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We conducted a petrologic study of apatite within eight unbrecciated, non-cumulate eucrites and two monomict, non-cumulate eucrites. These data were combined with previously published data to quantify the abundances of F, Cl, and H2O in the bulk silicate portion of asteroid 4 Vesta (BSV). Using a combination of apatite-based melt hygrometry/chlorometry and appropriately paired volatile/refractory element ratios, we determined that BSV has 3.0–7.2 ppm F, 0.39–1.8 ppm Cl, and 3.6–22 ppm H2O. The abundances of F and H2O are depleted in BSV relative to CI chondrites to a similar degree as F and H2O in the bulk silicate portion of the Moon. This degree of volatile depletion in BSV is similar to what has been determined previously for many moderately volatile elements in 4 Vesta (e.g., Na, K, Zn, Rb, Cs, and Pb). In contrast, Cl is depleted in 4 Vesta by a greater degree than what is recorded in samples from Earth or the Moon. Based on the Cl-isotopic compositions of eucrites and the bulk rock Cl/F ratios determined in this study, the eucrites likely formed through serial magmatism of a mantle with heterogeneous δ37Cl and Cl/F, not as extracts from a partially crystallized global magma ocean. Furthermore, the volatile depletion and Cl-isotopic heterogeneity recorded in eucrites is likely inherited, at least in part, from the precursor materials that accreted to form 4 Vesta and is unlikely to have resulted solely from degassing of a global magma ocean, magmatic degassing of eucrite melts, and/or volatile loss during thermal metamorphism. Although our results can be reconciled with the past presence of wide-scale melting on 4 Vesta (i.e., a partial magma ocean), any future models for eucrite petrogenesis involving a global magma ocean would need to account for the preservation of a heterogeneous eucrite source with respect to Cl/F ratios and Cl isotopes.

Background The Kilimanjaro region has one of the highest levels of reported alcohol intake per capita in Tanzania. Age at first drink has been found to be associated with alcohol problems in adulthood, but there is less information on the age of first drink in the Kilimanjaro region and its associations with alcohol-related consequences later in life. Furthermore, local alcohol cost and availability may influence the prevalence of alcohol use and alcohol use disorders. Method Data on the age of first drink, alcohol use disorder identification tool (AUDIT), number and type of alcohol consequences (DrInC), and perceived alcohol at low cost and high availability for children and adolescents were collected from an alcohol and health behavior survey of injury patients (N = 242) in Moshi, Tanzania. Generalized linear models were used to test age at first drink, perceived alcohol cost and availability, and their association with the AUDIT and DrInC scores, and current alcohol use, respectively. Results Consuming alcohol before age 18 was significantly associated with higher AUDIT and DrInC scores, with odds ratios of 1.22 (CI: 1.004, 1.47) and 1.72 (CI: 1.11, 2.63), respectively. Female gender is strongly associated with less alcohol use and alcohol consequences, represented by an odds ratio of 3.70 (CI: 1.72, 8.33) for an AUDIT score above 8 and an odds ratio of 3.84 (CI: 2.13, 6.67) with the DrInC score. Perceived high availability of alcohol for children is significantly related to higher alcohol use quantity, with the odds ratio of 1.6 (CI: 1.17, 2.20). Conclusions The first use of alcohol before the age of 18 is associated with higher alcohol use and alcohol-related adverse consequences. In Tanzania, age at first drink is an important target for interventions aiming to prevent negative alcohol-related consequences later in life.

"Skin popping" refers to the practice of injecting drugs, most commonly heroin, subcutaneously or into granulation tissue. Pharmaceutical tablets meant for oral consumption are modified into solutions for injection. Excipients-inactive substances that serve as vehicles for medication-are often not filtered out before injection and result in abscess formation, granulomatous inflammation, and scarring. Common excipients used in the production of pharmaceutical tablets include starch, microcrystalline cellulose, magnesium stearate, silica, and polyvinylpyrrolidone (PVP). Identification of these exogenous materials is valuable in confirming the diagnosis of skin popping, especially when patients may not be forthcoming about their drug use. We present a case of subcutaneous oral medication injection in which PVP and cellulose were identified by Fourier transform infrared spectroscopy. Considering the variable cutaneous manifestations of injection drug abuse, recognition of histopathologic and chemical characteristics of exogenous material from oral medications is helpful for diagnosis and intervention.

Background Magnetic nanoparticles (MNPs) hold promise for enhancing delivery of therapeutic agents, either through direct binding or by functioning as miniature propellers. Fluid-filled conduits and reservoirs within the body offer avenues for MNP-enhanced drug delivery. MNP clusters can be rotated and moved across surfaces at clinically relevant distances in response to a rotating magnet. Limited data are available regarding issues affecting MNP delivery by this mechanism, such as adhesion to a cellular wall. Research reported here was initiated to better understand the fundamental principles important for successful implementation of rotational magnetic drug targeting (rMDT). Methods Translational movements of four different iron oxide MNPs were tested, in response to rotation (3 Hz) of a neodymium-boron-iron permanent magnet. MNP clusters moved along biomimetic channels of a custom-made acrylic tray, by surface walking. The effects of different distances and cellular coatings on MNP velocity were analyzed using videography. Dyes (as drug surrogates) and the drug etoposide were transported by rotating MNPs along channels over a 10 cm distance. Results MNP translational velocities could be predicted from magnetic separation times. Changes in distance or orientation from the magnet produced alterations in MNP velocities. Mean velocities of the fastest MNPs over HeLa, U251, U87, and E297 cells were 0.24 ± 0.02, 0.26 ± 0.02, 0.28 ± 0.01, and 0.18 ± 0.03 cm/sec, respectively. U138 cells showed marked MNP adherence and an 87.1% velocity reduction at 5.5 cm along the channel. Dye delivery helped visualize the effects of MNPs as microdevices for drug delivery. Dye delivery by MNP clusters was 21.7 times faster than by diffusion. MNPs successfully accelerated etoposide delivery, with retention of chemotherapeutic effect. Conclusion The in vitro system described here facilitates side-by-side comparisons of drug delivery by rotating MNP clusters, on a human scale. Such microdevices have the potential for augmenting drug delivery in a variety of clinical settings, as proposed.

Objective The objective of this study was to document the simulated effect of dried distillers grains with solubles (DDGS) supplementation of Coastal bermudagrass (COS; Cynodon dactylon [L.] Pers.) and Tifton 85 bermudagrass (TIF; C. dactylon [L.] Pers. × Cynodon nlemfuensis Vanderyst) forage on in vitro gas production, in vitro true digestibility (IVTD), in vitro NDF digestibility (IVNDFD), and methane production. Materials and Methods Forage and DDGS were combined to represent 3 levels of supplemental DDGS (0, 0.25, or 1% BW), which resulted in ratios of forage:DDGS of 100:0, 87.5:12.5, and 50:50. Samples were incubated using the in vitro gas production technique, and headspace was sampled for quantification of methane concentration. The residue was rinsed in neutral detergent solution for determination of IVTD and IVNDFD. Results and Discussion Discrete lag times of both the exponential and logistic equations decreased linearly (P Implications and Applications Results indicated that DDGS might be supplemented to cattle for increased diet digestibility with an additional potential benefit of reduced methane production. Efficacy of DDGS was dependent on forage nutritive value.

Background Thrombotic events continue to be a major cause of morbidity and mortality worldwide. Tissue plasminogen activator (tPA) is used for the treatment of acute ischemic stroke and other thrombotic disorders. Use of tPA is limited by its narrow therapeutic time window, hemorrhagic complications, and insufficient delivery to the location of the thrombus. Magnetic nanoparticles (MNPs) have been proposed for targeting tPA delivery. It would be advantageous to develop an improved in vitro model of clot formation, to screen thrombolytic therapies that could be enhanced by addition of MNPs, and to test magnetic drug targeting at human-sized distances. Methods We utilized commercially available blood and endothelial cells to construct 1/8th inch (and larger) biomimetic vascular channels in acrylic trays. MNP clusters were moved at a distance by a rotating permanent magnet and moved along the channels by surface walking. The effect of different transport media on MNP velocity was studied using video photography. MNPs with and without tPA were analyzed to determine their velocities in the channels, and their fibrinolytic effect in wells and the trays. Results MNP clusters could be moved through fluids including blood, at human-sized distances, down straight or branched channels, using the rotating permanent magnet. The greatest MNP velocity was closest to the magnet: 0.76 ± 0.03 cm/sec. In serum, the average MNP velocity was 0.10 ± 0.02 cm/sec. MNPs were found to enhance tPA delivery, and cause fibrinolysis in both static and dynamic studies. Fibrinolysis was observed to occur in 85% of the dynamic MNP + tPA experiments. Conclusion MNPs hold great promise for use in augmenting delivery of tPA for the treatment of stroke and other thrombotic conditions. This model system facilitates side by side comparisons of MNP-facilitated drug delivery, at a human scale.

Objective To investigate the in vitro activation of the NLRP3 inflammasome within bladder urothelium by stone-forming components. Further, to describe the contributions of reactive oxygen species (ROS) and thioredoxin-interacting protein (TXNIP), an important structural component of the inflammasome, to this activation. Methods Urothelial cells were harvested and incubated overnight. For agonist studies, cells were treated with varying concentrations of calcium pyrophosphate (CPPD) and monosodium urate (MSU). For inhibitor studies, cells were treated with either N-acetylcysteine (NAC) (1 hr) or Verapamil (4 hrs) prior to incubation with either CPPD (62.5 ug/mL) or MSU (1.25 ug/mL) for 24 hrs. Untreated controls were incubated with ATP (1.25 mM) for 1 hr to maximally stimulate NLRP3 inflammasome activity (measured as caspase-1 cleavage of the fluorogenic substrate Ac-YVAD-AFC). Results are reported as a percentage of maximum ATP response. Results CPPD and MSU activate caspase-1 in urothelial cells in a dose-dependent manner, reaching ~50% and ~25% of the ATP response, respectively. Pre-treatment with the general ROS scavenger NAC reduces this activation in a dose-dependent manner. Additionally, activation was suppressed through treatment with Verapamil, a known downregulator of TXNIP expression. Conclusion The stone components CPPD and MSU activate NLRP3 in an ROS and TXNIP-dependent manner in bladder urothelium. These findings demonstrate the importance of ROS and TXNIP, and suggest that targeting either may be a way to decrease stone-dependent NLRP3 inflammation within the bladder.

Molybdenum disulfide (MoS2) monolayers with tertiary N atoms surrounding the single Mo-vacancy sites (MoS2_1VMo_3NS) sites have been found to exhibit outstanding adsorption activity and stability. While previous literature suggested the enhanced physical adsorption nature of CO2, N2 and H2O molecules on MoS2_1VMo_3NS sites due to promotional effects of tertiary nitrogen doping of 1 Mo-vacancy, this work highlights the adsorption and dissociation of CO2 and H2O on MoS2_1VMo_3NS sites, which are investigated using density functional theory (DFT). Compared with pure MoS2 (PMoS2), our DFT calculations reveal that the MoS2_1VMo_3NS are the most catalytically active sites. The interactions with CO2 and H2O are enhanced by the larger electron distribution with N dopants and neighboring S atoms. Climbing image nudged elastic band (Cl-NEB) and ab initio molecular dynamics (AIMD) analyses indicate that the interactions are exothermic and result in spontaneous molecular dissociation. Here, CO2 dissociates into CO* and O* on two N atoms with free energy barrier (ΔGa) of −0.27 eV; while H2O dissociates via two mechanisms: (1) into adsorbed OH* and H* species (ΔGa = 0.21 eV), and (2) into adsorbed O, H, H atoms (ΔGa = 0.10 eV). The computed ΔGa values are significantly lower than the threshold energy barrier for chemical reactions at room temperature (0.8 eV), which also indicates that CO2 and H2O dissociation is spontaneous at ambient temperature. This study shows the immense potential of MoS2_1VMo_3NS in the sustainable production of fuels and chemicals via the highly efficient dissociation of inert CO2 and H2O.

Ftz-f1 is an orphan member of the nuclear hormone receptor superfamily. A 20-hydroxyecdysone pulse allows ftz-f1 gene expression, which then regulates the activity of downstream genes involved in major developmental progression events. In honeybees, the expression of genes like vitellogenin (vg), prophenoloxidase and juvenile hormone-esterase during late pharate-adult development is known to be hormonally controlled in both queens and workers by increasing juvenile hormone (JH) titres in the presence of declining levels of ecdysteroids. Since Ftz-f1 is known for mediating intracellular JH signalling, we hypothesized that ftz-f1 could mediate JH action during the pharate-adult development of honeybees, thus controlling the expression of these genes. Here, we show that ftz-f1 has caste-specific transcription profiles during this developmental period, with a peak coinciding with the increase in JH titre, and that its expression is upregulated by JH and downregulated by ecdysteroids. RNAi-mediated knock down of ftz-f1 showed that the expression of genes essential for adult development (e.g. vg and cuticular genes) depends on ftz-f1 expression. Finally, a double-repressor hypothesis-inspired vg gene knock-down experiment suggests the existence of a positive molecular loop between JH, ftz-f1 and vg.

Apatite-melt partitioning experiments were conducted in a Deltech vertical-quench 1-bar furnace at 0 GPa and 950–1050 °C using an Fe-rich basaltic starting composition. Each experiment had a unique F:Cl ratio to assess the partitioning of F and Cl between apatite and melt, and the oxygen fugacity of all experiments were between IW and IW-1. Apatite-melt partitioning of F and Cl along the F-Cl binary join is investigated in particular to assess the effect of non-ideal mixing of apatite X-site components. The quenched melt and apatite from each experiment were analyzed by electron probe microanalysis. Several of our experiments exhibited evidence of silicate liquid immiscibility (SLI), so we also evaluated the effect of SLI on the partitioning of F and Cl between apatite and melt in those experiments. The F-Cl exchange equilibria between apatite and melt were variable with 𝐾(sup 𝐴𝑝−𝑀𝑒𝑙𝑡)(sub 𝑑𝐶𝑙−𝐹) values in the range of 0.08–0.21 across the F-Cl join. The 𝐾(sup 𝐴𝑝−𝑀𝑒𝑙𝑡)(sub 𝑑𝐶𝑙−𝐹) values decreased with decreasing F in apatite and melt. Notably, we did not observe evidence that SLI has a first-order effect on the behavior of F and Cl partitioning between apatite and melt. The observed drop in 𝐾(sup 𝐴𝑝−𝑀𝑒𝑙𝑡)(sub 𝑑𝐶𝑙−𝐹) values with decreasing F abundance in melt and apatite indicate that F becomes more compatible in apatite than Cl as there is less F in the system under nominally anhydrous conditions. This behavior can be explained by the presence of an off mirror F site in F-Cl apatite that only F can occupy, and this F site is required to stabilize the apatite structure in OH-poor systems. These results demonstrate a link between atomic arrangements of apatite X-site components, the thermodynamic mixing properties of apatite X-site components, and the values of apatite-melt exchange equilibria for apatite X-site components. These results also indicate that Cl-rich apatites (i.e., Cl > 0.1 structural formula units (sfu) of apatite X-site) with compositions near the F-Cl binary join (i.e.

Bobdownsite, IMA number 2008-037, was approved as a new mineral by the Commission on New Minerals, Nomenclature and Classification (CNMNC) as the fluorine endmember of the mineral whitlockite. The type locality of bobdownsite is in Big Fish River, Yukon Canada, and bobdownsite was reported to be the first naturally occurring mineral with essential monofluorophosphate (PO3F2-). The type specimen of bobdownsite has been reinvestigated by electron probe microanalysis (EPMA), and our data indicate that fluorine abundances are below detection in the mineral. In addition, we conducted detailed analysis of bobdownsite from the type locality by gas chromatography isotope ratio mass spectrometry, Raman spectroscopy, EPMA, and NMR spectroscopy. These data were compared with previously published data on synthetic monofluorophosphate salts. Collectively, these data indicate that bobdownsite is indistinguishable from whitlockite with a composition along the whitlockite-merrillite solid solution. Bobdownsite is therefore discredited as a valid mineral species. An additional mineral, krasnoite, has been purported to have monofluorophosphate components in its structure, but reexamination of those data indicate that F- in krasnoite forms bonds with Al, similar to OH- bonded to Al in perhamite. Consequently, krasnoite also lacks monofluorophosphate groups, and there are currently no valid mineral species with monofluorophosphate in their structure. We recommend that any future reports of new minerals that contain essential monofluorophosphate anions be vetted by abundance measurements of fluorine, vibrational spectroscopy (both Raman and FTIR), and where paramagnetic components are permissibly low, NMR spectroscopy. Furthermore, we emphasize the importance of using synthetic compounds containing monofluorophosphate anions as a point of comparison in the identification of minerals with essential monofluorophosphate. Structural data that yield satisfactory P-F bond lengths determined by X-ray crystallography, coupled with direct chemical analyses of fluorine in a material do not constitute sufficient evidence alone to identify a new mineral with essential monofluorophosphate anions.

Data from the Gamma-Ray Spectrometer (GRS) that flew on the MESSENGER spacecraft indicate that the O/Si weight ratio of Mercury's surface is 1.2 ± 0.1. This value is lower than any other celestial surface that has been measured by GRS and suggests that 12–20% of the surface materials on Mercury are composed of Si-rich, Si-Fe alloys. The origin of the metal is best explained by a combination of space weathering and graphite-induced smelting. The smelting process would have been facilitated by interaction of graphite with boninitic and komatiitic parental liquids. Graphite entrained at depth would have reacted with FeO components dissolved in silicate melt, resulting in the production of up to 0.4–0.9 wt.% CO from the reduction of FeO to Fe0—CO production that could have facilitated explosive volcanic processes on Mercury. Once the graphite-entrained magmas erupted, the tenuous atmosphere on Mercury prevented the buildup of CO over the lavas. The partial pressure of CO would have been sufficiently low to facilitate reaction between graphite and SiO2 components in silicate melts to produce CO and metallic Si. Although exotic, Si-rich metal as a primary smelting product is hypothesized on Mercury for three primary reasons: (1) low FeO abundances of parental magmas, (2) elevated abundances of graphite in the crust and regolith, and (3) the presence of only a tenuous atmosphere at the surface of the planet within the 3.5–4.1 Ga timespan over which the planet was resurfaced through volcanic processes.

Many studies of the flame speed of hydrocarbon and oxygenated fuels show that flame speed is very sensitive to formyl radical (HCO) reactions with small species, such as HCO + M = H + CO + M (R1), HCO + O2 = HO2 + CO (R2) and HCO + X = CO + XH (X = H, OH) (R3). Through comparison among experimental measurements and kinetic model predictions, this paper investigates CH2O flame speed sensitivities to the effects of HCO prompt dissociation and CO2 third-body participation in R1. The conditions considered include atmospheric and elevated pressures as well as lean, ultra lean, and rich fuel mixtures using 1,3,5-trioxane as the CH2O precursor. The experimental results provide key validation targets for CH2O and HCO chemistry and the R1 third-body coefficient of CO2 in flames. Five mechanisms, GRI Mech 3.0 (Smith et al., 1999), Li Mech (Li et al., 2007), USC Mech II (Wang et al., 2007), HP Mech (Shen et al., 2015), and Aramco Mech 1.3 (Metcalfe et al., 2013) are compared against the experimental data. Model predictions indicate that the prompt reaction pathway has a significant effect on the flame speed. With an increase in pressure or the addition of CO2, the kinetic between the prompt reaction and R1 slightly reduces the prompt radical dissociation effect. On the other hand, an increase of O2 mole fraction enhances the prompt effect on the flame speed. Comparisons among experiments and model predictions show that the HP Mech with the prompt reactions, USC Mech, and Li Mech have better predictions of the flame speed at lean, ultra-lean, rich, and lean with CO2 conditions than GRI Mech and Aramco Mech. However, the predictions of USC Mech and Li Mech with prompt reactions show increased discrepancy between experiments and predictions. This result indicates that by including a new reaction pathway, an optimized model may fail beyond the validated experimental conditions. On the other hand, an elementary rate-based, non-optimized model like HP Mech can improve the prediction by directly adding the missing prompt reaction pathway.

At Winchmore, single superphosphate fertiliser has been applied annually to grazed pasture plots since 1949. To determine whether or not cadmium (Cd) in the fertiliser had accumulated in the soil, samples were collected at intervals (0–0.075, 0.075–0.15, 0.15–0.25, 0.25–0.50, 0.50–0.75 and 0.75 –1.00 m) to a depth of 1 m, the Cd concentration and bulk density measured and Cd density calculated. The relationship between Cd density and depth was curvilinear and the slope or curvature increased with increasing fertiliser application rate. Nearly 100% of the Cd stock was located in a depth of 0–0.5 m and 36% in the uppermost 0.075 m depth. Leaching calculations using Burn’s equation accurately estimated the measured Cd stock’s vertical distribution. Estimating the inputs to soils from fertiliser and atmospheric deposition and the loss by leaching and outwash accounted for the measured Cd stock. We concluded Cd accumulated in these soils at a rate determined by the fertiliser’s Cd concentration and app...

Trypanosoma cruzi is the causative agent of Chagas disease and has a single mitochondrion, an organelle responsible for ATP production and the main site for the formation of reactive oxygen species (ROS). T. cruzi is an obligate intracellular parasite with a complex life cycle that alternates between vertebrate and invertebrate hosts, therefore the development of survival strategies and morphogenetic adaptations to deal with the various environments is mandatory. Over the years our group has been studying the vector-parasite interactions using heme as a physiological oxidant molecule that triggered epimastigote proliferation however, the source of ROS induced by heme remained unknown. In the present study we demonstrate the involvement of heme in the parasite mitochondrial metabolism, decreasing oxygen consumption leading to increased mitochondrial ROS and membrane potential. First, we incubated epimastigotes with carbonyl cyanide p-(trifluoromethoxy) phenylhydrazone (FCCP), an uncoupler of oxidative phosphorylation, which led to decreased ROS formation and parasite proliferation, even in the presence of heme, correlating mitochondrial ROS and T. cruzi survival. This hypothesis was confirmed after the mitochondria-targeted antioxidant ((2-(2,2,6,6 Tetramethylpiperidin-1-oxyl-4-ylamino)-2-oxoethyl) triphenylphosphonium chloride (MitoTEMPO) decreased both heme-induced ROS and epimastigote proliferation. Furthermore, heme increased the percentage of tetramethylrhodamine methyl ester (TMRM) positive parasites tremendously-indicating the hyperpolarization and increase of potential of the mitochondrial membrane (ΔΨm). Assessing the mitochondrial functional metabolism, we observed that in comparison to untreated parasites, heme-treated epimastigotes decreased their oxygen consumption, and increased the complex II-III activity. These changes allowed the electron flow into the electron transport system, even though the complex IV (cytochrome c oxidase) activity decreased significantly, showing that heme-induced mitochondrial ROS appears to be a consequence of the enhanced mitochondrial physiological modulation. Finally, the parasites that were submitted to high concentrations of heme presented no alterations in the ultrastructure. Consequently, our results suggest that heme released by the insect vector after the blood meal, modify epimastigote mitochondrial physiology to increase ROS as a metabolic mechanism to maintain epimastigote survival and proliferation.

In this paper, we report the first synthesis of hydroxyapatite (HAp) nano-rods derived from mussel shells by a facile sonochemical method. HAp nano-rods were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR). The photocatalytic activity of HAp nano-rods was investigated using Rhodamine B (RhB) dye for the first time. The results confirm that degradation efficiency of 86.8% for RhB was observed after 300 min in the presence of the HAp nano-rods photocatalyst.

There have been few studies examining indirect nitrous oxide emissions associated with nitrogen (N) leaching from agricultural soils. For agricultural drainage water, equals the water’s concentration in excess of the atmospheric value multiplied by the transfer velocity . Using this equation, tracers and chamber methods, and were measured from an agricultural drain. Estimates of were made by measuring water speed and depth using the relationship developed by O’Connor and Dobbins [1958. Mechanisms of reaeration in natural streams. Transactions of the American Society of Civil Engineers. 123:641–684]. The measurements and estimates were not significantly different and averaged 5 m d−1. Alternatively, for the method developed by the Intergovernmental Panel on Climate Change, equals the mass of N flowing in the water multiplied by an emission factor (EF). By additional measurements of the drain’s width, the water’s flow rate and nitrate () concentration, the estimated EF was 1.2 × 10−4 kg kg−1 .

Orbital data from the MESSENGER mission to Mercury have facilitated a new view of the planet's structure, chemical makeup, and diverse surface, and have confirmed Mercury's status as a geochemical endmember among the terrestrial planets. In this work, the most recent results from MESSENGER's X-Ray Spectrometer, Gamma-Ray Spectrometer, and Neutron Spectrometer have been used to identify nine distinct geochemical regions on Mercury. Using a variation on the classical CIPW normative mineralogy calculation, elemental composition data is used to constrain the potential mineralogy of Mercury's surface; the calculated silicate mineralogy is dominated by plagioclase, pyroxene (both orthopyroxene and clinopyroxene), and olivine, with lesser amounts of quartz. The range in surface compositions indicate that the rocks on the surface of Mercury are diverse and vary from komatiitic to boninitic. The high abundance of alkalis on Mercury's surface results in several of the nine regions being classified as alkali-rich komatiites and/or boninites. In addition, Mercury's surface terranes span a wide range of SiO 2 values that encompass crustal compositions that are more silica-rich than geochemical terranes on the Moon, Mars, and Vesta, but the range is similar to that of Earth. Although the composition of Mercury's surface appears to be chemically evolved, the high SiO 2 content is a primitive feature and a direct result of the planet's low oxygen fugacity.

SM and FJ are grateful to the Carnegie Institution of Washington for funding via the Carnegie Postdoctoral Fellowship programme which supported their time at the Geophysical Laboratory and the Department of Terrestrial Magnetism, respectively. FMM acknowledges funding from NASA’s Cosmochemistry program as well as NASA’s Planetary Science Research Program. SM also acknowledges funding from the NERC (NE/PO12167/1). The petrogenesis and relationship of diamondite to well-studied monocrystalline and fibrous diamonds are poorly understood yet would potentially reveal new aspects of how diamond-forming fluids are transported through the lithosphere and equilibrate with surrounding silicates. Of 22 silicate- and oxide-bearing diamondites investigated, most yielded garnet intergrowths (n = 15) with major element geochemistry (i.e. Ca–Cr) classifying these samples as low-Ca websteritic or eclogitic. The garnet REE patterns fit an equilibrium model suggesting the diamond-forming fluid shares an affinity with high-density fluids (HDF) observed in fibrous diamonds, specifically on the join between the saline–carbonate end-members. The δ13C values for the diamonds range from − 5.27 to − 22.48‰ (V-PDB) with δ18O values for websteritic garnets ranging from + 7.6 to + 5.9‰ (V-SMOW). The combined C–O stable isotope data support a model for a hydrothermally altered and organic carbon-bearing subducted crustal source(s) for the diamond- and garnet-forming media. The nitrogen aggregation states of the diamonds require that diamondite-formation event(s) pre-dates fibrous diamond-formation and post-dates most of the gem monocrystalline diamond-formation events at Orapa. The modelled fluid compositions responsible for the precipitation of diamondites match the fluid-poor and fluid-rich (fibrous) monocrystalline diamonds, where all grow from HDFs within the saline-silicic-carbonatitic ternary system. However, while the nature of the parental fluid(s) share a common lithophile element geochemical affinity, the origin(s) of the saline, silicic, and/or carbonatitic components of these HDFs do not always share a common origin. Therefore, it is wholly conceivable that the diamondites are evidence of a distinct and temporally unconstrained tectono-thermal diamond-forming event beneath the Kaapvaal craton. Publisher PDF

Reports of the beneficial roles of butyrate in cardiovascular diseases, such as atherosclerosis and ischemic stroke, are becoming increasingly abundant. However, the mechanisms of its bioactivities remain largely unknown. In this study, we explored the effects of butyrate on endothelial dysfunction and its potential underlying mechanism. In our study, ApoE-/- mice were fed with high-fat diet (HFD) for ten weeks to produce atherosclerosis models and concurrently treated with or without sodium butyrate daily. Thoracic aortas were subsequently isolated from C57BL/6 wild-type (WT), PPARδ-/-, endothelial-specific PPARδ wild-type (EC-specific PPARδ WT) and endothelial-specific PPARδ knockout (EC-specific PPARδ KO) mice were stimulated with interleukin (IL)-1β with or without butyrate ex vivo. Our results demonstrated that butyrate treatment rescued the impaired endothelium-dependent relaxations (EDRs) in thoracic aortas of HFD-fed ApoE-/- mice. Butyrate also rescued impaired EDRs in IL-1β-treated thoracic aorta ring ex vivo. Global and endothelial-specific knockout of PPARδ eliminated the protective effects of butyrate against IL-1β-induced impairment to EDRs. Butyrate abolished IL-1β-induced reactive oxygen species (ROS) production in endothelial cells while the inhibitory effect was incapacitated by genetic deletion of PPARδ or pharmacological inhibition of PPARδ. IL-1β increased NADPH oxidase 2 (NOX2) mRNA and protein expressions in endothelial cells, which were prevented by butyrate treatment, and the effects of butyrate were blunted following pharmacological inhibition of PPARδ. Importantly, butyrate treatment upregulated the miR-181b expression in atherosclerotic aortas and IL-1β-treated endothelial cells. Moreover, transfection of endothelial cells with miR-181b inhibitor abolished the suppressive effects of butyrate on NOX2 expressions and ROS generation in endothelial cells. To conclude, butyrate prevents endothelial dysfunction in atherosclerosis by reducing endothelial NOX2 expression and ROS production via the PPARδ/miR-181b pathway.

The duocarmycins belong to a class of agent which has great potential for use in cancer therapy. Their exquisite potency means they are too toxic for systemic use, and targeted approaches are required to unlock their clinical potential. In this study, we have explored seco-OH-chloromethylindoline (CI) duocarmycin-based bioprecursors for their potential for cytochrome P450 (CYP)-mediated cancer cell kill. We report on synthetic and biological explorations of racemic seco-CI-MI, where MI is a 5-methoxy indole motif, and dehydroxylated analogues. We show up to a 10-fold bioactivation of de-OH CI-MI and a fluoro bioprecursor analogue in CYP1A1-transfected cells. Using CYP bactosomes, we also demonstrate that CYP1A2 but not CYP1B1 or CYP3A4 has propensity for potentiating these compounds, indicating preference for CYP1A bioactivation.

IMPORTANCE Lithium is a first-line mood stabilizer for the treatment of bipolar affective disorder (BPAD). However, the efficacy of lithium varies widely, with a nonresponse rate of up to 30%. Biological response markers are lacking. Genetic factors are thought to mediate treatment response to lithium, and there is a previously reported genetic overlap between BPAD and schizophrenia (SCZ). OBJECTIVES To test whether a polygenic score for SCZ is associated with treatment response to lithium in BPAD and to explore the potential molecular underpinnings of this association. DESIGN, SETTING, AND PARTICIPANTS A total of 2586 patients with BPAD who had undergone lithium treatment were genotyped and assessed for long-term response to treatment between 2008 and 2013.Weighted SCZ polygenic scores were computed at different P value thresholds using summary statistics from an international multicenter genome-wide association study (GWAS) of 36 989 individuals with SCZ and genotype data from patients with BPAD from the Consortium on Lithium Genetics. For functional exploration, a cross-trait meta-GWAS and pathway analysis was performed, combining GWAS summary statistics on SCZ and response to treatment with lithium. Data analysis was performed from September 2016 to February 2017. MAIN OUTCOMES AND MEASURES Treatment response to lithiumwas defined on both the categorical and continuous scales using the Retrospective Criteria of Long-Term Treatment Response in Research Subjects with Bipolar Disorder score. The effect measures include odds ratios and the proportion of variance explained. RESULTS Of the 2586 patients in the study (mean [SD] age, 47.2 [13.9] years), 1478 were women and 1108 were men. The polygenic score for SCZ was inversely associated with lithium treatment response in the categorical outcome, at a threshold P < 5 ? 10-2. Patients with BPAD who had a low polygenic load for SCZ responded better to lithium, with odds ratios for lithium response ranging from 3.46 (95%CI, 1.42-8.41) at the first decile to 2.03 (95%CI, 0.86-4.81) at the ninth decile, compared with the patients in the 10th decile of SCZ risk. In the cross-trait meta-GWAS, 15 genetic loci that may have overlapping effects on lithium treatment response and susceptibility to SCZ were identified. Functional pathway and network analysis of these loci point to the HLA antigen complex and inflammatory cytokines. CONCLUSIONS AND RELEVANCE This study provides evidence for a negative association between high genetic loading for SCZ and poor response to lithium in patients with BPAD. These results suggest the potential for translational research aimed at personalized prescribing of lithium.

Iron oxide nanoparticles (IONs) hold promise for enhancing drug delivery for cancer, stroke, and other diseases. Here, we demonstrate the use of a multiple-lane tissue culture tray and rotating permanent magnet to study magnetically induced rotation and translation (MIRT) of magnetic microbeads (MBs). MBs are nanoparticle aggregates with single-crystalline magnetite cores which can be moved by surface traction. The MIRT tray was produced by additive manufacturing (3-D printing) or subtractive manufacturing (milling) of acrylic. The velocity of MBs in the MIRT tray through phosphate-buffered saline, culture media with fetal bovine serum (FBS), and 100 FBS was measured from 7.5 to 30cm above the rotating magnet. A maximum velocity of greater than 5cms occurred at a distance of 22.5cm. Cultured rabbit aortic endothelial cells, grown in lanes of the sterilized MIRT tray, cause some reduction in MB velocity. We conclude that MBs are easily rotated and moved at physiologic distances by the rotating permanent magnet. Thus, MIRT can potentially be used to direct MBs in clinical drug delivery, and the MIRT tray provides a convenient model system for testing variables which can affect ION movement.

Agricultural soils emit nitrous oxide (N 2 O), a greenhouse gas and the primary source of nitrogen oxides which deplete stratospheric ozone. Agriculture has been estimated to be the largest anthropogenic N 2 O source. In New Zealand (NZ), pastoral agriculture uses half the land area. To estimate the annual N 2 O emissions from NZ's agricultural soils, the nitrogen (N) inputs have been determined and multiplied by an emission factor (EF), the mass fraction of N inputs emitted as N 2 O N. To estimate the associated uncertainty, we developed an analytical method. For comparison, another estimate was determined by Monte Carlo numerical simulation. For both methods, expert judgement was used to estimate the N input uncertainty. The EF uncertainty was estimated by meta-analysis of the results from 185 NZ field trials. For the analytical method, assuming a normal distribution and independence of the terms used to calculate the emissions (correlation = 0), the estimated 95% confidence limit was ±57%. When there was a normal distribution and an estimated correlation of 0.4 between N input and EF, the latter inferred from experimental data involving six NZ soils, the analytical method estimated a 95% confidence limit of ±61%. The EF data from 185 NZ field trials had a logarithmic normal distribution. For the Monte Carlo method, assuming a logarithmic normal distribution for EF, a normal distribution for the other terms and independence of all terms, the estimated 95% confidence limits were −32% and +88% or ±60% on average. When there were the same distribution assumptions and a correlation of 0.4 between N input and EF, the Monte Carlo method estimated 95% confidence limits were −34% and +94% or ±64% on average. For the analytical and Monte Carlo methods, EF uncertainty accounted for 95% and 83% of the emissions uncertainty when the correlation between N input and EF was 0 and 0.4, respectively. As the first uncertainty analysis of an agricultural soils N 2 O emissions inventory using “country-specific” field trials to estimate EF uncertainty, this can be a potentially informative case study for the international scientific community.

The reactivity-promoting effect of trace nitrogen oxides (NOx) on post-induction oxidation of a synthetic natural gas (2% ethane in methane) has been experimentally studied in a high-pressure laminar flow reactor (HPLFR) at 10 ± 0.1 atm, nominal reaction temperature of 818 ± 5 K, and several equivalence ratios (φ ∼ 0.5, 1.0, and 2.0). Each set of experimental measurements was simulated using several literature C0–C2 + NOx kinetic models, both recent and legacy, using approaches shown to lead to robust interpretation of present experimental conditions. Coupling between the NOx and C0–C2 submodel components of these models varies significantly in both qualitative (mechanistic) and quantitative character. A comparison among the experimental measurements and modeling results serves to highlight important kinetic features particular to application-relevant natural gas oxidation in presence of trace (∼25 ppm) NOx. Additional insight is offered by a baseline experiment with no NOx perturbation, which shows that ...

Because of their loosely bound electrons, electrides offer physical properties useful in chemical synthesis and electronics. For these applications and others, nano-sized electrides offer advantages, but to-date no electride has been synthesized as a nanomaterial. We demonstrate experimentally that Ca$_2$N, a layered electride in which layers of atoms are separated by layers of a 2D electron gas (2DEG), can be exfoliated into two-dimensional (2D) nanosheets using liquid exfoliation. The 2D flakes are stable in a nitrogen atmosphere or in select organic solvents for at least one month. Electron microscopy and elemental analysis reveal that the 2D flakes retain the crystal structure and stoichiometry of the parent 3D Ca$_2$N. In addition, the 2D flakes exhibit metallic character and an optical response that agrees with DFT calculations. Together these findings suggest that the 2DEG is preserved in the 2D material. With this work, we bring electrides into the nano-regime and experimentally demonstrate a 2D electride, Ca$_2$N.

Nitrous oxide (N2O) emissions (EN2O) from drained peat soils used for pastoral agriculture have not been measured throughout the year in New Zealand. In response to this research gap, EN2O was measured fortnightly for 1 year in the Waikato region in a plot that was not grazed or nitrogen (N) fertilised. The time series was variable, the frequency distribution skewed and the fortnightly means correlated. To account for these factors, the data were loge transformed and an order 2 autoregressive model used to estimate a mean EN2O of 4.3 g N ha−1 d−1 and 95% confidence limits of 0.6–29.1 g N ha−1 d−1. There was a statistically significant, inverse relationship between EN2O and the depth to groundwater. In winter, when rainfall totalled 393 mm, EN2O and soil N content were significantly greater under a rain shelter designed to minimise N loss by leaching, than in an uncovered plot.

The pitting corrosion behavior of AISI 202 stainless steel (SS) – a low-nickel, austenitic SS grade, was investigated by means of cyclic voltammetry (CV) technique complemented by Scanning Electron Microscopy (SEM). From the starting potential, the current density decreases and changes its sign at the corrosion potential (Ecorr). The anodic response exhibits a well-defined anodic peak followed by a passive region. A noticeable increase in the anodic current density was observed after reaching the breakdown potential (Eb). The second anodic peak which may be attributed to onset of oxygen evolution was also observed. Moreover, the cyclic voltammograms revealed that hysteresis loop is absent for all the studied concentrations, indicating that AISI 202 SS in citric acid is highly resistant to pitting corrosion as also supported by the results of SEM. It was found out that the critical current density (icrit) increases with increasing citric acid concentration.

All materials which are intended to have in contact with food and other commodities produced or processed for human consumption are called food contact materials (FCM’s). Stainless steel (SS) – a widely known metallic FCM is used mainly in processing equipment, containers and household utensils. It is known for having numerous industrial and domestic applications worldwide due to its special characteristics of having notable corrosion resistance. However, this corrosion resistance is not all-encompassing since SS may still undergo degradation when subjected to a specific corrosion-inducing environment. SS may be classified according to its microstructure. If the atoms which make up the SS can be viewed as having a face-centered cubic structure, then the alloy is said to be austenitic. This SS grades include the conventional 300-series and the newly-developed 200-series. The former has superior corrosion resistance while the latter is far cheaper. In this study, the corrosion behavior of AISI 202 SS in two different levels of dissolved oxygen (O2) and three acid concentrations was investigated using electrochemical techniques, namely, open-circuit potential (OCP) measurements and electrochemical impedance spectroscopy (EIS). As the concentration of citric acid is increased, the measured OCP values of the alloy decreased and the polarization resistance (Rp) decreased, indicating decrease in alloy stability and decline in the corrosion resistance, respectively. With regards to effects of dissolved O2, results revealed that increasing the level of dissolved O2 has consequently increased the polarization resistance and shifted the OCP to more positive values. All the generated Nyquist plots exhibited a depressed capacitive loops indicating that corrosion in the designated solution occurred with charge transfer as the rate-determining step.

Rats display both fructose-conditioned flavor preference (CFP) and quinine conditioned flavor avoidance (CFA). Dopamine (D1 and D2), muscarinic and nicotinic, but not NMDA or opioid receptor antagonists reduced fructose-CFP expression. Dopamine D1, dopamine D2, muscarinic or NMDA, but not opioid or nicotinic receptor antagonists reduced fructose-CFP acquisition. Dopamine D1, NMDA, nicotinic or opioid, but not dopamine D2 or muscarinic receptor antagonists enhanced quinine-CFA acquisition. Baclofen (BAC), a GABAB receptor agonist, alternately enhances or reduces feeding under specific conditions. The present study examined whether systemic BAC administration mediated fructose-CFP expression and acquisition or quinine-CFA acquisition. Fructose-CFP expression studies trained rats with one flavor (CS+) in 8% fructose and 0.2% saccharin and a second (CS-) flavor in 0.2% saccharin, followed by vehicle (VEH) and BAC (0.5-5 mg/kg) preceding 2-bottle (CS+, CS-) 0.2% saccharin choice tests. Fructose-CFP acquisition studies administered VEH or BAC (3 or 5 mg/kg) prior to CS+ and CS- training sessions followed by six 2-bottle (CS+, CS-) 0.2% saccharin choice tests. Quinine-CFA acquisition studies administered VEH or BAC (3 or 5 mg/kg) prior to CS- (8% fructose+0.2% saccharin) and CS+ (fructose+saccharin+0.030% quinine) training sessions followed by six 2-bottle (CS-, CS+) fructose+saccharin choice tests. BAC (3 mg/kg) minimally (66%) reduced fructose-CFP expression. BAC failed to alter fructose-CFP acquisition. Quinine-CFA acquisition was enhanced by the 5 mg/kg BAC dose (15-25%) relative to VEH (34-48%). These data implicate GABAB receptor signaling in acquisition of quinine avoidance with minimal or no effects upon fructose preferences.

Global combustion characteristics of iso-dodecane (2,2,4,6,6-pentamethylheptane, iC12) are measured and compared to those of iso-octane (2,2,4-trimethylpentane, iC8), iso-cetane (2,2,4,4,6,8,8-heptamethylnonane, iC16) and a 50/50 molar blend of iC8/iC16. The fuels are experimentally characterized by measuring combustion property targets (derived cetane number and smoke point/threshold sooting index), reflected shock ignition delay times at 20 and 40 atm, and extinction limits of strained laminar diffusion flames at 1 atm. The derived cetane number (DCN) and threshold sooting index (TSI) of iC12 are measured to be 16.8 (±1) and 15.4 (±0.5), respectively. In addition to average molecular weight (MW) and overall hydrogen-to-carbon ratio (H/C ratio), the combustion property targets for iC12 are very nearly molar averages of those for iC8 and iC16. Values agree very well with the measured combustion property indicators for the 50/50 blend of iC8/iC16. Further analysis of fuel chemical functional group distributions also finds that the abundances of methylene and methyl groups in iC12 and the 50/50 blend of iC8/iC16 are identical, further supporting that the global combustion characteristics of iC12 can be emulated by the molar averaged mixture of iC8 and iC16. Measurements of reflected shock ignition delays show that the ignition delay times of iC12 are in close agreement with those of the 50/50 molar mixture of iC8/iC16 over a broad range of temperature conditions. It is also found that the ignition delays of the three neat iso-alkanes exhibit quantitatively identical behaviors for both high and low temperature regimes, an observation that can guide the construction of combustion kinetic models for iC12. Measurements of strained diffusion flame extinction and their interpretation by the transport-weighted enthalpy (TWE) metric also support that the high temperature chemical kinetic potentials of the three iso-alkanes are essentially identical. Moreover, it is shown that molecular diffusivity (inherent in molecular weight) is the major parameter that differentiates flame extinction behaviors amongst the three iso-alkanes. In summary, this experimental study further supports the utility and characteristics of combustion property target formulation concepts for producing mixtures that emulate the pre-vaporized global combustion properties of a specific target fuel. The work also points to a strong correlation of the combustion property target data for these iso-alkanes with methylene and methyl functional group distributions for each fuel.

Many nanoparticle-based carriers to atherosclerotic plaques contain peptides, lipoproteins, and sugars, yet the application of DNA-based nanostructures for targeting plaques remains infrequent. In this work, we demonstrate that DNA-coated superparamagnetic iron oxide nanoparticles (DNA-SPIONs), prepared by attaching DNA oligonucleotides to poly(ethylene glycol)-coated SPIONs (PEG-SPIONs), effectively accumulate in the macrophages of atherosclerotic plaques following an intravenous injection into apolipoprotein E knockout (ApoE–/–) mice. DNA-SPIONs enter RAW 264.7 macrophages faster and more abundantly than PEG-SPIONs. DNA-SPIONs mostly enter RAW 264.7 cells by engaging Class A scavenger receptors (SR-A) and lipid rafts and traffic inside the cell along the endolysosomal pathway. ABS-SPIONs, nanoparticles with a similarly polyanionic surface charge as DNA-SPIONs but bearing abasic oligonucleotides also effectively bind to SR-A and enter RAW 264.7 cells. Near-infrared fluorescence imaging reveals evident lo...

The sources and nature of organic carbon on Mars have been a subject of intense research. Steele et al. (2012) showed that 10 martian meteorites contain macromolecular carbon phases contained within pyroxene- and olivine-hosted melt inclusions. Here, we show that martian meteorites Tissint, Nakhla, and NWA 1950 have an inventory of organic carbon species associated with fluid-mineral reactions that are remarkably consistent with those detected by the Mars Science Laboratory (MSL) mission. We advance the hypothesis that interactions among spinel-group minerals, sulfides, and a brine enable the electrochemical reduction of aqueous CO2 to organic molecules. Although documented here in martian samples, a similar process likely occurs wherever igneous rocks containing spinel-group minerals and/or sulfides encounter brines.

Planar cell polarity (PCP) describes a cell-cell communication process through which individual cells coordinate and align within the plane of a tissue. In this study, we show that overexpression of Fuz, a PCP gene, triggers neuronal apoptosis via the dishevelled/Rac1 GTPase/MEKK1/JNK/caspase signalling axis. Consistent with this finding, endogenous Fuz expression is upregulated in models of polyglutamine (polyQ) diseases and in fibroblasts from spinocerebellar ataxia type 3 (SCA3) patients. The disruption of this upregulation mitigates polyQ-induced neurodegeneration in Drosophila We show that the transcriptional regulator Yin Yang 1 (YY1) associates with the Fuz promoter. Overexpression of YY1 promotes the hypermethylation of Fuz promoter, causing transcriptional repression of Fuz Remarkably, YY1 protein is recruited to ATXN3-Q84 aggregates, which reduces the level of functional, soluble YY1, resulting in Fuz transcriptional derepression and induction of neuronal apoptosis. Furthermore, Fuz transcript level is elevated in amyloid beta-peptide, Tau and α-synuclein models, implicating its potential involvement in other neurodegenerative diseases, such as Alzheimer's and Parkinson's diseases. Taken together, this study unveils a generic Fuz-mediated apoptotic cell death pathway in neurodegenerative disorders.

Heme crystallization as hemozoin represents the dominant mechanism of heme disposal in blood feeding triatomine insect vectors of the Chagas disease. The absence of drugs or vaccine for the Chagas disease causative agent, the parasite Trypanosoma cruzi, makes the control of vector population the best available strategy to limit disease spread. Although heme and redox homeostasis regulation is critical for both triatomine insects and T. cruzi, the physiological relevance of hemozoin for these organisms remains unknown. Here, we demonstrate that selective blockage of heme crystallization in vivo by the antimalarial drug quinidine, caused systemic heme overload and redox imbalance in distinct insect tissues, assessed by spectrophotometry and fluorescence microscopy. Quinidine treatment activated compensatory defensive heme-scavenging mechanisms to cope with excessive heme, as revealed by biochemical hemolymph analyses, and fat body gene expression. Importantly, egg production, oviposition, and total T. cruzi parasite counts in R. prolixus were significantly reduced by quinidine treatment. These effects were reverted by oral supplementation with the major insect antioxidant urate. Altogether, these data underscore the importance of heme crystallization as the main redox regulator for triatomine vectors, indicating the dual role of hemozoin as a protective mechanism to allow insect fertility, and T. cruzi life-cycle. Thus, targeting heme crystallization in insect vectors represents an innovative way for Chagas disease control, by reducing simultaneously triatomine reproduction and T. cruzi transmission., Author summary Chagas disease is a fatal illness caused by Trypanosoma cruzi parasites, which are transmitted by blood sucking triatomine insect vectors. Although blood is a natural food source for these insects, its digestion releases toxic products, which poses a dietary challenge for both triatomine insects and trypanosomes. To overcome this, triatomines eliminate these toxic blood products by a unique process of heme crystallization into hemozoin that take place in their digestive tract. Here we describe that this detoxification process represents the major mechanism for redox balance control, and is necessary to allow triatomine insect reproduction, and Trypanosoma cruzi infection. Disruption of heme crystallization in triatomine insects thus represents a new venue for Chagas disease control, by targeting at the same time insect reproduction and parasite transmission.

Calcium intake during adolescence is important for attainment of peak bone mass. Lactose maldigestion is an autosomal recessive trait, leading to lower calcium intake. The Adequate Calcium Today study aimed to determine if a school-based targeted behavioral intervention over one year could improve calcium intake and bone mass in early adolescent girls. The school-randomized intervention was conducted at middle schools in six states over one school year. A total of 473 girls aged 10–13 years were recruited for outcome assessments. Bone mineral content (BMC) was determined by dual energy X-ray absorptiometry. Dietary calcium intake was assessed with a semi-quantitative food frequency questionnaire. Baseline calcium intake and BMC were not significantly different between groups. After the intervention period, there were no differences in changes in calcium intake and BMC at any site between groups. An unanticipated outcome was a greater increase in spinal BMC among lactose digesters than lactose maldigesters in the intervention schools only (12 months) (6.9 ± 0.3 g vs. 6.0 ± 0.4 g, p = 0.03) and considering the entire study period (18 months) (9.9 ± 0.4 vs. 8.7 ± 0.5 g, p < 0.01). Overall, no significant differences between the intervention and control schools were observed. However, lactose digesters who received the intervention program increased bone mass to a greater extent than lactose maldigesters.

Nonsteroidal anti-inflammatory drugs (NSAIDs) adversely interact with aspirin, diminishing its antiplatelet effect and potentially placing patients at an increased risk for recurrent thrombotic events. This crossover study aimed to determine whether the topical NSAID diclofenac epolamine 1.3% patch or oral diclofenac 50 mg interfered with the antiplatelet effects of aspirin 325 mg. Twelve healthy men and women aged 18-50 were included. Participants were randomized into 5 treatment arms: aspirin, diclofenac potassium 50 mg, diclofenac patch, diclofenac potassium plus ASA 325 mg, and diclofenac patch plus aspirin. Platelet responsiveness was determined using whole-blood impedance aggregation (WBA) to collagen 1 μg/mL and arachidonic acid (AA) 0.5 mM and was sampled every 2 hours. No significant difference in platelet function was observed following the diclofenac patch and aspirin vs aspirin alone. Oral diclofenac produced a mixed effect with significant reduction in platelet inhibition at hour 2 and hour 8 following aspirin administration. Topical diclofenac does not significantly interfere with the antiplatelet effects of aspirin and may be a safer alternative to the oral formulation.

Soil aeration effects on the efficacy of dicyandiamide (DCD) at reducing reactive nitrous oxide (N2O) fluxes from ruminant urine patches have not been assessed. We tested the null hypothesis that increasing soil aeration and dissolved organic carbon (DOC) levels, following ruminant urine deposition, would reduce DCD efficacy, as determined from measurements of N2O fluxes. Soil aeration was controlled (−1 or −10 kPa, the former being wetter and less aerated) within a factorial experiment that also included DCD and ruminant urine (700 kg N ha−1) treatments, destructively sampled over 40 days. Increased soil aeration corresponded with a decrease in DCD efficacy. However, contrary to the null hypothesis, increasing soil DOC concentrations following urine application did not correspond with greater DCD degradation rates. In fact, at −1 kPa applying urine increased the DCD half-life from 23.5 (±3.0) to 53.3 (±7.5) days, while at −10 kPa the DCD half-life was not affected by urine application (14.9 [±2.9] and 16...

Apatite-melt partitioning experiments were conducted in a piston-cylinder press at 1.0–1.2 GPa and 950–1000 °C using an Fe-rich basaltic starting composition and an oxygen fugacity within the range of ΔIW-1 to ΔIW+2. Each experiment had a unique F:Cl:OH ratio to assess the partitioning as a function of the volatile content of apatite and melt. The quenched melt and apatite were analyzed by electron probe microanalysis and secondary ion mass spectrometry techniques. The mineral-melt partition coefficients ( D values) determined in this study are as follows: D FAp-Melt = 4.4–19, D ClAp-Melt = 1.1–5, D OHAp-Melt = 0.07–0.24. This large range in values indicates that a linear relationship does not exist between the concentrations of F, Cl, or OH in apatite and F, Cl, or OH in melt, respectively. This non-Nernstian behavior is a direct consequence of F, Cl, and OH being essential structural constituents in apatite and minor to trace components in the melt. Therefore mineral-melt D values for F, Cl, and OH in apatite should not be used to directly determine the volatile abundances of coexisting silicate melts. However, the apatite-melt D values for F, Cl, and OH are necessarily interdependent given that F, Cl, and OH all mix on the same crystallographic site in apatite. Consequently, we examined the ratio of D values (exchange coefficients) for each volatile pair (OH-F, Cl-F, and OH-Cl) and observed that they display much less variability: K dCl-FAp-Melt = 0.21 ± 0.03, K dOH-FAp-Melt= 0.014 ± 0.002, and K dOH-ClAp-Melt= 0.06 ± 0.02. However, variations with apatite composition, specifically when mole fractions of F in the apatite X-site were low ( X F < 0.18), were observed and warrant additional study. To implement the exchange coefficient to determine the H2O content of a silicate melt at the time of apatite crystallization (apatite-based melt hygrometry), the H2O abundance of the apatite, an apatite-melt exchange K d that includes OH (either OH-F or OH-Cl), and the abundance of F or Cl in the apatite and F or Cl in the melt at the time of apatite crystallization are needed (F if using the OH-F K d and Cl if using the OH-Cl K d). To determine the H2O content of the parental melt, the F or Cl abundance of the parental melt is needed in place of the F or Cl abundance of the melt at the time of apatite crystallization. Importantly, however, exchange coefficients may vary as a function of temperature, pressure, melt composition, apatite composition, and/or oxygen fugacity, so the combined effects of these parameters must be investigated further before exchange coefficients are applied broadly to determine volatile abundances of coexisting melt from apatite volatile abundances.

Experimental degassing of H-, F-, Cl-, C-, and S-bearing species from volatile-bearing magma of lunar composition at low pressure and f O 2 close to the quartz-iron-fayalite buffer (QIF) indicates that the composition of the fluid/vapor phase that is lost changes over time. A highly H-rich vapor phase is exsolved within the first 10 min of degassing leaving behind a melt that is effectively dehydrated. Some Cl, F, and S is also lost during this time, presumably as HCl, HF, and H 2 S gaseous species; however much of the original inventory of Cl, F, and S components are retained in the melt. After 10 min, the exsolved vapor is dry and dominated by S- and halogen-bearing phases, presumably consisting of metal halides and sulfides, which evolves over time toward F enrichment. This vapor evolution provides important constraints on the geochemistry of volatile-bearing lunar phases that form subsequent to or during degassing. The rapidity of H loss suggests that little if any OH-bearing apatite will crystallize from surface or near surface (~7m) melts and that degassing of lunar magmas will cause the compositions of apatites to evolve first toward the F-Cl apatite binary and eventually toward end-member fluorapatite during crystallization. During the stage of loss of primarily H component from the melt, Cl would have been lost primarily as HCl, which is reported not to fractionate Cl isotopes at magmatic temperatures (Sharp et al. 2010). After the loss of H-bearing species, continued loss of Cl would result in the degassing of metal chlorides, which have been proposed as a mechanism to fractionate Cl isotopes (Sharp et al. 2010). After the onset of metal chloride degassing, the δ 37 Cl of the melt would necessarily increase to +6 (82% Cl loss), +8 (85% Cl loss), and +20‰ (95% Cl loss) at 1, 4, and 6 h, respectively, which was approximated using a computed trajectory of δ 37 Cl values in basalt during degassing of FeCl 2 . This strong enrichment of 37 Cl in the melt after metal chloride volatilization is fully consistent with values measured for the non-leachates of a variety of lunar samples and would be reflected in apatites crystallized from a degassing melt. Our results suggest that a range in δ 37 Cl from 0 to >20‰ is expected in lunar apatite, with heavy enrichment being the norm. While 95% loss in the initial Cl content of the melt (280 ppm Cl left in the melt) would cause an increase to +20‰ in δ 37 Cl, the ability to measure this increase in a lunar sample is ultimately dependent upon the starting Cl abundances and whether or not a mechanism exists to concentrate the remaining Cl such that it can be subsequently analyzed with sufficient accuracy. Therefore, the higher the starting Cl abundances in the initial melts, the heavier δ 37 Cl values that can be measurably preserved. Importantly, such enrichments can occur in spite of high initial hydrogen contents, and therefore, our experiments demonstrate that elevated values of δ 37 Cl cannot be used as supporting evidence for an anhydrous Moon. Furthermore, if the H-bearing vapor has a significant H 2 component, this process should also result in strong enrichment of δD in the residual magmas that reach the lunar surface or near-surface environment. Apatites within some mare basalts exhibit elevated δD of 1000 ‰ depending on the initial value (Tartese and Anand 2013) in addition to the δ 37 Cl values, but elevated δ 37 Cl values are accompanied by only modest enrichments in δD in apatites from samples of the highlands crust (McCubbin et al. 2015a).

Analytical temperature rising elution fractionation (TREF) of linear polyethylene (PE) samples with different densities was done in 1-chloronaphthalene using a gel permeation chromatograph (GPC) coupled with a gas chromatograph. The corrected peak elution temperatures completed the previously obtained data in trichlorobenzene, xylene, and dibutoxymethane. A mathematical correlation was found for diluted linear PE samples between the α parameter of the Mark-Houwink-Sakurada equation governing the retention time in GPC, the bulk melting temperature measured by differential scanning calorimetry (DSC), and the TREF peak elution temperature. The extrapolation to the melting temperature measured by DSC gives α = 0.5, thus confirming the hypothesis that polymer conformations in the melt are similar to those in a theta solvent.

Recent developments on the temperature rising elution fractionation (TREF) technique, understanding the impact strength of polyethylene blends based on their chemical structure, as well as ongoing discussions on REACH legislation regarding the oligomer fraction of polymers, are all reasons for better comprehension of the separation mechanism in TREF. To achieve this goal, two carefully chosen blends of linear metallocene polyethylene were analyzed by TREF over a large domain of crystallization rates. The results allowed updating the “onion skin” model for the crystallization kinetics during the cooling step of TREF. The advantages and limitations of the TREF technique for different applications are discussed.

Objectives To develop a urodynamic model incorporating external urethral sphincter (EUS) electromyography (EMG) in awake rats. Materials and Methods Bladder catheters and EUS EMG electrodes were implanted in female Sprague Dawley rats. Assessments were performed in awake, lightly restrained rats on postoperative day 12–14. Measurements were repeated in the same rat on day 16 under urethane anaesthesia. Urodynamics and EUS EMG were performed simultaneously. In addition, serum creatinine and bladder histology was assessed. Results No significant differences in urodynamic parameters were found between bladder catheter only vs bladder catheter and EUS EMG electrode groups. Urethane anaesthesia evoked prominent changes in both urodynamic parameters and EUS EMG. Serum creatinine was within the normal limits in all rats. Bladder weight and bladder wall thickness were significantly increased in both the bladder catheter only and the bladder catheter and EUS EMG group compared with controls. Conclusions Our novel urodynamic model allows repetitive measurements of both bladder and EUS function at different time points in the same rat under fully awake conditions and opens promising avenues to investigate lower urinary tract dysfunction in a translational approach.

Essential oil produced by aromatic plants is affected by many environmental factors including nitrogen (N), phosphorus (P), and watering frequency. Salvia officinalis (sage) is an aromatic plant widely used in the food, medicine and cosmetic industries. We studied effects of N, P, and irrigation frequency on essential oil content and composition of sage. In a field experiment in a plastic tunnel N and P were each supplied at four rates (0, 40, 80, 120 kg N ha−1; 0, 30, 60, 90 kg P ha−1) and the plants were watered every 1, 2, or 4 weeks. The treatments did not affect essential oil content. Fifty-four compounds were identified in the essential oil. N and watering frequency affected the production of β-pinene, and interactive effects were noted for NxP on α-and β-thujones, and for Nx irrigation frequency on α-thujone. Negative correlation was identified between 1,8-cineole and viridiflorol. The percentage of camphor was higher than the recommended threshold by ISO standard for trade of sage essential oil.

Aspirin remains the standard for stroke prophylaxis. However, as many as 20%-25% of patients may fail to show a full response to aspirin. Ideally, patients who are resistant to aspirin could be identified, then receive an increased dose of aspirin or be changed to an alternative therapy more efficiently. We have developed an in vitro assay that may make this possible. Healthy volunteers (n = 13) between 18 and 50 years of age were tested for both ex vivo and in vivo responses to aspirin. Dimethyl sulfoxide (DMSO) was selected as the solvent for aspirin in the assay. DMSO can exhibit antiplatelet effects, necessitating the use of a concentration low enough to avoid such antiplatelet effects. Blood samples were tested against DMSO 0%, 0.05%, 0.5%, and 1% w/v with and without aspirin 0, 50, and 100 μM. The effects of both agents were measured via whole-blood aggregometry. A 3-dimensional response model described the data well, quantifying the combinatorial effect of DMSO and aspirin on platelet aggregation. Across all participants, baseline aggregation stimulated with collagen 1 μM or arachidonate 0.5 mM was approximately 18 and 13 Ω, respectively. The response model showed that 0.05% DMSO with 100 μM aspirin would provide platelet aggregation of 3.4 Ω. A DMSO concentration of 0.05% in the absence of aspirin would result in no discernable effects on platelet aggregation (17.7 Ω). Overall, the use of 100 μM of aspirin in 0.05% DMSO provides a robust method to test for ex vivo inhibition of platelet aggregation.

The geochemistry of halogens on Mars gives insight into the composition of the martian mantle, igneous evolution of the martian crust, aqueous processes on the martian surface, and the overall habitability of the planet. Halogen abundances have been measured from martian meteorites, in situ by landers and rovers, and from orbital missions around Mars. The bulk rock abundances of halogens have been determined for many martian meteorite samples including all petrological five types (nakhlites, chassignites, shergottites, orthopyroxenites, and regolith breccias). Measurements of basaltic martian meteorites (i.e., shergottites and regolith breccias) provide important insights into halogen abundances in mantle and crustal reservoirs. Fluorine, Cl, Br, and I have been detected in silicate, phosphate, sulfate, oxide, and halide group minerals in martian meteorites. These halogen-bearing minerals are found in melt inclusions, as secondary hydrothermal or aqueous alteration products, or in the interstices between cumulus igneous silicates. Measurements from meteorites and from martian missions indicate that Cl is the most abundant halogen on and in Mars. Measurements from landed missions suggest that Cl is commonly present in oxychlorine compounds (e.g., perchlorate and chlorate salts), whereas measurements from orbit have identified both oxychlorine minerals and halite. Halite is constrained to local depressions in the ancient southern highlands, suggesting precipitation from the evaporation of water in closed basins at ~3.5–4 Ga. The presence of oxychlorine minerals on the martian surface has important implications for the habitability of present day Mars because oxychlorine minerals may deliquesce to create seasonal deposits of liquid water. Furthermore, oxychlorine compounds are considered both a resource and potential hazard to the eventual human exploration of Mars.

Analytical temperature rising elution fractionation (TREF) is a complementary technique of gel permeation chromatography (GPC) for the analysis of polyolefin structure. By connecting a high-temperature GPC with a gas chromatograph (GC) oven it is possible to build a fast analytical TREF, which permits a dramatic reduction in analysis time by directly injecting the polymer solution onto the cold column, as compared with the traditional TREF in which the slow cooling step usually takes more than 40 h. The method was successfully applied on six commercial random and homo polypropylenes for which similar thermograms were obtained for fast- and slow-cooling TREF. The obtained results show subtle differences in the behavior of polypropylene melting in solution as compared with previously analyzed polyethylene. The most important is the difference of 12.6°C between the melting temperatures in the presence of trichlorobenzene and xylene, which is much higher for polypropylene than the 3.7°C measured for polyethylene.

Ignition characteristics in the form of derived cetane numbers (DCN) of (hydro) furanic species are investigated experimentally in an Ignition Quality Tester. Further, quantum chemistry calculations at CBS-QB3 level of theory are applied to determine bond dissociation energies (BDEs) and thereby suggest the initial reactions of the ignition process for all of these fuels. Using the calculated BDEs, it is found that the ignition characteristics are similar among furans and among tetrahydrofurans, but strongly differ between these molecular classes. It is shown that the ignition behavior of aromatic furans is determined by the ring structure, which correlates with a negligible side chain influence. Hence, furan fuel structures can be chosen with respect to feasibility of the production pathways and engine compatibility. On the contrary, the side chain length for tetrahydrofurans defines the potential application paradigm. Tetrahydrofurans with short side chains are candidates for SI application, whereas 2-butyltetrahydrofuran may be a candidate for diesel application. The influence of the number and location of double bonds in the ring is illustrated with the additional study of dihydrofurans, and the influence of other functional groups is evaluated for (tetrahydro) furfuryl alcohols. To investigate possible fuel application scenarios, a second part of this study investigates DCNs of furanic fuel blends in n-heptane and diesel fuel. A DCN mixing rule is found to be approximately linear and for blends with up to 20 mol% furans, the side chain structure (alkyl, alcohol) has no distinct influence on the blend DCN.

Systemic dopamine (DA) D1 (SCH23390: SCH) and D2 (raclopride: RAC) antagonists blocked fructose-conditioned flavor preference (CFP) acquisition and expression. Fructose-CFP acquisition was eliminated by medial prefrontal cortex (mPFC) SCH and mPFC or amygdala (AMY) RAC. Fructose-CFP expression was reduced following SCH or RAC in AMY or nucleus accumbens (NAc). The present study examined fructose-CFP acquisition and expression following SCH and RAC in the medial orbital frontal cortex (MOFC), another ventral tegmental area DA target. For fructose-CFP acquisition, five groups of rats received vehicle, SCH (24 or 48 nmol) or RAC (24 or 48 nmol) in the MOFC 0.5 h prior to 8 training sessions with one flavor (CS+/Fs) mixed in 8% fructose and 0.2% saccharin, and another flavor (CS−/s) mixed in 0.2% saccharin. In six 2-bottle choice tests in 0.2% saccharin, similar fructose-CFP preferences occurred in groups trained with vehicle (76–77%), SCH24 (69–78%), SCH48 (70–74%) and RAC48 (85–92%). RAC24-trained rats displayed significant CS+ preferences during the first (79%) and third (71%), but not second (58%) test pair. For fructose-CFP expression, rats similarly trained with CS+/Fs and CS− solutions received 2-bottle choice tests following MOFC injections of SCH or RAC (12–48 nmol). CS+ preference expression was significantly reduced by RAC (48 nmol: 58%), but not SCH relative to vehicle (78%). A control group receiving RAC in the dorsolateral prefrontal cortex displayed fructose-CFP expression similar to vehicle. These data demonstrate differential frontal cortical DA mediation of fructose-CFP with mPFC D1 and D2 signaling exclusively mediating acquisition, and MOFC D2 signaling primarily mediating expression.