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Phase transition from asymmetric to symmetric dimer structure on the Si(001) surface at high temperature.

The dimer configurations on the Si(001) surface at high temperatures have been investigated using the rocking curve of reflection high-energy electron diffraction. The Si(001) surface shows a displacive phase transition around 900 K, where a well-known asymmetric (tilted) dimer structure on the Si(001) at room temperature transforms to a symmetric dimer structure around 900 K. The metallic feature of the Si(001) surface above 900 K can be explained by the phase transition.

Journal Article↗

Phase transition in a healthy human heart rate.

A healthy human heart rate displays complex fluctuations which share characteristics of physical systems in a critical state. We demonstrate that the human heart rate in healthy individuals undergoes a dramatic breakdown of criticality characteristics, reminiscent of continuous second order phase transitions. By studying the germane determinants, we show that the hallmark of criticality--highly correlated fluctuations--is observed only during usual daily activity, and a breakdown of these characteristics occurs in prolonged, strenuous exercise and sleep. This finding is the first reported discovery of the dynamical phase transition phenomenon in a biological control system and will be a key to understanding the heart rate control system in health and disease.

Adult↗

Barotropic phase transitions of dioleoylphosphatidylcholine and stearoyl-oleoylphosphatidylcholine bilayer membranes.

In order to understand the effect of cis unsaturation on the thermotropic and barotropic phase behavior of phospholipid bilayer membranes, the phase transitions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC), 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) bilayer membranes were observed by high-pressure optical method. With respect to DOPC bilayer membrane, the so-called main transition between the liquid crystalline (Lalpha) and the lamellar gel (Lbeta) phases was observed in water at above 0 degrees C under high pressure, in addition to the transition between the Lalpha and the lamellar crystalline (L(C)) phases in 50% aqueous ethylene glycol. The pressure of main transition increased linearly with an increase in temperature. Extrapolation of temperature (T)-pressure (P) phase boundary to ambient pressure suggests the temperature of the main transition to be -40.3 degrees C, which has never been found by the DSC method. On the other hand, the temperature of L(C)/Lalpha phase transition in 50% aqueous ethylene glycol was found to be -12.0 degrees C at ambient pressure. The main transition temperatures for DSPC, SOPC and DOPC are 55.6, 6.7 and -40.3 degrees C, respectively, at ambient pressure. The substitution of cis unsaturated chain for saturated chains of DSPC brings about the depression of the main transition temperature by about 48 (+/-1) degrees C for each chain. The volume changes (deltaV) associated with the transitions were calculated from the transition enthalpy (deltaH) and the slope of T-P diagram (dT/dP) by means of the Clapeyron-Clausius equation. The value of deltaV for the main transition of SOPC bilayer membranes was reduced to half the volume change for DSPC bilayers, which means the introduction of the cis double bond in the acyl chain of lipids brings about the reduction of deltaV because of the disordered packing of unsaturated chains in the gel phase of lipid bilayer membranes.

Biophysical Phenomena↗

Gel to liquid crystalline phase transition promotes a conformational reorganization of Ca2+, Mg2+-ATPase from sarcoplasmic reticulum in dimyristoylphosphatidylcholine reconstituted systems.

Sarcoplasmic reticulum Ca2+, Mg2+-ATPase has been reconstituted in membranes highly enriched in dimyristoylphosphatidylcholine. According to electron microscopy data these membranes form vesicles of an average diameter of 1000 +/- 200 A. These reconstituted membranes show hysteretic behavior in some physical-chemical properties, such as light scattering and fluorescence when labeled with iodoacetamidofluorescein and with N-iodoacetyl-N'-(5-sulfo-1-naphthyl) ethylenediamine. Hysteretic behavior in catalytic activity can also be inferred from the kinetic data presented in this paper, because the temperature dependence of the Ca2+, Mg2+-ATPase activity is altered by a mild thermal pretreatment of the samples. Furthermore, it was noticed that the Ca2+-dependent ATPase activity of these complexes, when assayed above the phase transition temperature (Tc) of the lipid matrix, showed a lag phase in the minute time scale range. On the basis of these findings, it is suggested that the gel-to-liquid crystalline phase transition of the lipid is able to shift the conformational equilibrium E----E* of Ca2+, Mg2+-ATPase. The fact that the -SH reactivity against 5,5'-dithio-bis-nitrobenzoic acid of these complexes is also altered by preincubation above Tc for several minutes also supports that lipid melting induces a conformational change in Ca2+, Mg2+-ATPase.

Ca(2+) Mg(2+)-ATPase↗

Investigation of sodium sulfate phase transitions in a porous material using humidity- and temperature-controlled X-ray diffraction.

Crystals growing in confined spaces can generate stress and are a major cause of damage in porous materials. To investigate such deleterious processes, appropriate in situ techniques are required. This paper describes the use of X-ray diffractometry under controlled conditions of temperature and relative humidity (RH-XRD) for the direct observation of phase transition reactions in a porous substrate. An improved environmental chamber without temperature gradients is presented and applied to the investigation of phase transformations in the system Na2SO4 + H2O. This salt is generally considered as particularly damaging and frequently used in accelerated weathering tests. It is demonstrated that RH-XRD can be successfully applied for the direct observation of several relevant phase transitions in glass frits used as porous substrates. The conversion of Na2SO4(III) to Na2SO4(V) and the hydration of Na2SO4(V) both proceed fairly rapidly as true solid-state reactions without deliquescence of the educt phases. In contrast, crystallization from solution is kinetically hindered as there is a strong tendency of aqueous Na2SO4 to form supersaturated solutions also in narrow pores. The important implications of this behavior of the salt are also briefly discussed in the paper.

Journal Article↗

Rigorous location of phase transitions in hard optimization problems.

It is widely believed that for many optimization problems, no algorithm is substantially more efficient than exhaustive search. This means that finding optimal solutions for many practical problems is completely beyond any current or projected computational capacity. To understand the origin of this extreme 'hardness', computer scientists, mathematicians and physicists have been investigating for two decades a connection between computational complexity and phase transitions in random instances of constraint satisfaction problems. Here we present a mathematically rigorous method for locating such phase transitions. Our method works by analysing the distribution of distances between pairs of solutions as constraints are added. By identifying critical behaviour in the evolution of this distribution, we can pinpoint the threshold location for a number of problems, including the two most-studied ones: random k-SAT and random graph colouring. Our results prove that the heuristic predictions of statistical physics in this context are essentially correct. Moreover, we establish that random instances of constraint satisfaction problems have solutions well beyond the reach of any analysed algorithm.

Journal Article↗

Effect of the phase transition on the transbilayer movement of dimyristoyl phosphatidylcholine in unilamellar vesicles.

Dimyristoyl phosphatidylcholine rapidly exchanges between vesicles at 37 degrees C without vesicle fusion. The rate of the transbilayer movement of dimyristoyl phosphatidylcholine in sonicated vesicles has been measured employing 13C NMR using N-13CH3-labeled lipids which are introduced into the outer monolayer of non-labeled vesicles by a phosphatidylcholine exchange protein. The rate of transbilayer movement of dimyristoyl phosphatidylcholine shows a distinct maximum (half-time 4 h) in the temperature range at which the hydrocarbon phase transition occurs. The activation energy of the flip-flop rate above the phase transition is 23.7 +/- 2.0 kcal/mol.

Biological Transport↗

Effect of a phase transition on the binding of 1-anilino-8-naphthalenesulfonate to phospholipid membranes.

The binding of 1-anilino-8-naphthalenesulfonate (ANS) to dipalmitoyl-phosphatidycholine (DPPC)-sonicated vesicles was measured by a fluorimetric method in the vicinity of the gel-to-liquid crystalline phase transition temperature (Tm). A similar measurement was performed on large multimellar DPPC vesicles through equilibrium dialysis. Both measurements demonstrated anomalous dye binding in the temperature region of the Tm and slightly above (prefreezing region). The amount of ANS bound at this temperature region was in excess of what would be expected based on extrapolation of the high temperature binding data; just below the Tm, the amount of bound dye decreased abruptly. The fluorimetric studies on vesicles also indicated that inner monolayer binding of ANS was markedly inhibited below the Tm. The possibility that the increase in bound dye in the prefreezing region was caused by enhanced lateral compressibility, density fluctuations, or additional binding sites at the boundary of transient gel-like clusters is discussed and the general topic of anomalous increases in various membrane processes in the vicinity of a phase transition is briefly reviewed.

Anilino Naphthalenesulfonates↗

Detection of phase transitions and cooperative interactions by Avrami analysis of sigmoid biological time curves for muscle, nerve, growth, firefly, and infrared phosphorescence of green leaves, melanin, and cytochrome C.

A simple graphical analysis of sigmoid biological time curves for K+ leakage from muscle and nerve, for muscle tension and myosin ATPase, for animal, plant and bacterial growth, for firefly light flash, and for 3 micron infrared phosphorescence from green leaves, melanin, and cytochrome c shows good curve fits to the Avrami equation for phase transition kinetics. The congruences imply that the analyzed processes are rate-limited by cooperative interactions and phase transitions. That implication is strengthened and its potential usefulness enhanced by the finding that the Avrami exponents of the above biological processes are not randomly distributed but cluster about certain values indicating (in the context of the Avrami theory) whether the spread of the new phase from nuclei within the old phase occurs in one, two, or three dimensions. The implication is further strengthened by the finding that similar types of biological processes show similar values of the Avrami exponent.

Adenosine Triphosphate↗

Phase transition in a radiation-matter interaction with recoil and collisions.

The standard model introduced to describe the collective atomic recoil of an ensemble of atoms interacting with a strong electromagnetic field has been here extended by the inclusion of collisions with a buffer gas. As a result, we find that in the thermodynamic limit the coherent emission of radiation exhibits a continuous phase transition upon increasing the pump intensity. The output laser field is strictly larger than 0 only above a critical value. We find that the transition is not associated with the onset of spatial ordering but rather with the onset of a synchronization between the polarization phase and spatial position. A coherence parameter is introduced to characterize the phase transition.

Journal Article↗

Reversible phase transitions in emulsified nanostructured lipid systems.

Aqueous submicron-sized dispersions of the binary monolinolein/water system, which are stabilized by means of a polymer, internally possess a distinct nanostructure. Taking this as our starting point, we were able to demonstrate for the first time that the internal structure of the dispersed particles can be tuned by temperature in a reversible way. Upon increasing the temperature, the internal structure undergoes a transition from cubic via hexagonal to fluid isotropic, the so-called L2 phase, and vice versa. Intriguingly, in addition to the structural changes in topology, the particles expel (take up) water to (from) the aqueous continuous phase when increasing (decreasing) the temperature in a reversible way. At each temperature, the internal structure of the dispersed particles corresponds very well to the structure observed in nondispersed binary monolinolein with excess water. This agreement is independent of any thermal history (including phase transitions), which proves that the structures in the dispersed particles actually are in thermodynamic equilibrium with the surrounding water phase.

Cryoelectron Microscopy↗

Bend and splay elastic constants at a reentrant isotropic-calamitic-nematic phase transition.

By measuring the ratio between the major and minor axes of closed elliptical loops created by a magnetic field, the ratio between the bend (K33) and splay (K11) elastic constants of a lyotropic mixture of potassium laurate, decanol, and water in the calamitic nematic phase is measured as a function of temperature. Since these systems present two nematic-isotropic phase transitions--the usual one, at high temperatures, and a reentrant one, at low temperatures--such measurements are used to compare the behavior of these elastic constants at the neighborhoods of these two distinct regions, which have in common the vanishing of the order parameter. The experimental data have revealed the existence of two elastic constant branches, characterizing a distinct low- and high-temperature behavior. To explain such asymmetry we support that, because of the lyotropic nature of the compound, the micellar variation, which is mainly responsible for the reentrant phase, plays a distinct role at these two phase transitions.

Journal Article↗

Fourier transform infrared spectroscopy as a probe for the study of the hydration of lipid self-assemblies. II. Water binding versus phase transitions.

The gradual hydration of phospholipid films can be effectively probed by Fourier transform infrared (FTIR) spectroscopy (cf. part I of this series). The hydration-induced changes observed for lipid IR-absorption bands are probably composed of contributions arising from the effects of both the direct binding of water molecules and the thereby caused conformational changes and phase transitions in the lipid molecules and assemblies, respectively. In this article, an attempt is made to attribute some of the more indicative spectroscopic results to these molecular and supermolecular processes with a view to separating their individual contributions to the relevant spectroscopic data. This is done by considering a series of suitable PLs consisting of the palmitoyl and oleoyl lecithins, DPPC, DOPC, POPC, and OPPC, and one cephalin, DOPE. This choice of PCs and DOPE means that at room temperature and different degrees of hydration, several phase states including lamellar gel and liquid crystalline as well as certain nonlamellar phases are covered. The separation of the water-binding and phase-transition contributions to the FTIR-spectroscopic data, we believe, is clearly demonstrated by interpreting the hydration-dependent wavenumber shifts of the nu C=O band of the PCs. Carbonyl groups are affected to a more significant degree for lipids arrayed in the L alpha phase than in the gel phase. A number of spectral features reveal the lyotropically triggered chain-melting transition as well as other structural rearrangements of PCs. This is discussed in detail and demonstrates the excellent sensitivity of the FTIR methodology for the study of such systems.

1,2-Dipalmitoylphosphatidylcholine↗

Applications of moving window two-dimensional correlation spectroscopy to analysis of phase transitions and spectra classification.

Our recently proposed idea of moving window two-dimensional (2D) correlation spectroscopy, which partitions a data set into series of relatively small submatrices (windows) and calculates their covariance maps in succession, is tested for three convoluted data set. Phase-transition temperatures of oleic acid and poly-(N-isopropylacrylamide) in an aqueous solution are sought by analyzing covariances of their temperature-dependent near-infrared and infrared spectra, respectively, while Raman spectra of three kinds of polyethylene (PE) pellets are investigated to find the spectral differences among them and to classify randomly ordered spectra by a sample-sample (SS) covariance map. The criterion of mean of standard deviation of covariance matrices is used as an indicator of the crucial information present in these matrices so that only a few of them are discussed in details. The results are obtained quickly after very simple calculations and are studied at length. The baseline variation is not removed prior to the calculations but is found to be of use for the determination of the phase-transition temperatures. Randomly ordered Raman spectra of the PE pellets are classified by innovatively used and interpreted SS slice spectra, with the relation to principal component analysis discussed.

Journal Article↗

Effects of COR6.6 and COR15am polypeptides encoded by COR (cold-regulated) genes of Arabidopsis thaliana on dehydration-induced phase transitions of phospholipid membranes.

Cold acclimation of Arabidopsis thaliana includes the expression of cold-regulated (COR) genes and the accumulation of COR polypeptides. The hydration characteristics of two COR polypeptides, COR6.6 and COR15am, have been determined and their effects on the dehydration-induced liquid crystalline-to-gel and lamellar-to-hexagonal II phase transitions in phospholipid mixtures have been examined. After dehydration at osmotic pressures between 8 and 150 MPa, the water content of the COR polypeptides was less than that of bovine serum albumin, with COr15am the least hydrated: bovine serum albumin > COR6.6 > COR15am. Neither COR6.6 nor COR15am altered the dehydration-induced gel lamellar --> fluid lamellar phase transition temperature of either dipalmitoylphosphatidylcholine or dioleoylphosphatidylcholine (DOPC). In multilamellar vesicles of dioleoylphosphatidylethanolamine:DOPC (1:1, mol:mol) prepared by either freeze-thaw or reverse-phase evaporation methods, neither COR6.6, COR15am, nor bovine serum albumin altered the incidence of the dehydration-induced formation of the inverted hexagonal phase as a function of osmotic pressure. However, a specific ultrastructural alteration--the formation of a striated surface morphology in the lamellar domains--was observed in mixtures of dioleoylphosphatidylethanolamine:DOPC that were dehydrated in the presence of COR15am. Nevertheless, neither COR6.6 nor COR15am appears to participate in a specific protein-phospholipid interaction that alters the dehydration-induced phase behavior of phospholipid vesicles.

Arabidopsis↗

Nonanalytic microscopic phase transitions and temperature oscillations in the microcanonical ensemble: an exactly solvable one-dimensional model for evaporation.

We calculate exactly both the microcanonical and canonical thermodynamic functions (TDFs) for a one-dimensional model system with piecewise constant Lennard-Jones type pair interactions. In the case of an isolated N-particle system, the microcanonical TDFs exhibit (N - 1) singular (nonanalytic) microscopic phase transitions of the formal order N/2, separating N energetically different evaporation (dissociation) states. In a suitably designed evaporation experiment, these types of phase transitions should manifest themselves in the form of pressure and temperature oscillations, indicating cooling by evaporation. In the presence of a heat bath (thermostat), such oscillations are absent, but the canonical heat capacity shows a characteristic peak, indicating the temperature-induced dissociation of the one-dimensional chain. The distribution of complex zeros of the canonical partition may be used to identify different degrees of dissociation in the canonical ensemble.

Journal Article↗

Tooth eruption: the phase transition theory on biological formation of an orderly structure.

The mechanism of the formation of an orderly structure from random elements in organ development was clarified by studying the maturation of the dental arch in the human mandible. First, an application of methods established in statistical physics to a system of organ development was made possible, and then, the mathematical procedures for quantitative study of the structure and development of the dental arch were established in relation to radiographic data. The experimental results demonstrate that a parallel arrangement of the longitudinal axes of the lateral teeth is formed co-operatively in the dental arch. As formulation of the results to mathematical relations, the regulatory process was expressed by a non-linear Langevin equation of order parameter denoting an angle between longitudinal axes of the individual teeth. It follows that the orderly structure evolves with a change in thermodynamic potential; that is, the establishment of order in a phase transition. We propose the concept that organ differentiation is a phase transition in a dissipative system, with the decrease of gene activity substituted for temperature.

Adolescent↗

Effect of spatial bias on the nonequilibrium phase transition in a system of coagulating and fragmenting particles.

We examine the effect of spatial bias on a nonequilibrium system in which masses on a lattice evolve through the elementary moves of diffusion, coagulation, and fragmentation. When there is no preferred directionality in the motion of the masses, the model is known to exhibit a nonequilibrium phase transition between two different types of steady state, in all dimensions. We show analytically that introducing a preferred direction in the motion of the masses inhibits the occurrence of the phase transition in one dimension, in the thermodynamic limit. A finite-size system, however, continues to show a signature of the original transition, and we characterize the finite-size scaling implications of this. Our analysis is supported by numerical simulations. In two dimensions, bias is shown to be irrelevant.

Journal Article↗