H-ARA-C by 20% relative to HEPES suspension. Neither frequency of electromagnetic radiation had any detectable effect on liposome permeability or the location of the phase transition in the presence or absence of FCS.

Cytarabine↗
PubMed2003

Phase transition in the Ising model on a small-world network with distance-dependent interactions.

We study the collective behavior of an Ising system on a small-world network with the interaction J(r) proportional to r(-alpha), where r represents the Euclidean distance between two nodes. In the case of alpha=0 corresponding to the uniform interaction, the system is known to possess a phase transition of the mean-field nature, while the system with the short-range interaction (alpha-->infinity) does not exhibit long-range order at any finite temperature. The Monte Carlo simulations are performed at various values of alpha, and the critical value alpha(c) beyond which the long-range order does not emerge is estimated to be 0. Thus, concluded is the absence of a phase transition in the system with the algebraically decaying interaction r(-alpha) for any nonzero positive value of alpha.

Journal Article↗
PubMed2003

Nonequilibrium phase transition in a self-activated biological network.

We present a lattice model for a two-dimensional network of self-activated biological structures with a diffusive activating agent. The model retains basic and simple properties shared by biological systems at various observation scales, so that the structures can consist of individuals, tissues, cells, or enzymes. Upon activation, a structure emits a new mobile activator and remains in a transient refractory state before it can be activated again. Varying the activation probability, the system undergoes a nonequilibrium second-order phase transition from an active state, where activators are present, to an absorbing, activator-free state, where each structure remains in the deactivated state. We study the phase transition using Monte Carlo simulations and evaluate the critical exponents. As they do not seem to correspond to known values, the results suggest the possibility of a separate universality class.

Allosteric Site↗
PubMed2001

Phase transitions in a model for the formation of herpes simplex ulcers.

The critical properties of a cellular automaton model describing the spreading of infection of the herpes simplex virus in corneal tissue are investigated through the dynamic Monte Carlo method. The model takes into account different cell susceptibilities to the viral infection, as suggested by experimental findings. In a two-dimensional square lattice the sites are associated with two distinct types of cells, namely, permissive and resistant to the infection. While a permissive cell becomes infected in the presence of a single infected cell in its neighborhood, a resistant cell needs to be surrounded by at least R>1 infected or dead cells in order to become infected. The infection is followed by the death of the cells resulting in ulcers whose forms may be dendritic (self-limited clusters) or amoeboid (percolating clusters) depending on the degree of resistance R of the resistant cells as well as on the density of permissive cells in the healthy tissue. We show that a phase transition between these two regimes occurs only for R>/=5 and, in addition, that the phase transition is in the universality class of the ordinary percolation.

Ganglia↗
PubMed2005

Kinetics of lamellar-to-cubic and intercubic phase transitions of pure and cytochrome c containing monoolein dispersions monitored by time-resolved small-angle X-ray diffraction.

We investigated the effect of incorporation of a small aqueous peripheral membrane protein (cyt c) into the three-dimensional periodic nanochannel structures formed by the lipid monoolein (MO) on its rich phase behavior as a function of temperature, pressure, and protein concentration using synchrotron X-ray small-angle diffraction. By simultaneous use of the pressure-jump relaxation technique and time-resolved synchrotron X-ray diffraction, we also studied the kinetics of various lipid mesophase transformations of the system for understanding the mechanistic pathways of their formation influenced by the protein-lipid interactions. Cyt c incorporated into the bicontinuous cubic phase Ia3d of MO has a significant effect on the lipid structure and the pressure stability of the system already at low protein concentrations. Concentrations higher than 0.2 wt % of cyt c led to an increase in interfacial curvature due to interaction of the protein with the lipid headgroups. This promotes the formation of a new, probably partially micellar cubic phase of crystallographic space group P4(3)32. Upon pressurization, the P4(3)32 phase undergoes a phase transition to a cubic Pn3m phase with smaller partial specific volume. Increase in protein concentration increases the pressure stability of the P4(3)32 phase. The formation of this phase from the cubic phase Pn3m is a slow process taking many seconds and having a time lag in the beginning. It seems to occur as a two-state process without ordered intermediate states. At temperatures above 60 degrees C, the P4(3)32 phase is unable to accommodate the unfolded protein and transforms to a bicontinuous cubic Ia3d phase. Time-resolved small-angle X-ray scattering studies show that the L(alpha) --> Ia3d transition in pure MO dispersions under limited hydration conditions occurs within a time interval of 1 s at 35 degrees C preceded by a lag phase of 1.5 s. The Ia3d cubic phase initially forms with a much larger lattice constant due to hydration and experiences an initially lower curvature that relaxes within about 1 s. Interestingly, no other cubic phases are involved as intermediates in the transition, i.e., the gyroid cubic phase is able to form directly from the L(alpha) phase. The mechanism behind the L(alpha) --> Ia3d transition in pure MO dispersions has been discussed within the framework of recent stalk models for membrane fusion. In the presence of cyt c, the L(alpha) --> Ia3d transition is much slower. The rather long relaxation times of the order of seconds are probably due to a kinetic trapping of the system and limitation by the transport and redistribution of water and lipid in the evolving new lipid phases. We also studied the transition from the pure lamellar L(alpha) phase to the Ia3d-P4(3)32 two phase region and observed a rather complex transition behavior with transient lamellar and cubic intermediate states.

Crystallization↗
PubMed1977

Phase transitions of phospholipid bilayers from an unsaturated fatty acid auxotroph of Escherichia coli.

Total phospholipids were extracted from cells of temperature sensitive unsaturated fatty acid auxotrophs of Escherichia coli (K-12 UFAts) grown at 28degrees C (PL28), and at 42degrees C in the presence of 2% KCl as an osmotic stabilizer (PL42 (KCl)). From the analysis of fatty acids, it was shown that the content of unsaturated fatty acids of PL42 (KCl) is only 9% of the total fatty acids, while that of PL28 is 54%. The thermal phase transitions of the bilayers prepared from the phospholipid fractions were studied by proton magnetic resonance. The line widths of the methylene signals and the sums of the methylene and methyl signal intensities were plotted against reciprocal values of absolute temperature 1/T or temperature itself. From the plots phase transitions were detected at about 19degrees C for PL28 and at 43degrees C for PL42 (KCl). In spite of its complex composition of fatty acids a highly cooperative transition was observed in the case of PL42 (KCl). It was also suggested that the phospholipids bilayers in the biomembranes of this strain at the growth temperature (42 degrees C) are in the state where the gel and liquid crystalline phases coexist.

Cell Membrane↗
PubMed1981

Interactions of La2+ with phosphatidylserine vesicles: binding, phase transition, leakage, 31P-NMR and fusion.

The interaction of La2+ with phosphatidylserine vesicles is studied by differential scanning calorimetry, 140La binding, 31P-NMR chemical shifts and relaxation rates, carboxyfluorescein and [14C]sucrose release, X-ray diffraction and freeze-fracture electron microscopy. In the presence of La3+ concentrations above 1 mM and an incubation temperature of 38 degrees C, i.e., at the phase transition temperature of the complex La/phosphatidylserine, the binding ratio of La/lipid exceeds a 1/3 ratio, reaching saturation at a 1/2 ratio. Analysis, employing a modified Gouy-Chapman equation, indicates a significant increase in the intrinsic binding constant of La/phosphatidylserine when the La3+ concentrations exceeds the threshold concentration for leakage. The analysis illustrates that at the molecular level the binding of La3+ can be comparable to or even weaker than that of Ca2+, but that even when present at smaller concentrations La3+ competes with and partially displaces Ca2+ from membranes or other negatively charged surfaces. The results suggest that the sequence La3+ greater than Ca2+ greater than Mg2+ reflects both the binding strength of these cations to phosphatidylserine as well as their ability to induce leakage, enhancement of 31P spin-lattice relaxation rates, fusion and other structural changes. The leakage, fusion, and other structural changes are more pronounced at the phase transition temperature of the La/lipid complex.

Electron Spin Resonance Spectroscopy↗
PubMed2004

Friction and second-order phase transitions.

A microscopic model is studied numerically to describe wearless dry friction without thermal fluctuations between atomically flat contact interfaces. The analysis is based on a double-chain model with a Lennard-Jones interaction between the chains which are the respective upper flexible monolayers of the rigid bulk systems. Whereas below a critical interaction strength epsilon(c) the system exhibits a frictionless state, it offers static friction above epsilon(c) . Introducing an appropriate order parameter function we demonstrate the analogy of the critical behavior to a phase transition of second order. The order parameter is related to a hull function describing uniquely the incommensurate ground state of the model. The breakdown of analyticity of the hull function is identified with the phase transition. Critical exponents are calculated and the validity of finite-size scaling is displayed.

Journal Article↗