Two-state and continuous phase transitions in lipid bilayers A time-resolved X-ray diffraction study

Structural changes associated with transition from one phase to another have been examined in several lipid-water systems using time-resolved X-ray diffraction methods. Two types of transition mechanism can be recognized on the basis of scattering originating from the packing of the hydrocarbon chains. Two-state transitions are characterized by coexistence of the wide-angle scattering patterns of the initial and final phases throughout the transition region. Continuous transitions, on the other hand, take place through a series of intermediate states that are believed to arise from deformation of the hydrocarbon chain lattice as one phase transforms into another. Two-state processes are observed as subgel to liquid crystal transitions, and continuous transformations are typical of subgel to gel phase transitions. Examples of these transition types are presented and other transitions that do not appear to conform to either of these mechanisms are described.     

Two-state and continuous phase transitions in lipid bilayers A time-resolved X-ray diffraction study

Structural changes associated with transition from one phase to another have been examined in several lipid-water systems using time-resolved X-ray diffraction methods. Two types of transition mechanism can be recognized on the basis of scattering originating from the packing of the hydrocarbon chains. Two-state transitions are characterized by coexistence of the wide-angle scattering patterns of the initial and final phases throughout the transition region. Continuous transitions, on the other hand, take place through a series of intermediate states that are believed to arise from deformation of the hydrocarbon chain lattice as one phase transforms into another. Two-state processes are observed as subgel to liquid crystal transitions, and continuous transformations are typical of subgel to gel phase transitions. Examples of these transition types are presented and other transitions that do not appear to conform to either of these mechanisms are described.     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

Detailed Investigation of the Structural,Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano‐Triggered Single‐Crystal‐to‐Single‐Crystal Phase Transitions

Mechano‐induced phase transitions in organic crystalline materials, which can alter their properties, have received much attention. However, most mechano‐responsive molecular crystals exhibit crystal‐to‐amorphous phase transitions, and the intermolecular interaction patterns in the daughter phase are difficult to characterize. We have investigated phenyl(phenylisocyanide)gold(I) ( 1 ) and phenyl(3,5‐dimethylphenylisocyanide)gold(I) ( 2 ) complexes, which exhibit a mechano‐triggered single‐crystal‐to‐single‐crystal phase transition. Previous reports of complexes 1 and 2 have focused on the relationships between the crystalline structures and photoluminescence properties; in this work we have focused on other aspects. The face index measurements of complexes 1 and 2 before and after the mechano‐induced phase transitions have indicated that they undergo non‐epitaxial phase transitions without a rigorous orientational relationship between the mother and daughter phases. Differential scanning calorimetry analyses revealed the phase transition of complex 1 to be enthalpically driven by the formation of new aurophilic interactions. In contrast, the phase transition of complex 2 was found to be entropically driven, with the closure of an empty void in the mother phase. Scanning electron microscopy observation showed that the degree of the charging effect of both complexes 1 and 2 was changed by the phase transitions, which suggests that the formation of the aurophilic interactions affords more effective conductive pathways. Moreover, flash‐photolysis time‐resolved microwave conductivity measurements revealed that complex 1 increased in conductivity after the phase change, whereas the conductivity of complex 2 decreased. These contrasting results were explained by the different patterns in the aurophilic interactions. Finally, an intriguing disappearing polymorphism of complex 2 has been reported, in which a polymorph form could not be obtained again after some period of time, even with repeated trials. The present studies provide us with a variety of hitherto unknown insights into mechano‐responsive molecular crystals, which help us to understand the phase transition behaviors upon mechanical stimulation and establish rational design principles.     

Effect of temperature on the surface phase behavior of n-hexadecyl dihydrogen phosphate in adsorption layers at the air-water interface

We present the adsorption kinetics and the surface phase behavior of n-hexadecyl dihydrogen phosphate (n-HDP) at the air-water interface by film balance and Brewster angle microscopy (BAM). A phase diagram, which shows a triple point at about 25.8 degrees C, is constructed by measuring the surface pressure (pi)-time (t) adsorption isotherms. Below 25.8 degrees C, each of the pi-t curves shows a plateau at about zero surface pressure indicating the existence of a first-order phase transition. The BAM observation confirms the order of this phase transition by presenting two-surface phases during this plateau. However, the BAM observation also shows clearly another second-order phase transition from an isotropic phase to a mosaic-textured liquid condensed (LC) phase. The initial phase is a gas (G) phase. Considering the peculiarity of the middle phase, we suggest this phase as an intermediate (I) phase. Above the triple point, the pi-t curves predict the existence of two-step first-order phase transitions. Similar to the results at lower temperatures, the BAM images show two-surface phases during these first-order phase transitions together with a second-order phase transition from an isotropic phase to an LC phase. These transitions are classified as a first-order G-LE (liquid expanded) phase transition, which is followed by another first-order LE-I phase transition. The second-order phase transition is an I-LC phase transition. Contrary to these results, at 36 degrees C both the pi-t measurements and the BAM observation present only two first-order phase transitions, which are G-LE at zero surface pressure and LE-LC transition at higher surface pressure. The shape of the domains during the main transitions shows a peculiar change from a circular at 20 degrees C to an elongated at 24 degrees C and finally to a circular shape at 36 degrees C. Such a change in the domain shapes has been explained considering the dehydration effect at higher temperatures as well as the nature of phases.     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

 用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

How many phases and phase transitions do exist in Gibbs adsorption layers at the air-water interface?

Four different phases and four different first-order phase transitions have been shown to exist in Gibbs adsorption layers of mixtures containing n-hexadecyl dihydrogen phosphate (n-HDP) and L-arginine (L-arg) at a molar ratio of 1:2. These conclusions have been made from surface pressure-time (pi-t) adsorption isotherms measured with a film balance and from monolayer morphology observed with a Brewster angle microscopy (BAM). The observed four phases are gas (G), liquid expanded (LE), liquid condensed (LC) and LC' phases. Three first-order phase transitions are G-LE, LE-LC and LC-LC'. However, the thermodynamically allowed G-LC phase transition in a 1.2 x 10(-4) M mixture at 2 degrees C, which is below the so-called triple point, is kinetically separated into the G-LE and LE-LC phase transitions. The most interesting observation is that the homogeneous LC phase shows a new first-order phase transition named as LC-LC' at 2 or 5 degrees C. The LE and LC phases represent circular and fractal shaped domains, respectively, whereas the LC' phase shows very bright, anisotropic and characteristic shaped domains.     

Second-order phase transitions in amorphous gallium clusters

Ion mobility and calorimetry measurements have been used to probe the nature of the phase transitions in gallium clusters with 29-55 atoms. While most clusters appear to undergo a first-order transition between solidlike and liquidlike phases, a few show the signature of melting without a significant latent heat. These transitions appear to be the finite size analogue of a second-order phase transition, and they presumably occur for some cluster sizes because their solidlike phase is amorphous.     

Structural phase transitions in pentacosane C25H52

The pentacosane undergoes a series of structural phase transitions in addition to the melting transition according to an x-ray scattering study. A phenomenological theory is developed to describe the structural phase transitions between different phases observed in pentacosane. We present a detailed analysis of the different phases and analyze the temperature anomalies of the elastic constants and heat capacity. The thermodynamic anomalies on the different phase transitions are described by the coupling between the order parameters and the elastic strains. The theoretical predictions are found to be in good qualitative agreement with experimental results.     

Quinaldine: Accessing two crystalline polymorphs via the supercooled liquid

Quinaldine (2-methyl quinoline) is a liquid at room temperature, which can be supercooled to reach finally the glassy state. By heating the glass above the glass transition temperature T(g) = 180 K the sample performs two subsequent transitions into, likewise, dielectrically active phases. Thus, the reorientational relaxations of these phases as well as the kinetics of the phase transitions can be tracked in a highly resolved way by dielectric spectroscopy. X-ray diffraction analysis clearly shows two structurally different crystalline phases in addition to the supercooled liquid. Calorimetric measurements support the notion of first order phase transitions, occurring irreversibly in the supercooled regime, and suggest that the intermediate crystalline phase is metastable, too. Analyzing the quite distinct dielectric relaxation strengths, we discuss the possible nature of the two crystalline phases. Additionally, a very similar behavior to quinaldine is observed for 3-methyl quinoline, indicating a broad field of polymorphism among the quinoline derivatives.     

Light induced shifts of ferroelectric mesophase transitions

Several series of recently synthesized chiral azobenzene liquid crystals exhibit transitions driven by both illumination and temperature: some compounds can be 'melted' from the SmC* phase to the isotropic phase by increasing illumination only; according to the phase sequences, SmA, TGBA, N*, and blue phases are also involved in such behaviour. The observed phenomena are reversible and transition temperatures are reproducible in identical light conditions. Some specific transitions have been studied. Their temperatures can be lowered to 10 degrees below the dark transition values by increasing the illumination of samples. Under illumination, those transitions exhibit first order behaviour.     

Light induced shifts of ferroelectric mesophase transitions

Several series of recently synthesized chiral azobenzene liquid crystals exhibit transitions driven by both illumination and temperature: some compounds can be 'melted' from the SmC* phase to the isotropic phase by increasing illumination only; according to the phase sequences, SmA, TGBA, N*, and blue phases are also involved in such behaviour. The observed phenomena are reversible and transition temperatures are reproducible in identical light conditions. Some specific transitions have been studied. Their temperatures can be lowered to 10 degrees below the dark transition values by increasing the illumination of samples. Under illumination, those transitions exhibit first order behaviour.     

Investigation of poly[oligo(ethylene glycol)diacrylates] as potential stationary phases in GC

Poly[oligo(ethylene glycol)diacrylate]s were investigated as potential candidates for application as stationary phases in capillary gas chromatography. Depending on the molar mass of the monomer, up to three different phase transitions were observed in calorimetric scans of the polymers. Two transitions have been identified as the glass transition and melting of crystallites while the nature of the third effect remains unknown. The new stationary phases demonstrate a good separating ability and selectivity in the viscous‐elastic state, i.e. at temperatures above the glass transition and melting points. The new polymeric stationary phases possess selectivity similar to conventional PEG columns but provide better thermal stability than conventional PEG stationary phases.     

Phase-ordering kinetics of the liquid-liquid transition in single-component molecular liquids

Recently it has been revealed that even a single-component liquid can have more than two liquid states. The transition between these liquid states is called the "liquid-liquid transition." Most known liquid-liquid transitions occur at temperatures and pressures which are difficult to access experimentally, so the physical nature of the transition, particularly the kinetics, has remained elusive. However, the recent discovery of liquid-liquid transitions in molecular liquids opens up a possibility to study the kinetics in detail. Here, we report the first phase field simulation on the kinetics of a liquid-liquid transition and its direct comparison with experimental results of the molecular liquids. Both nucleation-growth-type and spinodal-decomposition-type liquid-liquid transformation observed experimentally are well reproduced by numerical simulation based on a two-order-parameter model of liquid that regards the liquid-liquid transition as the cooperative formation of locally favored structures. Thus, phase field calculations may allow us to predict the kinetics of liquid-liquid transitions and the resulting spatiotemporal change of various physical properties of the liquid, such as density and refractive index.     

A pressure-jump time-resolved X-ray diffraction study of cubic-cubic transition kinetics in monoolein

In the past two decades, the geometric pathways involved in the transformations between inverse bicontinuous cubic phases in amphiphilic systems have been extensively theoretically modeled. However, little experimental data exists on the cubic-cubic transformation in pure lipid systems. We have used pressure-jump time-resolved X-ray diffraction to investigate the transition between the gyroid QGII and double-diamond QDII phases in mixtures of 1-monoolein in 30 wt % water. We find for this system that the cubic-cubic transition occurs without any detectable intermediate structures. In addition, we have determined the kinetics of the transition, in both the forward and reverse directions, as a function of pressure-jump amplitude, temperature, and water content. A recently developed model allows (at least in principle) the calculation of the activation energy for lipid phase transitions from such data. The analysis is applicable only if kinetic reproducibility is achieved, at least within one sample, and achievement of such kinetic reproducibility is shown here, by carrying out prolonged pressure-cycling. The rate of transformation shows clear and consistent trends with pressure-jump amplitude, temperature, and water content, all of which are shown to be in agreement with the effect of the shift in the position of the cubic-cubic phase boundary following a change in the thermodynamic parameters.     

X-ray kinematography of phase transformations of three-component lipid mixtures: a time-resolved synchrotron X-ray scattering study using the pressure-jump relaxation technique

By using the pressure-jump relaxation technique in combination with time-resolved synchrotron small-angle X-ray diffraction (TRSAXS), the kinetics of lipid phase transformations of ternary lipid mixtures serving as model systems of heterogeneous raftlike membranes were investigated. To this end, we first established the temperature-pressure phase diagram of a model lipid raft mixture, 1,2-dioleoyl- sn-glycero-3-phosphatidylcholine (DOPC)/1,2-dipalmitoyl- sn-glycero-3-phosphatidylcholine (DPPC)/cholesterol (1:2:1), using Fourier transform infrared spectroscopy and SAXS, covering the pressure range from 1 bar to 10 kbar at temperatures in the range from 7 to 80 degrees C. We then studied the kinetics of interlamellar phase transitions of the ternary lipid system involving transitions from the fluidlike (liquid-disordered, l d) phase to the liquid-ordered (l o)/liquid-disordered (l d) two-phase coexistence region as well as between the two- and three-phase coexistence regions of the system, where also solid-ordered phases (s o) are involved. The phase transition from the all-fluid l d phase to the l o+l d two-phase coexistence region turns out to be rather rapid. Phases appear or disappear within the 25 ms time resolution of the technique, followed by a slow lattice relaxation process, which, depending on the pressure-jump amplitude, takes several seconds. Contrary to many one-component phospholipid phase transitions, the kinetics of the l d <--> l o+l d transition follows a similar time scale and mechanism for the pressurization and depressurization direction. A similar behavior is observed for the phase transition kinetics of the s o+l o+l d <--> l o+l d transformation and even for the s o+l o+l d <--> l d transformation, jumping across the l o+l d two-phase region. All transitions are fully reversible, and no intermediate states are populated. As indicated by the complex relaxation profiles observed, the overall rates observed seem to reflect the effect of coupling of various dynamical processes through the transformation, involving fast conformational changes in the sub-millisecond time regime and slow relaxation of the lattices growing, probably being largely controlled by the transport and redistribution of water into and in the new phases of the multilamellar vesicle assemblies.     

Raman scattering study of high-pressure phase transition in thiourea

A high-pressure Raman spectroscopic study of phase transitions in thiourea is reported. The changes in the Raman spectra with increasing and decreasing pressure have been followed to a maximum pressure of approximately 11 GPa. We observe several changes in the spectra including splitting of modes, appearance of new modes, and sudden change in the slope of the frequency-pressure curve at several pressures. On the basis of this study, we propose the existence of three more transitions in this system to phases VII, VIII, and IX at approximately 1, 3, and 6.1 GPa, respectively, in addition to the V-VI phase transition at 0.35 GPa reported earlier. All the transitions have been found to be completely reversible. We interpret these changes in terms of symmetry-lowering phase transitions.     

Branchings of the fully symmetrical solution of the molecular field equation in liquid crystals

A general scheme has been constructed to study the branching of the fully symmetrical solution of the molecular field equation in the case when the molecular coordinates parametrise a certain group Q. A relationship is established between these branchings and the phase transitions. Branchings corresponding to the formation of orientationally ordered and spatially modulated structures are studied explicitly. Special attention is paid to phase transitions from the isotropic liquid to nematic and cholesteric phases. Characteristics of these transitions (for example Curie temperature, order of transition, and symmetry of the phase formed) have been related to the intermolecular potential energy and the pair correlation function.     

四氯合铜酸二烷基铵相变的热分析和红外光谱

用DSC和TG研究了(n-C_nH_(2n+1)NH_3)_2CuCl_4(n=7-12)(记为C_nM)配合物的热稳定性和固-固相变。由红外光谱讨论了C_9Cu三个相的性质。发现C_nM的热稳定性呈奇偶效应; 主相变峰温随链长增长而升高; 相变总ΔH和ΔS也随链增长而加大; 当n≤9时, 高温相为部分无序相; 而n≤10时, 高温相为构象无序相。C_9Cu的主相变主要源自链间堆积结构变化。而在307.7 K的相变主要与烃链有序-无序变化有关。