Binding of dipyridamole to phospholipid vesicles: a fluorescence study

Binding and localization of the vasodilator and antitumor drug coactivator dipyridamole (DIP) and one of its derivatives, RA25, to phospholipid vesicles of DMPC (dimyristoylphosphatidylcholine) and DPPC (dipalmitoylphosphatidylcholine) was studied using fluorescence spectroscopy as well as quenching of fluorescence. The analysis of fluorescence data indicates that neutral dipyridamole binds to the phospholipids in their liquid crystalline phase with an association constant of 950 M(-1) and 1150 M(-1) to DMPC and DPPC, respectively. Protonation of DIP leads to a 3-fold reduction of the association constant. For the gel phospholipid phase, the binding is smaller (a factor of 2), independently of pH, suggesting that the more flexible lipid packing in the liquid crystalline phase facilitates the binding of the drug. The association constant of RA25 neutral form is considerably lower than for DIP, being around 295 M(-1). Fluorescence quenching with nitroxides TEMPO and stearic acid doxyl derivatives suggests the localization of DIP to be closer to the 5th carbon of alkyl chain. The quenching effect of 5-DSA below the lipid phase transition suggests that a strong static quenching may be operative. The quenching effect of 16-DSA is almost as great as that for 5-DSA below the phase transition, being even higher above the phase transition. This effect is probably due to the trans-gauche isomerization of the stearic acid nitroxide, making the encounter of its paramagnetic fragment with the DIP chromophore possible. Our data are consistent with DIP location close to the bilayer surface in the border of hydrophobic-polar heads interface which is similar to the data in micellar systems. In the case of RA25, the drug is in the outer part of the head group interface being much exposed to the aqueous phase and being significantly less accessible to the membrane nitroxide quenchers.     

Misinterpretation of body sensations in panic disorder

Cognitive accounts of panic predict that panic disorder patients will be particularly prone to misinterpret autonomic sensations. Several studies have produced results consistent with this prediction, but each is open to alternative interpretation. To clarify matters, 2 studies administered the Body Sensations Interpretation Questionnaire (BSIQ) to panic patients and controls. Panic patients were more likely to interpret ambiguous autonomic sensations as signs of immediately impending physical or mental disaster and were more likely than other anxiety disorder patients and nonpatients to believe these interpretations. In a 3rd study, a brief version of the BSIQ was shown to have satisfactory test-retest reliability, to change with treatment, and to discriminate treatments that varied in their effects on panic.     

Continuously extruded micro‐textured polypropylene films

The continuous extrusion of micro‐textured isotactic polypropylene (i‐PP) film and its tribological properties are reported. As analyzed by scanning electron microscopy, a rectangular‐semicircular micro‐patterned die successfully produced extruded cast‐films with hill‐like micro‐texture. Such films displayed static and kinetic coefficients of friction (COF_s and COF_k) values of 0.247 ± 0.028 and 0.245 ± 0.003, respectively, for a steel fixture sliding along the micro‐texture of the film. The equivalent COF_s and COF_k values for non‐textured (NT) films were 0.369 ± 0.036 and 0.340 ± 0.024, respectively, confirming that textured films displayed a reduction in COF of about 30%. For textured and NT films sliding on textured films, the COF_k values were even lower at 0.161 ± 0.013 and 0.113 ± 0.004, which represents about 20–40% reduction as compared with that for the NT‐NT counterparts. Films coated with a silicone lubricant displayed COF_s and COF_k values of 0.334 ± 0.042 and 0.099 ± 0.012, respectively, for NT films sliding over lubricated NT films, and 0.426 ± 0.031 and 0.063 ± 0.006, respectively, for textured films sliding over lubricated textured films. The COF_k values for textured/non‐lubricated films approach those of NT/lubricated films, indicating that micro‐textured polypropylene films may be used in environmentally sensitive applications where lubricants and fluorinated additives may not be used for reducing friction. POLYM. ENG. SCI., 54:2147–2154, 2014. © 2013 Society of Plastics Engineers     

Lithium fuel cells:: I. Lithium/poly(organophosphazene) membrane anodes in KOH and seawater

The main goal of our research project is to design safe, high energy and power density lithium/water systems. We explored the feasibility of substituting the natural bilayer (formed on the lithium surface when lithium is in contact with water), for a thin polymeric film. By substituting the natural bilayer film we hope to reduce the parasitic reactions occurring at the lithium/water interface, thus yielding an increase in the anodic efficiency. We investigated the effect of placing or casting a thin, (lithium/ion-conducting) polymer layer on the lithium metal surface. This paper is part one in a series of two papers. Paper I presents the results obtained with a lithium/polymer system, where the polymer was a monolayer of a polyphosphazene with 90% trifluoromethylphenoxy and 10% lithium carboxyphenoxy side groups (Polymer 4), or a multilayer film formed of one layer of poly[bis(methoxyethoxyethoxy)phosphazene] (MEEP) and one to three layers of Polymer 4 containing from 0 to 75 wt.% of lithium triflate salts. Paper II presents results obtained when the polymer layers were prepared using a polymer with equal amounts of methoxyethoxyethoxy and phenoxy side groups containing from 0 to 75 wt.% of lithium triflate salts. Phosphazene membranes have been designed and tailored to allow lithium ion conduction and prevent water migration to the surface of lithium metal. The phosphazene membranes enhance the safety of an aqueous lithium cell by inhibiting (or reducing) the reaction of lithium with water that evolves hydrogen at the anode. Original tests of lithium/phosphazene systems led to unpredictable open circuit voltages (OCVs). When the adhesion of the membrane to the lithium metal was improved, the OCV stabilized. The OCVs for the half-cell of lithium polymer aqueous electrolytes varies between −3.1 and −2.8 V_SCE, depending on the membrane. The current densities for this polymer system are in the range of 10⁻⁶-10⁻³ A/cm². The Columbic anodic efficiency is assumed to be near 100%—as hydrogen evolution is not measurable. Some of the polymeric membranes developed pinholes with use. Layered systems have also been designed to avoid the development of pinholes over time. In this paper, we present the results obtained by using polyphosphazenes with a 9:1 ratio of trifluoromethylphenoxy and p-carboxyphenoxy side groups and the lithium salt of the carboxylate function. Poly(organophosphazene) membranes with a single layer and a multilayer structure were tested in 8 M KOH or synthetic seawater for up to 5 days.     

Solubility of Si3N4 in Liquid SiO2

The nitrogen solubility in the SiO₂-rich liquid in the metastable binary SiO₂-Si₃N₄ system has been determined by analytical TEM to be 1%–4% of N/(O + N) at 1973–2223 K. Analysis of the near edge structure of the electron energy loss peak indicates that nitrogen is incorporated into the silicate network rather than being present as molecular N₂. A regular solution model with a positive enthalpy of mixing for the liquid was used to match the data for the metastable solubility of N in the presence of crystalline Si₃N₄ and to adjust the computed phase diagram. The solubility of Si₃N₄ in fused SiO₂ is far less than reported in liquid silicates also containing Al, Mg, and/or Y. Apparently, these cations act as modifiers that break anion bridges in the silicate network and, thereby, allow further incorporation of Si₃N₄ without prohibitive amounts of network cross-linking. Finally, indications emerged regarding the diffuse nature of the Si₃N₄-SiO₂ interface that leads to amorphous regions of higher N content.     

Effects of Interface Roughness on Residual Stresses in Thermal Barrier Coatings

Using a newly developed object-oriented finite-element analysis method, both an actual microstructure and model microstructures of a plasma-sprayed thermal barrier coating system were numerically simulated to analyze the full-field residual stresses of this coating system. Residual stresses in the actual microstructure were influenced by both the irregular top-coat/bond-coat interface and cracks in the top coat. By treating the microcracked top coat as a more-compliant solid microstructure, the effects of the irregular interface on residual stresses were examined. These results then could be compared to results that have been obtained by analyzing a model microstructure with a sinusoidal interface, which has been considered by some earlier investigators.     

Elevated Circulating and Placental SPINT2 Is Associated with Placental Dysfunction

Biomarkers for placental dysfunction are currently lacking. We recently identified SPINT1 as a novel biomarker; SPINT2 is a functionally related placental protease inhibitor. This study aimed to characterise SPINT2 expression in placental insufficiency. Circulating SPINT2 was assessed in three prospective cohorts, collected at the following: (1) term delivery (n = 227), (2) 36 weeks (n = 364), and (3) 24–34 weeks’ (n = 294) gestation. SPINT2 was also measured in the plasma and placentas of women with established placental disease at preterm (<34 weeks) delivery. Using first-trimester human trophoblast stem cells, SPINT2 expression was assessed in hypoxia/normoxia (1% vs. 8% O2), and following inflammatory cytokine treatment (TNFα, IL-6). Placental SPINT2 mRNA was measured in a rat model of late-gestational foetal growth restriction. At 36 weeks, circulating SPINT2 was elevated in patients who later developed preeclampsia (p = 0.028; median = 2233 pg/mL vs. controls, median = 1644 pg/mL), or delivered a small-for-gestational-age infant (p = 0.002; median = 2109 pg/mL vs. controls, median = 1614 pg/mL). SPINT2 was elevated in the placentas of patients who required delivery for preterm preeclampsia (p = 0.025). Though inflammatory cytokines had no effect, hypoxia increased SPINT2 in cytotrophoblast stem cells, and its expression was elevated in the placental labyrinth of growth-restricted rats. These findings suggest elevated SPINT2 is associated with placental insufficiency.     

Comparison of Hydraulic-Burst and Ball-on-Ring Tests for Measuring Biaxial Strength

The statistics of failure of the hydraulic-burst (HB) test were compared with those of the ball-on-ring (BOR) test. Polycrystalline Al₂O₃ tape-cast specimens, both square and circular, in two different sizes, were tested. Both the mean strengths and the Weibull moduli from the BOR tests were approximately twice the values from the HB tests. The area (volume) under stress is much larger for the HB test than the BOR test; therefore, the HB data can be considered as a low-probability-of-failure, low-strength tail of the BOR curve that has a lower Weibull modulus than the high-stress portion. Thus, BOR tests give a misleading picture of improvements in mechanical strength, because of changes in the fabrication and handling of substrates. However, previous observations that the incidence of edge and support failures was very high in the HB test were confirmed. Also, the apparent strength of the HB specimens was affected more strongly by size and shape than was that of the BOR specimens.