Temperature-concentration Phase Diagram Research Articles

Field-induced effects and ferroelectric critical endpoint in (K0.95Li0.05)(Nb1–x Ta x )O3 single crystals

Dielectric permittivities under dc biasing fields in the temperature range between –169 °C and 75 °C have been investigated in (K0.95Li0.05)(Nb1–x Ta x )O3 (KLNT–x, x = 71% and 74%). Field-induced ferroelectric phase transitions in KLNT–x have been clarified in the dc field applied along the [001] c direction (in the cubic coordinate). The ferroelectric critical endpoints in KLNT–71% and KLNT–74% have been determined to be 43.5 °C, 3.0 kV cm−1, and 30.3 °C, 2.0 kV cm−1, respectively. The tricritical point at which the first-order phase transition changes to the second-order phase transition has been estimated at 10.4 °C and x = 77.4% in the temperature–concentration phase diagram. The field-induced phase transitions and dielectric tunabilities have been discussed on the basis of the Landau-type free energy density.

Microfluidics-Based Drying-Wetting Cycles to Investigate Phase Transitions of Small Molecules Solutions.

Drying-wetting cycles play a crucial role in the investigation of the origin of life as processes that both concentrate and induce the supramolecular assembly and polymerization of biomolecular building blocks, such as nucleotides and amino acids. Here, we test different microfluidic devices to study the dehydration-hydration cycles of the aqueous solutions of small molecules, and to observe, by optical microscopy, the insurgence of phase transitions driven by self-assembly, exploiting water pervaporation through polydimethylsiloxane (PDMS). As a testbed, we investigate solutions of the chromonic dye Sunset Yellow (SSY), which self-assembles into face-to-face columnar aggregates and produces nematic and columnar liquid crystal (LC) phases as a function of concentration. We show that the LC temperature-concentration phase diagram of SSY can be obtained with a fair agreement with previous reports, that droplet hydration-dehydration can be reversibly controlled and automated, and that the simultaneous incubation of samples with different final water contents, corresponding to different phases, can be implemented. These methods can be further extended to study the assembly of diverse prebiotically relevant small molecules and to characterize their phase transitions.

Chirality transfer to harness mesophase transitions in liquid crystal mixtures containing an oxadiazole derivative

ABSTRACT Chiral liquid crystal mixtures are an important field of research in the development of these materials. The main advantage of chiral liquid crystal mixtures is their ability to produce an optically active three-dimensional structure. Moreover, 1,3,4-oxadiazoles have been widely used as electron-transporting/hole-blocking materials or emitting layers in electroluminescent diodes and nonlinear optical materials owing to their interesting properties. Here, we investigate the phase transitions in a mixture of a chiral oxadiazole derivative liquid crystal, EOS-12, and a traditional nematic liquid crystal, E7. EOS-12 is miscible with the E7 matrix at all concentrations. The mesomorphic properties of these mixtures were studied using differential scanning calorimetry (DSC), polarised optical microscopy (POM) and digital colourimetry analysis. In addition, the cholesteric pitch is measured using the Grandjean-Cano technique and photophysical studies were performed in solutions and films. Mixtures show polymorphism depending on the concentration and temperature: nematic, chiral nematic, TGBA*, and smectic phases. A temperature-concentration phase diagram was established using POM. Stabilisation of the SmA phase is observed with a greater temperature range than the constituents of the mixture. According to these results, the properties of the mixture can be used to create various material functionalities, depending on the composition of the mixture.

From valence fluctuations to long-range magnetic order in EuPd2(Si1−xGex)2 single crystals

${\mathrm{EuPd}}_{2}{\mathrm{Si}}_{2}$ is a valence-fluctuating system undergoing a temperature-induced valence crossover at ${T}_{V}^{\ensuremath{'}}\ensuremath{\approx}160\phantom{\rule{4pt}{0ex}}\mathrm{K}$. We present the successful single-crystal growth using the Czochralski method for the substitution series ${\mathrm{EuPd}}_{2}{({\mathrm{Si}}_{1\ensuremath{-}x}{\mathrm{Ge}}_{x})}_{2}$, with substitution levels $x\ensuremath{\le}0.15$. A careful determination of the germanium content revealed that only half of the nominal concentration is built into the crystal structure. From thermodynamic measurements it is established that ${T}_{V}^{\ensuremath{'}}$ is strongly suppressed for small substitution levels and antiferromagnetic order from stable divalent europium emerges for $x\ensuremath{\gtrsim}0.10$. The valence transition is accompanied by a pronounced change of the lattice parameter $a$ of order 1.8%. In the antiferromagnetically ordered state below ${T}_{N}=47\phantom{\rule{4pt}{0ex}}\mathrm{K}$, we find sizable magnetic anisotropy with an easy plane perpendicular to the crystallographic $c$ direction. An entropy analysis revealed that no valence fluctuations are present for the magnetically ordered materials. Combining the obtained thermodynamic and structural data, we construct a concentration-temperature phase diagram demonstrating a rather abrupt change from a valence-fluctuating to a magnetically ordered state in ${\mathrm{EuPd}}_{2}{({\mathrm{Si}}_{1\ensuremath{-}x}{\mathrm{Ge}}_{x})}_{2}$.

Hydrogen-bonding polymer complexation: Coacervation interfered with gelation

Complexation between polymers of different species in a common solvent is a fundamental process in various applications such as functional polymeric membrane and drug delivery, yet the understanding of energetics, phase behaviors, and kinetics of polymer complexation is rather challenging partially due to the multi-component nature of the system. In this work, we investigate the hydrogen-bonding complexation of poly(acrylic acid) (PAA) and poly(vinylpyrrolidone) (PVPON) in different solvents, and identify a variety of phase states, including homogenous solution, solid precipitate, liquid–liquid separation, gelation, and kinetically trapped structures. Among different solvents, N-methyl-2-pyrrolidone (NMP) has a similar structure to the repeating unit of PVPON and the complexation in NMP almost has no heat, suggesting the process is driven by entropy. The PAA/PVPON-NMP system exhibits an upper critical solution temperature; specifically, as the temperature decreases, a homogeneous solution first becomes opalescent, then undergoes a liquid–liquid separation, and finally undergoes a liquid–gel separation. On the other hand, when the polymer concentration is above a threshold, a homogenous solution turns into a gel directly without involving liquid–liquid separation with decreasing temperature. Accordingly, we construct a temperature–concentration phase diagram that shows how the gelation interplays with coacervation. This work provides a broad vision on phase behaviors of polymer complexation.

Thermodynamics, morphology and molecular structure of molecular compounds in trisamide triarylamine organogels and pseudo-organogels.

In this paper, potentially-gelling binary systems are investigated by DSC, X-ray and Electron microscopy in order to assess their gel status and the role of the Hansen solubility parameter. The low molecular weight organogelator is a Triarylamine Trisamide (TATA) while the solvents consist of a series of halogeno-ethanes and of toluene. Temperature-concentration phase diagrams are mapped out from DSC traces. They reveal the existence of one or more TATA/solvent molecular compounds. The X-ray data, that display different diffraction patterns depending on the solvent and the temperature, show the existence of different molecular structures, and thus confirm the outcome of the T-C phase diagram. Tentative molecular organizations are also discussed in light of previous results obtained in the solid state. The morphology by TEM on dilute systems, and TEM on more concentrated systems highlight the degree of physical cross-links, which leads one to regard some systems as pseudo-gels.

The structural and magnetic features of perovskite oxides La1–xSrxMnO3+δ (x = 0.05, 0.10, 0.20) depending on the strontium doping content and heat treatment

Sr-doped (0<x < 0.2) ceramic samples of the lanthanum manganite oxides were obtained via sol-gel method to investigate the influence of doping on structural, magnetic end electronic responses, and their correlations. Synthesized samples of non-stoichiometric compositions are rhombohedral single-phase. After annealing the formation of a phase-separated system as a mixture of orthorhombic phases was found. The R-3c and PnmaI, PnmaII* and PnmaII phases have been studied using Mössbauer spectroscopy, XRD, SEM analysis and magnetic measurements. The magnetic temperature-concentration phase diagram of La1–xSrxMnO3+δ (x = 0.05, 0.10, 0.20) was obtained.The Jahn-Teller effect or the orbital order breaking, as well as the competition between Mn3+–O2—Mn4+ double- and Mn3+–O2-–Mn3+ superexchange interaction was demonstrated under the effect of cation doping compound and interstitial oxygen value (δ). The relaxation character of the Mössbauer spectra and the type of magnetization dependences revealed nanosized magnetic clusters with fluctuation of their magnetic moment in all perovskite phases. Results are interpreted in terms of matrix – clusters: regions of sample with ferromagnetic type of ordering (cluster) exist in antiferromagnetically or ferromagnetically (with different exchange parameter) ordered matrix. Exchange interaction frustrations of the cluster with the matrix can lead to relaxation behavior of the magnetic moment of the cluster. The clusters size vary from about 3.9 to 5.7 nm. All samples are characterized by the presence of particles agglometates with a typical size about 0.4–0.8 μm; for annealed samples additional non-conducting regions with 80–220 nm in size were found. It is shown that the annealing time significantly affects the production of materials with determined properties and be useful in the applied field in technological processes.

A Spectrophotometric Turbidity Assay to Study Liquid-Liquid Phase Separation of UBQLN2 In Vitro.

Liquid-liquid phase separation (LLPS) is hypothesized to be the underlying mechanism for how membraneless organelles or biomolecular condensates form inside both prokaryotic and eukaryotic cells. Protein LLPS is a biophysical process during which proteins demix from homogeneous solution to form protein-dense droplets with liquid-like properties. Disruptions to LLPS, such as changes to material properties of condensates or physicochemical parameters for LLPS onset, are implicated in neurodegenerative diseases and cancer. Therefore, it is essential to determine the physicochemical parameters that promote protein LLPS. Here, we present our UV-Vis spectrophotometric turbidity assay to characterize the temperature and concentration dependence of LLPS for UBQLN2, a protein that undergoes LLPS via homotypic interactions in vitro and forms stress-induced condensates in cells. Mutations in UBQLN2 cause amyotrophic lateral sclerosis (ALS) and disrupt UBQLN2 LLPS. We present a detailed expression and purification protocol for a C-terminal construct of UBQLN2 and how we use microscopy to image UBQLN2 LLPS. We use our UV-Vis assay to construct temperature-concentration phase diagrams for wild-type and mutant UBQLN2 constructs to determine the effects of domain deletions and/or mutations on UBQLN2 phase separation.

Droplet Microfluidics for the Label-Free Extraction of Complete Phase Diagrams and Kinetics of Liquid-Liquid Phase Separation in Finite Volumes.

Liquid-liquid phase separation of polymer and protein solutions is central in many areas of biology and material sciences. Here, an experimental and theoretical framework is provided to investigate the thermodynamics and kinetics of liquid-liquid phase separation in volumes comparable to cells. The strategy leverages droplet microfluidics to accurately measure the volume ofthe dense phase generated by liquid-liquid phase separation of solutions confined in micro-sized compartments. It is shown that the measurement of the volume fraction of the dense phase at different temperatures allows the evaluation of the binodal lines that determine the coexistence region of the two phases in the temperature-concentration phase diagram. By applying a thermodynamic model of phase separation in finite volumes, it is further shown that the platform can predict and validate kinetic barriers associated with the formation of a dense droplet in a parent dilute phase, therefore connecting thermodynamics and kinetics of liquid-liquid phase separation.

Phase behavior of the sodium lauryl glutamate: effects of the temperature and concentration

Abstract The physical and chemical properties of sodium lauryl glutamate were systematically investigated in this work. To determine the critical micelle concentration (CMC) of sodium lauryl glutamate, the surface tension was measured using the Wilhelmy plate method. The Krafft point was determined using the ultraviolet/visible spectrophotometer. The effect of pH on the solute in the solution was studied using potentiometric titration. The critical packing parameter (CPP) and Gibbs free energy (ΔG) of micelle formation were calculated using the corresponding parameters. The temperature-concentration phase diagram of sodium lauryl glutamate was constructed using the dynamic light scattering system (DLS) and polarised optical microscopy (POM). The calculated theoretical data were combined with the actual observed data from the phase diagram. Finally, the phase behaviour of sodium lauryl glutamate was determined.

Effect of solvent isomers on the gelation properties of tri-aryl amine organogels and their hybrid thermoreversible gels with poly[vinyl chloride

The gelation properties of tri-aryl amine (TATA) in two isomers of dichlorobenzene, namely ortho-dichlorobenzene (o-DCB) and meta-dichlorobenzene (m-DCB), have been studied by calorimetry for mapping out the temperature-concentration phase diagram. It is shown that both systems behave differently, yet both form molecular compounds. The occurrence of these compounds is further demonstrated by neutron diffraction in o-DCB. Depending on the isomer used, X-ray investigations highlight a difference in the position of the diffraction peaks. The morphology observed by scanning electron microscopy reveals fibrillar systems in both cases, yet the fibrils' cross-sections are far larger in m-DCB with respect to o-DCB. The body of these results is discussed in light of current opinions on the role of the solvent. Ternary gels obtained with PVC have also been investigated by means of the same experimental approach. Calorimetry investigations and X-ray diffraction data show no significant difference for the behavior of the TATA moiety. The morphology studied by scanning electron microscopy allows one to distinguish clearly the TATA fibrils and the PVC network. This again confirms the possibility of preparing functional materials with an organogelator and a polymer through the making of hybrid gels.

Self assembling cluster crystals from DNA based dendritic nanostructures

Cluster crystals are periodic structures with lattice sites occupied by several, overlapping building blocks, featuring fluctuating site occupancy, whose expectation value depends on thermodynamic conditions. Their assembly from atomic or mesoscopic units is long-sought-after, but its experimental realization still remains elusive. Here, we show the existence of well-controlled soft matter cluster crystals. We fabricate dendritic-linear-dendritic triblock composed of a thermosensitive water-soluble polymer and nanometer-scale all-DNA dendrons of the first and second generation. Conclusive small-angle X-ray scattering (SAXS) evidence reveals that solutions of these triblock at sufficiently high concentrations undergo a reversible phase transition from a cluster fluid to a body-centered cubic (BCC) cluster crystal with density-independent lattice spacing, through alteration of temperature. Moreover, a rich concentration-temperature phase diagram demonstrates the emergence of various ordered nanostructures, including BCC cluster crystals, birefringent cluster crystals, as well as hexagonal phases and cluster glass-like kinetically arrested states at high densities.

Novel method for automatic search for stable ordered phases in multicomponent systems

The discovery of high entropy alloys (HEAs) dramatically increased the number of new commercial materials. Today, multicomponent systems are some of the main objects of research in the field of materials science. However, their chemical complexity significantly complicated the materials modeling, so conventional simulations techniques are hardly applicable. In this paper, we propose a rapid high-throughput approach for an automatic detection for stable ordered structures in multicomponent alloys. High computational efficiency is achieved through the use of a novel low-rank interatomic potential. The approach was verified on several binary temperature-concentration phase diagrams. Then it was applied to search for secondary phases in CoFeNiCr, which is believed to be a single-phase high-entropy alloy. As a result, we detected the ordering of Ni and Cr in CoFeNiCr and similar alloys in a wide range of temperatures and compositions.

Modulation of the Molecular Structure of Tri-aryl Amine Fibrils in Hybrid Poly[vinyl chloride] Gel/Organogel Systems

This paper reports on the thermodynamics through mapping out temperature–concentration phase diagrams and the molecular structure and the morphology of binary organogels prepared with trisamide triarylamine (TATA) in tetrachloroethane and on their ternary thermoreversible hybrid gels formed with polyvinyl chloride (PVC). For low PVC contents, the TATA organogel moiety behaves as in the binary systems, while for higher PVC contents, the thermal behavior is significantly altered with the appearance of a nonvariant event. The molecular structure of the TATA assemblies is compared with that observed in the bulk solid state. Three molecular packings are observed in the bulk, whose crystalline lattices are tentatively derived. Structure I obtained after the crystallization–purification process is seen to transform at higher temperature into structure II. By cooling, structure III is obtained, which transforms reversibly into structure II on heating. The metastability of structure I leads one to contemplate the possible formation of molecular compounds during the crystallization–purification process in the presence of chlorinated solvents, the more so as the crystalline structures in the gels turn out to exhibit high similarities. Finally, the morphology observation reveals that the TATA fibrils and the PVC matrix can be well identified for low PVC contents, while for higher PVC contents, one essentially observes the TATA fibrils

A theoretical study on the stability of the classical phases of surfactant-water systems in the temperature-concentration phase diagram

In the present study, we have used a mean field theory that is also a modified Ginzburg-Landau expansion in the order parameter. Single mode expansion of the order parameter were taken and written in terms of the reciprocal lattice vectors corresponding to the first reflection of the classical phases in such a way that the corresponding contour plot exhibits the required features of the respective phases. ’Wolfram Mathematica 8.0’ software was used for calculations and the free energy optimizations. The present theory stabilizes the classical phases in the concentration – temperature phase diagram. And percentage of the stabilized area for the lamellar, hexagonal, and BCC phases, are found to be 35.41%, 42.98%, and 21.61%, respectively.

Effect of a Good buffer on the fate of metastable protein-rich droplets near physiological composition

Metastable protein-rich microdroplets are produced from liquid-liquid phase separation (LLPS) of protein aqueous solutions. These globules can be intermediates for the formation of other protein-rich phases. Lysozyme aqueous solutions undergo LLPS around 0 °C in the presence of NaCl near physiological conditions. Here, it is shown that insertion of small amounts of 4-(2-hydroxyethyl)-1-piperazineethanesulfonate (HEPES, 0.1 M) as a second additive to lysozyme-NaCl-water solutions near physiological ionic strength (0.2 M) is an essential step for triggering conversion of protein-rich droplets into another phase. Specifically, LLPS induced by cooling reproducibly leads to a rapid and high-yield formation of compact tetragonal crystalline microparticles only in the presence of HEPES. These microcrystals exhibit small size (1-3 μm), narrow size distribution and guest-binding properties. The temperature-concentration phase diagram shows a characteristic topology with LLPS boundary metastable with respect to tetragonal microcrystals, which in turn become less stable than rod-shaped orthorhombic crystals above 40 °C. Interestingly, dynamic light scattering, hydrogen-ion titrations and isothermal titration calorimetry reveal that lysozyme-HEPES interactions were found to be weakly attractive and exothermic. Our findings indicate that additives of salting-in type can represent an important factor controlling the fate of metastable protein-rich microdroplets relevant to drug formulations, femtosecond crystallography, and potential implications in protein-driven cytoplasmic compartmentalization.

Physical Aspects of Organogelation: A Point of View.

The physics side of organogelation is broached through three main aspects, thermodynamics (formation and melting), structure (morphology and molecular organization), and rheology. A definition of a gel is first discussed so as to delimit the field of investigation; namely, systems constituted of fibril-like entities. It is again highlighted that gel formation occurs through first-order transitions, chiefly by homogeneous nucleation. A deeper knowledge of the system is thus achieved by mapping out the temperature–concentration phase diagram. Some experimental diagrams are shown, while diagrams likely to pertain to these systems are presented. The molecular arrangement is basically crystallization that occurs in a preferred direction, hence the formation of fibrils. The effects of the solvent type, the quenching process of the solution are discussed with respect to the morphology and the crystal structure. Finally, the rheological properties are tackled. Notions of critical gelation concentration and percolation are debated. The interest of mapping out the temperature–concentration phase diagram is emphasized, particularly for understanding the variation of the gel modulus with temperature.

Tuning the miscibility of water in imide-based ionic liquids.

Liquid-liquid phase behavior measurements were performed for binary mixtures of water and ionic liquids (ILs) containing the same 1-ethyl-3-methylimidazolium ([C2mim]+) cation and different imide-based anions, having symmetric (bis(fluorosulfonyl)imide ([FSI]-)) or asymmetric structures (2,2,2-trifluoromethylsulfonyl-N-cyanoamide ([TFSAM]-) and 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide ([TSAC]-)). An inversion of phase behavior was observed: while below ∼298 K, the miscibility of water in the studied ILs increases according to the order [C2mim][TSAC] < [C2mim][FSI] < [C2mim][NTf2], for temperatures above ∼303 K, the reverse trend is observed [C2mim][NTf2] < [C2mim][FSI] < [C2mim][TSAC]. In turn, above ∼306 K the [C2mim][TFSAM] is completely miscible with H2O in all ranges of concentrations. The obtained results also revealed an unusual water solubility variation of 11% in [C2mim][FSI], and 20% in [C2mim][TSAC], when the system temperature was changed by less than 1 K, around 298 K and 301 K, respectively. Molecular Dynamics (MD) simulations were used to understand the IL-water interactions and rationalize the experimental observations. These results suggested that the miscibility trends are mainly related to the ability of the water molecules to form water-anion and water-water aggregates in solution.

Molecular theory of liquid-crystal ordering in rod-coil diblock copolymers.

Molecular-statistical theory of rod-coil diblock copolymers is proposed using the general density functional approach which enables one to consider the cases of both weak and strong segregation. The free energy of the system is expressed as a functional of the phase-space densities of rod and coil monomers, which depend on the orientational and translational order parameters. Temperature-concentration phase diagrams are obtained and the profiles of all order parameters are calculated numerically by minimizing the polymer free energy. The lamellar phase is shown to possess strong orientational order which is partially induced by the phase structural anisotropy. The enhanced stability of the lamellar phase is determined by a combination of the microphase separation effects and the emergence of long-range smectic order.

Single Amino Acid Substitutions in Stickers, but Not Spacers, Substantially Alter UBQLN2 Phase Transitions and Dense Phase Material Properties.

UBQLN2 450-624 oligomerizes and undergoes temperature-responsive liquid-liquid phase transitions following a closed-loop temperature-concentration phase diagram. We recently showed that disease-linked mutations to UBQLN2 450-624 impart highly varying effects to its phase behavior, ranging from little change to significant decrease of saturation concentration and formation of gels and aggregates. However, how single mutations lead to these properties is unknown. Here, we use UBQLN2 450-624 as a model system to study the sequence determinants of phase separation. We hypothesized that UBQLN2 450-624 regions previously identified to promote its oligomerization are the "stickers" that drive interchain interactions and phase separation. We systematically investigated how phase behavior is affected by all 19 possible single amino acid substitutions at three sticker and two "spacer" (sequences separating stickers) positions. Overall, substitutions to stickers, but not spacers, substantially altered the shape of the phase diagram. Within the sticker regions, increasing hydrophobicity decreased saturation concentrations at low temperatures and enhanced oligomerization propensity and viscoelasticity of the dense phase. Conversely, substitutions to acidic residues at all positions greatly increased saturation concentrations. Our data demonstrate that single amino acid substitutions follow a molecular code to tune phase transition behavior of biopolymers.