Structural studies of cyclic ureas: 3. Enthalpy of formation of barbital

A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5′-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard () molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as −(753.0 ± 1.8) kJ · mol⁻¹. The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid–solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ · mol⁻¹. The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as −(635.8 ± 1.9) kJ · mol⁻¹. This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes.     

Distinct dynamic behaviors of water molecules in hydrated pores

Water molecules confined inside narrow pores are of great importance in understanding the structure, stability, and function of water channels. Here we report that besides the H-bonding water that structures the pore, the permanent presence of a significant, fast-moving fraction of incompletely H-bonded water molecules inside the pore should control the free entry and exit of water. This is achieved by means of complementary DSC and solid-state NMR studies. We also present compelling evidence from X-ray diffraction data that the cluster formed by six water molecules in the most stable cage-like structure is sufficiently hydrophobic to be stably adsorbed in a nonpolar environment.     

Effect of conjugated linoleic acid immobilization on the hemocompatibility of cellulose acetate membrane

Conjugated linoleic acid (CLA) was covalently immobilized onto cellulose acetate (CA) membranes. The effects of CLA immobilization on the blood coagulation, platelet aggregation, and oxidative stress were evaluated using human blood. The resulting CLA grafting CA membranes were characterized with X-ray photoelectronic spectroscopy (XPS). The complete blood count (CBC) and coagulation time (CT) was evaluated in vitro for the hemocompatibility. Human serum albumin (HSA) and human plasma fibrinogen (HPF) was evaluated for the protein affinity. The production of reactive oxygen species (ROS) was measured by chemiluminescence (CL) method to evaluate the oxidative stress. The results showed that the CLA-immobilizing CA membrane could keep the CBC values more stable than unmodified CA membrane. The CLA-immobilized CA membranes also showed longer CT and less adsorption of plasma proteins. CLA-immobilized CA membrane could keep the CL counts of hydrogen peroxide and superoxide values more stable than unmodified CA membrane. These results suggest that a CLA-immobilized CA membrane could offer protection for patients against oxidative stress and would be helpful for reducing the dosage of anticoagulant during hemodialysis.     

A thermodynamic study of GPI-anchored and soluble form of alkaline phosphatase films at the air-water interface

Glycosylphosphatidyl inositol (GPI) anchored proteins are localized and clustered on the outer layer of the plasma membranes forming microdomains. Among them, mammalian alkaline phosphatases (AP-GPI) are widely distributed enzymes. They can also exist as soluble proteins without anchor (APs). Using the Langmuir film technique, we study the thermodynamic properties of monolayers for both protein forms at the air-buffer interface. The enzymatic activity is maintained at the interface but the adsorption of the two forms of AP is very different. AP-GPI presents a higher surface activity and a larger molecular area than the soluble form. The molecular area deduced for high surface pressures suggests a different organization of the monolayers for these two forms. APs molecules seem to adsorb as a multilayer at the interface while AP-GPI appear to be orientated with the major axis parallel to the interface. This orientation allows the accessibility of AP-GPI enzymatic sites that are turned in direction of the subphase as in vivo where the active sites must be turned outside of the membrane.     

CAD-based calibration and shape measurement with stereoDIC

A new calibration procedure is proposed for a stereovision setup. It uses the object of interest as the calibration target, provided the observed surface has a known definition (e.g., its CAD model). In a first step, the transformation matrices needed for the calibration of the setup are determined assuming that the object conforms to its CAD model. Then the 3D shape of the surface of interest is evaluated by deforming the a priori given freeform surface. These two steps are performed via an integrated approach to stereoDIC. The measured 3D shape of a machined Bézier patch is validated against data obtained by a coordinate measuring machine. The feasibility of the calibration method’s application to large surfaces is shown with the analysis of a 2-m² automotive roof panel.     

PENTATRAP: a novel cryogenic multi-Penning-trap experiment for high-precision mass measurements on highly charged ions

The novel five-Penning-trap mass spectrometer Pentatrap is developed at the Max-Planck-Institut für Kernphysik (MPIK), Heidelberg. Ions of interest are long-lived highly charged nuclides up to bare uranium. Pentatrap aims for an accuracy of a few parts in 10¹² for mass ratios of mass doublets. A physics program for Pentatrap includes Q-value measurements of β-transitions relevant for neutrino physics, stringent tests of quantum electrodynamics in the regime of extreme electric fields, and a test of special relativity. Main features of Pentatrap are an access to a source of highly charged ions, a multi-trap configuration, simultaneous measurements of frequencies, a continuous precise monitoring of magnetic field fluctuations, a fast exchange between different ions, and a highly sensitive cryogenic non-destructive detection system. This article gives a motivation for the new mass spectrometer Pentatrap, presents its experimental setup, and describes the present status.     

Neutron spin echo measurements of monolayer and capillary condensed water in MCM-41 at low temperatures

Neutron spin echo measurements of monolayer and capillary condensed heavy water (D(2)O) confined in MCM-41 C10 (pore diameter 2.10 nm) were performed in a temperature range of 190-298 K. The intermediate scattering functions were analyzed by the Kohlrausch-Williams-Watts stretched exponential function. The relaxation times of confined D(2)O in the capillary condensed state follow remarkably well the Vogel-Fulcher-Tammann equation between 298 and 220 K, whereas below 220 K they show an Arrhenius type behavior. That is, the fragile-to-strong (FTS) dynamic crossover occurs, which has never been seen in experiments on bulk water. On the other hand, for monolayer D(2)O, the FTS dynamic crossover was not observed in the temperature range measured. The FTS dynamic crossover observed in capillary condensed water would take place in the central region of the pore, not near the pore surface. Because the tetrahedral-like water structure in the central region of the pore is more preserved than that near the pore surface, the FTS dynamic crossover would be concerned with the tetrahedral-like water structure.     

Tackiness and cohesive failure of granular pastes: Mechanistic aspects

Granular pastes are dense dispersions of non-colloidal grains in a simple or a complex fluid. Typical examples are the coating, gluing or sealing mortars used in building applications. We study the rupture of a thick layer of mortar paste in a simple pulling test where the paste is confined between two flat surfaces. It is shown that, depending on the rheological properties of the paste and the plate separation velocity, two main failure modes are obtained. The first mode is the inwards shear flow of the paste with viscous fingering instabilities, similarly to what has been observed with Newtonian fluids and with non-Newtonian colloidal suspensions or polymer solutions. The second failure mode is stemming from the expansion of bubbles, similarly to what has been observed in soft adhesive polymer layers and, more recently, in highly viscous fluids. It is shown that the crossover between the two failure modes is determined by the conditions required to generate a pressure drop able to trigger the growth of pre-existing micro-bubbles smaller than the inter-granular distance.     

First observation of B(s)(0) → J/ψη and B(s)(0) → J/ψη'

We report first observations of B(s)(0) → J/ψη and B(s)(0) → J/ψη'. The results are obtained from 121.4 fb(-1) of data collected at the Υ(5S) resonance with the Belle detector at the KEKB e+ e- collider. We obtain the branching fractions B(B(s)(0) → J/ψη)=[5.10±0.50(stat)±0.25(syst)(-0.79)(+1.14)(N(B(s)(*) B(s)(*))]×10(-4), and B(B(s)(0) → J/ψη')=[3.71±0.61(stat)±0.18(syst)(-0.57)(+0.83)(N(B(s)(*) B(s)(*))]×10(-4). The ratio of the two branching fractions is measured to be (B(B(s) → J/ψη'))/(B(B(s) → J/ψη))=0.73±0.14(stat)±0.02(syst).     

Irradiation-induced formation of nanocrystallites with C15 Laves phase structure in bcc iron

A three-dimensional periodic structure is proposed for self-interstitial clusters in body-centered-cubic metals, as opposed to the conventional two-dimensional loop morphology. The underlying crystal structure corresponds to the C15 Laves phase. Using density functional theory and interatomic potential calculations, we demonstrate that in α-iron these C15 aggregates are highly stable and immobile and that they exhibit large antiferromagnetic moments. They form directly in displacement cascades, and they can grow by capturing self-interstitials. They thus constitute an important new element to account for when predicting the microstructural evolution of iron base materials under irradiation.