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

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

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

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

Medicinal Chemistry of Oligonucleotide Drugs - Milestones of the Past and Visions for the Future

The oligonucleotide therapeutics field has blossomed in recent years, with thirteen approved drugs today and the promise of accelerated growth in coming years. Much of the progress in this field is due to advances in the medicinal chemistry of oligonucleotides,combined with a judicious choice of molecular targets and disease areas. In this perspective, we describe the growth of this new class of drugs highlighting selected milestones in oligonucleotide medicinal chemistry

Tool Support for Design Science Research—Towards a Software Ecosystem: A Report from a DESRIST 2017 Workshop

The information systems (IS) field contains a rich body of knowledge on approaches, methods, and frameworks that supports researchers in conducting design science research (DSR). It also contains some consensus about the key elements of DSR projects—such as problem identification, design, implementation, evaluation, and abstraction of design knowledge. Still, we lack any commonly accepted tools that address the needs of DSR scholars who seek to structure, manage, and present their projects. Indeed, DSR endeavors, which are often complex and multi-faceted in nature and involve various stakeholders (e.g., researchers, developers, practitioners, and others), require the support that such tools provide. Thus, to investigate the tools that DSR scholars actually need to effectively and efficiently perform their work, we conducted an open workshop with DSR scholars at the 2017 DESRIST conference in Karlsruhe, Germany, to debate 1) the general requirement categories of DSR tool support and 2) the more specific requirements. This paper reports on the results from this workshop. Specifically, we identify nine categories of requirements that fall into the three broad phases (pre-design, design, and post design) and that contribute to a software ecosystem for supporting DSR endeavors

The emergence of functional microcircuits in visual cortex.

Sensory processing occurs in neocortical microcircuits in which synaptic connectivity is highly structured and excitatory neurons form subnetworks that process related sensory information. However, the developmental mechanisms underlying the formation of functionally organized connectivity in cortical microcircuits remain unknown. Here we directly relate patterns of excitatory synaptic connectivity to visual response properties of neighbouring layer 2/3 pyramidal neurons in mouse visual cortex at different postnatal ages, using two-photon calcium imaging in vivo and multiple whole-cell recordings in vitro. Although neural responses were already highly selective for visual stimuli at eye opening, neurons responding to similar visual features were not yet preferentially connected, indicating that the emergence of feature selectivity does not depend on the precise arrangement of local synaptic connections. After eye opening, local connectivity reorganized extensively: more connections formed selectively between neurons with similar visual responses and connections were eliminated between visually unresponsive neurons, but the overall connectivity rate did not change. We propose a sequential model of cortical microcircuit development based on activity-dependent mechanisms of plasticity whereby neurons first acquire feature preference by selecting feedforward inputs before the onset of sensory experience--a process that may be facilitated by early electrical coupling between neuronal subsets--and then patterned input drives the formation of functional subnetworks through a redistribution of recurrent synaptic connections

Helicobacter pylori Adapts to Chronic Infection and Gastric Disease via pH-Responsive BabA-Mediated Adherence

International audienceThe BabA adhesin mediates high-affinity binding of Helicobacter pylori to the ABO blood group antigen-glycosylated gastric mucosa. Here we show that BabA is acid responsive-binding is reduced at low pH and restored by acid neutralization. Acid responsiveness differs among strains; often correlates with different intragastric regions and evolves during chronic infection and disease progression; and depends on pH sensor sequences in BabA and on pH reversible formation of high-affinity binding BabA multimers. We propose that BabA's extraordinary reversible acid responsiveness enables tight mucosal bacterial adherence while also allowing an effective escape from epithelial cells and mucus that are shed into the acidic bactericidal lumen and that bio-selection and changes in BabA binding properties through mutation and recombination with babA-related genes are selected by differences among individuals and by changes in gastric acidity over time. These processes generate diverse H. pylori subpopulations, in which BabA's adaptive evolution contributes to H. pylori persistence and overt gastric disease