Finite-temperature critical point of a glass transition.
Ontology highlight
ABSTRACT:
SUBMITTER: Elmatad YS
PROVIDER: S-EPMC2919917 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Liquids cooled towards the glass transition temperature transform into amorphous solids that have a wide range of applications. While the nature of this transformation is understood rigorously in the mean-field limit of infinite spatial dimensions, the problem remains wide open in physical dimensions. Nontrivial finite-dimensional fluctuations are hard to control analytically, and experiments fail to provide conclusive evidence regarding the nature of the glass transition. Here, we develop Monte Carlo methods for two-dimensional glass-forming liquids that allow us to access equilibrium states at sufficiently low temperatures to directly probe the glass transition in a regime inaccessible to experiments. We find that the liquid state terminates at a thermodynamic glass transition which occurs at zero temperature and is associated with an entropy crisis and a diverging static correlation length. Our results thus demonstrate that a thermodynamic glass transition can occur in finite dimensional glass-formers.
| S-EPMC6447585 | biostudies-literature
Project description:Recent heightened interest in inhaled bacteriophage (phage) therapy for combating antibacterial resistance in pulmonary infections has led to the development of phage powder formulations. Although phages have been successfully bioengineered into inhalable powders with preserved bioactivity, the stabilization mechanism is yet unknown. This paper reports the first study investigating the stabilization mechanism for phages in these powders. Proteins and other biologics are known to be preserved in dry state within a glassy sugar matrix at storage temperatures (T s) at least ~50°C below the glass transition temperature (T g). This is because at (T g - T s) >50°C, molecules are sufficiently immobilized with reduced reactivity. We hypothesized that this glass stabilization mechanism may also be applicable to phages comprising mostly of proteins. In this study, spray dried powders of Pseudomonas phage PEV20 containing lactose and leucine as excipients were stored at 5, 25 or 50°C and 15 or 33% relative humidity (RH), followed by assessment of bioactivity (PEV20 stability) and physical properties. PEV20 was stable with negligible titer loss after storage at 5°C/15% RH for 250?days, while storage at 33% RH caused increased titer losses of 1 log10 and 3 log10 at 5 and 25°C, respectively. The plasticizing effect of water at 33% RH lowered the T g by 30°C, thus narrowing the gap between T s and T g to 19-28°C, which was insufficient for glass stabilization. In contrast, the (T g - T s) values were higher (range, 46-65°C) under the drier condition of 15% RH, resulting in the improved stability which corroborated with the vitrification hypothesis. Furthermore, phage remained stable (?1 log10) when the (T g - T s) value lay between 26-48°C, but became inactivated as the value fell below 20°C. In conclusion, this study demonstrated that phage can be sufficiently stabilized in spray dried powders by keeping the (T g - T s) value above 46°C, thus supporting the vitrification hypothesis that phages are stabilized by immobilization inside a rigid glassy sugar matrix. These findings provide a guide to better manufacture and storage practices of inhaled phage powder products using for translational medicines.
| S-EPMC7237144 | biostudies-literature
Project description:It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity ? on temperature T. In an Arrhenius plot, ln ? vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover ?(×), where ?(×) has the same value, ?(×) ? 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ? ?(-1) breaks down and is replaced by a fractional form D/T ? ?(-?), with ? ? 0.85.
| S-EPMC3012472 | biostudies-literature
Project description:The glass transition temperature (Tg) is a key property that dictates the applicability of conjugated polymers. The Tg demarks the transition into a brittle glassy state, making its accurate prediction for conjugated polymers crucial for the design of soft, stretchable, or flexible electronics. Here we show that a single adjustable parameter can be used to build a relationship between the Tg and the molecular structure of 32 semiflexible (mostly conjugated) polymers that differ drastically in aromatic backbone and alkyl side chain chemistry. An effective mobility value, ζ, is calculated using an assigned atomic mobility value within each repeat unit. The only adjustable parameter in the calculation of ζ is the ratio of mobility between conjugated and non-conjugated atoms. We show that ζ correlates strongly to the Tg, and that this simple method predicts the Tg with a root-mean-square error of 13 °C for conjugated polymers with alkyl side chains.
| S-EPMC7021822 | biostudies-literature
Project description:We propose a chemical language processing model to predict polymers' glass transition temperature (Tg) through a polymer language (SMILES, Simplified Molecular Input Line Entry System) embedding and recurrent neural network. This model only receives the SMILES strings of a polymer's repeat units as inputs and considers the SMILES strings as sequential data at the character level. Using this method, there is no need to calculate any additional molecular descriptors or fingerprints of polymers, and thereby, being very computationally efficient. More importantly, it avoids the difficulties to generate molecular descriptors for repeat units containing polymerization point '*'. Results show that the trained model demonstrates reasonable prediction performance on unseen polymer's Tg. Besides, this model is further applied for high-throughput screening on an unlabeled polymer database to identify high-temperature polymers that are desired for applications in extreme environments. Our work demonstrates that the SMILES strings of polymer repeat units can be used as an effective feature representation to develop a chemical language processing model for predictions of polymer Tg. The framework of this model is general and can be used to construct structure-property relationships for other polymer properties.
| S-EPMC8201381 | biostudies-literature
Project description:It is generally believed that only intermolecular, elastically-effective crosslinks influence elastomer properties. The role of the intramolecular modifications of the polymer chains is marginalized. The aim of our study was the characterization of the structural parameters of cured elastomers, and determination of their influence on the behavior of the polymer network. For this purpose, styrene-butadiene rubbers (SBR), cured with various curatives, such as DCP, TMTD, TBzTD, Vulcuren®, DPG/S₈, CBS/S₈, MBTS/S₈ and ZDT/S₈, were investigated. In every series of samples a broad range of crosslink density was obtained, in addition to diverse crosslink structures, as determined by equilibrium swelling and thiol-amine analysis. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to study the glass transition process, and positron annihilation lifetime spectroscopy (PALS) to investigate the size of the free volumes. For all samples, the values of the glass transition temperature (Tg) increased with a rise in crosslink density. At the same time, the free volume size proportionally decreased. The changes in Tg and free volume size show significant differences between the series crosslinked with various curatives. These variations are explained on the basis of the curatives' structure effect. Furthermore, basic structure-property relationships are provided. They enable the prediction of the effect of curatives on the structural parameters of the network, and some of the resulting properties. It is proved that the applied techniques-DSC, DMA, and PALS-can serve to provide information about the modifications to the polymer chains. Moreover, on the basis of the obtained results and considering the diversified curatives available nowadays, the usability of "part per hundred rubber" (phr) unit is questioned.
| S-EPMC5456841 | biostudies-other
Project description:Epoxy-based powder coatings are an attractive alternative to solvent-borne coatings. Here, in-house synthesized low glass transition temperature (Tg) particles containing epoxy resin and polymethyl methacrylate formed coatings at room temperature upon impact with a surface. Suspension polymerization was used to prepare particles as a function of diglycidyl ether of bisphenol A (DGEBA) and methyl methacrylate ratios. Higher incorporation of DGEBA decreased the Tg to below ~20°C and eliminated the need to heat the particles and/or aluminum substrates to form coatings. Using an electrostatic powder coating apparatus, a ~70% particle deposition efficiency was achieved on aluminum substrates heated to 200°C. Whereas, at room temperature, high-speed single particle impact experiments proved that particle bonding occurred at a critical velocity of 438 m/s, comparable to commercial cold spray technologies. The in-house synthesized particles used in this study hold potential in traditional and emerging additive manufacturing applications.
| S-EPMC6342499 | biostudies-literature
Project description:Pathogenic bacteria such as Salmonella enterica exhibit high desiccation tolerance, enabling long-term survival in low water activity (aw) environments. Although there are many reports on the effects of low aw on bacterial survival, the mechanism by which bacteria acquire desiccation tolerance and resistance to heat inactivation in low-aw foods remains unclear. We focused on the glass transition phenomenon, as bacteria may acquire environmental tolerance by state change due to glass transition. In this study, we determined the glass transition temperature (Tg) in S. enterica serovars under different aw conditions using thermal rheological analysis (TRA). The softening behaviour associated with the state change of bacterial cells was confirmed by TRA, and Tg was determined from the softening behaviour. Tg increased as the aw decreased in all S. enterica serovars. For example, while the Tg of five S. enterica serovars was determined as 35.16°C to 57.46°C at 0.87 aw, the Tg of all the five serovars increased by 77.10°C to 83.30°C at 0.43 aw. Furthermore, to verify the thermal tolerance of bacterial cells, a thermal inactivation assay was conducted at 60°C for 10 min under each aw condition. A higher survival ratio was observed as aw decreased; this represented an increase in Tg for Salmonella strains. These results suggest that the glass transition phenomenon of bacterial cells would associate with environmental tolerance.
| S-EPMC7259547 | biostudies-literature
Project description:Liquid-liquid transition, a phase transition of one liquid phase to another with the same composition, provides a key opportunity for investigating the relationship between liquid structures and dynamics. Here we report experimental evidences of a liquid-liquid transition in glass-forming La50Al35Ni15 melt above its liquidus temperature by (27)Al nuclear magnetic resonance including the temperature dependence of cage volume fluctuations and atomic diffusion. The observed dependence of the incubation time on the degree of undercooling is consistent with a first-order phase transition. Simulation results indicate that such transition is accompanied by the change of bond-orientational order without noticeable change in density. The temperature dependence of atomic diffusion revealed by simulations is also in agreement with experiments. These observations indicate the need of two-order parameters in describing phase transitions of liquids.
| S-EPMC4510689 | biostudies-literature
Project description:Blood is the basic medium in the existence, evolution and physiological balance of animals and represents the biochemical "Internet" of the body; at least human blood exhibit the presence of an emergent phase that is highly unusual. Homeostasis, the state of the optimal functioning of the body, is maintained in living organisms by many chemical and physical conditions, particularly temperature. However, no regulatory mechanism has been identified that has led to a predetermined (molecularly encoded) optimal, individually variable, very specific temperature of around 36 °C. Additionally, the homeostatic temperature range, which is kept within predetermined limits, is merely an empirical fact. In the following, I will show that the reference temperature that is necessary to achieve homeostasis can be established, and a preset homeostatic range can be determined, using an original experimental method and refined tools of mathematical physics related to the nonlinear measures of the complexity of human blood. Moreover, signatures of a macroscopic coherent state in a non-equilibrium system at a critical temperature are obtained.
| S-EPMC8599461 | biostudies-literature