Hydrogen Bond Induced Nonmonotonic Composition Behavior of the Glass Transition in Aqueous Binary Mixtures

The glass transition temperature, T(g), of a binary mixture commonly varies monotonically between the T(g)s of its two components. However, mixtures of strongly associating liquids can instead exhibit a nonmonotonic T(g) variation. The origins of such nonideal mixing behavior have often been correlated with composition dependent structural variations. For binary mixtures between a hydrogen- (H-) bonded liquid and water, however, such behavior is generally not well understood. The ubiquity and importance of aqueous mixtures both in nature and in man-made applications stresses the needed for a better understanding. We here demonstrate nonmonotonic T(g) variations in binary mixtures of n-propylene glycol monomethyl ethers (nPGMEs) and water, where the composition dependent T(g) show maxima within an intermediate composition range. We show that these T(g) maxima correspond to crossovers in the composition dependence of the step amplitude in the isobaric heat capacity at T(g). We further demonstrate that the observed effects are caused by H-bond interactions involving the nPGME hydroxyl group. We can account for our obervations using a simple model based on two effects due to the added water: (i) an H-bond induced formation of effective relaxing entities and (ii) a plasticizing effect at high water contents

Calorimetric and relaxation properties of xylitol-water mixtures

We present the first broadband dielectric spectroscopy (BDS) and differential scanning calorimetry study of supercooled xylitol-water mixtures in the whole concentration range and in wide frequency (10(-2)-10(6) Hz) and temperature (120-365 K) ranges. The calorimetric glass transition, T-g, decreases from 247 K for pure xylitol to about 181 K at a water concentration of approximately 37 wt. %. At water concentrations in the range 29-35 wt. % a plentiful calorimetric behaviour is observed. In addition to the glass transition, almost simultaneous crystallization and melting events occurring around 230-240 K. At higher water concentrations ice is formed during cooling and the glass transition temperature increases to a steady value of about 200 K for all higher water concentrations. This Tg corresponds to an unfrozen xylitol-water solution containing 20 wt. % water. In addition to the true glass transition we also observed a glass transition-like feature at 220 K for all the ice containing samples. However, this feature ismore likely due to ice dissolution [A. Inaba and O. Andersson, Thermochim. Acta, 461, 44 (2007)]. In the case of the BDS measurements the presence of water clearly has an effect on both the cooperative a-relaxation and the secondary beta-relaxation. The a-relaxation shows a non-Arrhenius temperature dependence and becomes faster with increasing concentration of water. The fragility of the solutions, determined by the temperature dependence of the a-relaxation close to the dynamic glass transition, decreases with increasing water content up to about 26 wt. % water, where ice starts to form. This decrease in fragility with increasing water content is most likely caused by the increasing density of hydrogen bonds, forming a network-like structure in the deeply supercooled regime. The intensity of the secondary beta-relaxation of xylitol decreases noticeably already at a water content of 2 wt. %, and at a water content above 5 wt. % it has been replaced by a considerably stronger water (w) relaxation at about the same frequency. However, the similarities in time scale and activation energy between the w-relaxation and the beta-relaxation of xylitol at water contents below 13 wt. % suggest that the w-relaxation is governed, in some way, by the beta-relaxation of xylitol, since clusters of water molecules are rare at these water concentrations. At higher water concentrations the intensity and relaxation rate of the w-relaxation increase rapidly with increasing water content (up to the concentration where ice starts to form), most likely due to a rapid increase of small water clusters where an increasing number of water molecules interacting with other water molecules

Behaviour of an Intumescing System Subjected to Different Heating Conditions

Previous studies have indicated that the expansion of fire seals and fire stoppers will be dependent on the heat exposure. Standardized methods for classification includes exposure to a rapid heat exposure of the product that is tested, but this might not always be the worst case scenario for the product. In this paper a series of tests are presented in order to study how a graphite based intumescing system, intended for cavities, reacts when subjected to fire conditions different form that in the standardised method EN 1366-4. Two different experimental setups, a cone calorimeter at Lund University and a small-scale furnace at SP Fire Technology, were used in the tests. The start of expansion reaction in the tested fire stopper was around 180°C. The start of reaction temperature is rather independent of the incident heat flux, while expansion rate is clearly dependent on the incident heat flux. Furthermore, the studied fire stopper performed well in the small-scale furnace because the graphite expanded enough to give the same protection, although it is preheated or wet, as when subjected to a heat exposure similar to ISO 834. These results are good but they are only considered valid for the studied system and for the given situation. Future research is needed in order to study how other types of intumescing fire protection systems work when subjected to realistic fire environments

Dielectric secondary relaxation of water in aqueous binary glass-formers

The dielectric relaxation of water in glassy aqueous binary mixtures exhibits an Arrhenius behaviour with a nearly universal activation energy. We here demonstrate that its characteristic relaxation time follows a remarkably general functional dependence on the weight fraction of water for a wide range of molecular systems

Effects of Water Contamination on the Supercooled Dynamics of a Hydrogen-Bonded Model Glass Former

Broad-band dielectric spectroscopy is a commonly used tool in the study of glass-forming liquids. The high sensitivity of the technique together with the wide range of probed time scales makes it a powerful method for investigating the relaxation spectra of liquids. One particularly important class of glass-forming liquids that is often studied using this technique consists of liquids dominated by hydrogen (H) bond interactions. When investigating such liquids, particular caution has to be taken during sample preparation due to their often highly hygroscopic nature. Water can easily be absorbed from the atmosphere, and dielectric spectroscopy is a very sensitive probe of such contamination due to the large dipole moment of water. Our knowledge concerning the effects of small quantities of water on the dielectric properties of these commonly investigated liquids is limited. We here demonstrate the effects due to the presence of small amounts of water on the dielectric response of a typical H-bonded model glass former, tripropylene glycol. We show how the relaxation processes present in the pure liquid are affected by addition of water, and we find that a characteristic water induced relaxation response is observed for water contents as low as 0.15 wt %. We stress the importance of careful purification of hygroscopic liquids before experiments and quantify what the effects are if such procedures are not undertaken

MASQOT: a method for cDNA microarray spot quality control

BACKGROUND: cDNA microarray technology has emerged as a major player in the parallel detection of biomolecules, but still suffers from fundamental technical problems. Identifying and removing unreliable data is crucial to prevent the risk of receiving illusive analysis results. Visual assessment of spot quality is still a common procedure, despite the time-consuming work of manually inspecting spots in the range of hundreds of thousands or more. RESULTS: A novel methodology for cDNA microarray spot quality control is outlined. Multivariate discriminant analysis was used to assess spot quality based on existing and novel descriptors. The presented methodology displays high reproducibility and was found superior in identifying unreliable data compared to other evaluated methodologies. CONCLUSION: The proposed methodology for cDNA microarray spot quality control generates non-discrete values of spot quality which can be utilized as weights in subsequent analysis procedures as well as to discard spots of undesired quality using the suggested threshold values. The MASQOT approach provides a consistent assessment of spot quality and can be considered an alternative to the labor-intensive manual quality assessment process

Metabolite Signature during Short-Day Induced Growth Cessation in Populus

The photoperiod is an important environmental signal for plants, and influences a wide range of physiological processes. For woody species in northern latitudes, cessation of growth is induced by short photoperiods. In many plant species, short photoperiods stop elongational growth after a few weeks. It is known that plant daylength detection is mediated by Phytochrome A (PHYA) in the woody hybrid aspen species. However, the mechanism of dormancy involving primary metabolism remains unclear. We studied changes in metabolite profiles in hybrid aspen leaves (young, middle, and mature leaves) during short-day-induced growth cessation, using a combination of gas chromatography–time-of-flight mass spectrometry, and multivariate projection methods. Our results indicate that the metabolite profiles in mature source leaves rapidly change when the photoperiod changes. In contrast, the differences in young sink leaves grown under long and short-day conditions are less distinct. We found short daylength induced growth cessation in aspen was associated with rapid changes in the distribution and levels of diverse primary metabolites. In addition, we conducted metabolite profiling of leaves of PHYA overexpressor (PHYAOX) and those of the control to find the discriminative metabolites between PHYAOX and the control under the short-day conditions. The metabolite changes observed in PHYAOX leaves, together with those in the source leaves, identified possible candidates for the metabolite signature (e.g., 2-oxo-glutarate, spermidine, putrescine, 4-amino-butyrate, and tryptophan) during short-day-induced growth cessation in aspen leaves

Feasibility of Bariatric Surgery as a Strategy for Secondary Prevention in Cardiovascular Disease: A Report from the Swedish Obese Subjects Trial

Aims. Evaluation of bariatric surgery as secondary prevention in obese patients with ischemic heart disease (IHD). Methods. Analysis of data from 4047 subjects in the Swedish Obese Subjects (SOSs) study. Thirty-five patients with IHD are treated with bariatric surgery (n = 21) or conventional treatment (n = 14). Mean follow-up is 10.8 years. Results. Bariatric surgery resulted in sustained weight loss during the study period. After 2 years, the surgery group displayed significant reductions in cardiovascular risk factors, relief from cardiorespiratory symptoms, increments in physical activity, and improved quality of life. After 10 years, recovery from hypertension, diabetes, physical inactivity, and depression was still more common in the surgery group. There were no signs of increased cardiovascular morbidity or mortality in the surgery group. Conclusion. Bariatric surgery appears to be a safe and feasible treatment to achieve long-term weight loss and improvement in cardiovascular risk factors, symptoms, and quality of life in obese subjects with IHD

Large out-of-plane spin-orbit torque in topological Weyl semimetal candidate TaIrTe4

Topological quantum materials, with novel spin textures and broken crystal symmetries are suitable candidates for spintronic memory technologies. Their unique electronic properties, such as protected surface states and exotic quasiparticles, can provide an out-of-plane spin polarized current needed for external field free magnetization switching of magnets with perpendicular magnetic anisotropy. Conventional spin-orbit torque materials, such as heavy metals and topological insulators, provide only an in-plane spin polarized current, and recently explored materials with lower crystal symmetries provide very low out-of-plane spin polarized current components, which is not suitable for energy-efficient spin-orbit torque (SOT) applications. Here, we demonstrate a large out-of-plane damping-like SOT at room temperature using a topological Weyl semimetal candidate TaIrTe4 with a lower crystal symmetry. We performed spin-orbit torque ferromagnetic resonance (STFMR) experiments in a TaIrTe4/Ni80Fe20 heterostructure and observed a large out-of-plane damping-like SOT efficiency. The out-of-plane spin Hall conductivity is estimated to be an order of magnitude higher than the reported values in other materials. These findings of high spin Hall conductivity and large out-of-plane SOT efficiency are suitable for the development of energy efficient and external field-free spintronic devices