2,239 research outputs found

    Chaotic Jets

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    The problem of characterizing the origin of the non-Gaussian properties of transport resulting from Hamiltonian dynamics is addressed. For this purpose the notion of chaotic jet is revisited and leads to the definition of a diagnostic able to capture some singular properties of the dynamics. This diagnostic is applied successfully to the problem of advection of passive tracers in a flow generated by point vortices. We present and discuss this diagnostic as a result of which clues on the origin of anomalous transport in these systems emerge.Comment: Proceedings of the workshop Chaotic transport and complexity in classical and quantum dynamics, Carry le rouet France (2002

    Electrochemical titrations and reaction time courses monitored in situ by magnetic circular dichroism spectroscopy

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    Magnetic circular dichroism (MCD) spectra, at ultraviolet–visible or near-infrared wavelengths (185–2000 nm), contain the same transitions observed in conventional absorbance spectroscopy, but their bisignate nature and more stringent selection rules provide greatly enhanced resolution. Thus, they have proved to be invaluable in the study of many transition metal-containing proteins. For mainly technical reasons, MCD has been limited almost exclusively to the measurement of static samples. But the ability to employ the resolving power of MCD to follow changes at transition metal sites would be a potentially significant advance. We describe here the development of a cuvette holder that allows reagent injection and sample mixing within the 50-mm-diameter ambient temperature bore of an energized superconducting solenoid. This has allowed us, for the first time, to monitor time-resolved MCD resulting from in situ chemical manipulation of a metalloprotein sample. Furthermore, we report the parallel development of an electrochemical cell using a three-electrode configuration with physically separated working and counter electrodes, allowing true potentiometric titration to be performed within the bore of the MCD solenoid

    Comparative Study of the Protective Effect of Granulated Sugar and Garri Meal on Petroleum-induced Changes of Lipid Profiles in Albino Rats (Rattusnorvegicus)

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    Crude oil contaminated diet has been reported to induced changes in lipid profile of rats. In this study, 60 albino rats in 6 groups were fed with crude oil contaminated sugar-garri diets at varied concentrations to monitor petroleum-induce lipid profile changes using standard methods. The lipid profiles estimated were total cholesterols, triglycerides, high density lipoprotein cholesterol and Low density lipoproteincholesterol.The data showed that, the levels of total cholesterol (Mmol/l) increased from 2.89+0.08 in sugar fed rats compared with 3.05+0.12 in Gari fed rats. The concentration of triglycerides(Mmol/l) reduced from 1.10+0.51 in sugar fed rats to 1.06 + 0.03 in Gari fed rats while the high density lipoprotein cholesterol(Mmol/l) concentration of 2. 01+0.08 was significantly higher than 1.89 + 0.03 in Gari fed rats (P<0.05).There was no significant difference in Low density lipoprotein cholesterol (Mmol/l) concentrations of 0.68+0.11 in sugar fed rats compared with 0.83 + 0.10 in Gari fed rats. The effect of pre-treatment of the diet with sugar reduced petroleum-induce changes in lipid profile than gari during the exposure of the albino rats to the petroleum diet suggesting that sugarcould possibly ameliorate petroleum-induce changes in lipid profile as shown by the significantlowering of the cholesterol and Low density lipoprotein cholesterol than gari in albino rats. Keywords: lipid, Petroleum, Sugar, Gari, Cassava, Change

    Outbreak of West Nile virus causing severe neurological involvement in children, Nuba Mountains, Sudan, 2002.

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    An atypical outbreak of West Nile virus (WNV) occurred in Ngorban County, South Kordophan, Sudan, from May to August 2002. We investigated the epidemic and conducted a case-control study in the village of Limon. Blood samples were obtained for cases and controls. Patients with obvious sequelae underwent cerebrospinal fluid (CSF) sampling as well. We used enzyme-linked immunosorbent assay (ELISA) and neutralization tests for laboratory diagnosis and identified 31 cases with encephalitis, four of whom died. Median age was 36 months. Bivariate analysis did not reveal any significant association with the risk factors investigated. Laboratory analysis confirmed presence of IgM antibodies caused by WNV in eight of 13 cases, indicative of recent viral infection. The unique aspects of the WNW outbreak in Sudan, i.e. disease occurrence solely among children and the clinical domination of encephalitis, involving severe neurological sequelae, demonstrate the continuing evolution of WNV virulence. The spread of such a virus to other countries or continents cannot be excluded

    Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins

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    Bioinorganic canon states that active-site thiolate coordination promotes rapid electron transfer (ET) to and from type 1 copper proteins. In recent work, we have found that copper ET sites in proteins also can be constructed without thiolate ligation (called “type zero” sites). Here we report multifrequency electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), and nuclear magnetic resonance (NMR) spectroscopic data together with density functional theory (DFT) and spectroscopy-oriented configuration interaction (SORCI) calculations for type zero Pseudomonas aeruginosa azurin variants. Wild-type (type 1) and type zero copper centers experience virtually identical ligand fields. Moreover, O-donor covalency is enhanced in type zero centers relative that in the C112D (type 2) protein. At the same time, N-donor covalency is reduced in a similar fashion to type 1 centers. QM/MM and SORCI calculations show that the electronic structures of type zero and type 2 are intimately linked to the orientation and coordination mode of the carboxylate ligand, which in turn is influenced by outer-sphere hydrogen bonding

    Comparative effectiveness of abatacept versus tocilizumab in rheumatoid arthritis patients with prior TNFi exposure in the US Corrona registry

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    BACKGROUND: We compared the effectiveness of abatacept (ABA) vs tocilizumab (TCA) in tumor necrosis factor inhibitor (TNFi) experienced patients. METHODS: We identified rheumatoid arthritis (RA) patients from a large observational US cohort (1 January 2010-31 May 2014) who had discontinued at least one TNFi and initiated ABA or TCZ in moderate or high disease activity based on the Clinical Disease Activity Index (CDAI) and had no prior exposure to the comparator drug. Using propensity score matching (1:1) stratified by prior TNF use (1 TNFi vs ≥2 TNFis), effectiveness at 6 months after initiation was evaluated. Mean change in CDAI over 6 months following initiation was the primary outcome, with secondary outcomes of achievement of low disease activity/remission (CDAI ≤ 10) and mean change in modified Health Assessment Questionnaire (mHAQ) score. RESULTS: The 264 pairs of propensity score-matched ABA and TCZ initiators were well matched with no substantial differences in the baseline characteristics, defined as standardized differences \u3e0.1 in the stratification. Both treatment groups had similar mean change in CDAI at 6 months (-11.3 in ABA vs -9.9 in TCZ; mean difference -1.27, 95% CI -3.65, 1.11). Similar proportions of both treatment groups achieved low disease activity/remission (adjusted odds ratio for ABA vs TCZ 0.99, 95% CI 0.69, 1.43). Mean change in mHAQ was -0.12 in ABA initiators vs -0.11 in TCZ initiations (mean difference -0.01, 95% CI -0.09, 0.06). CONCLUSIONS: Patients receiving either ABA or TCZ had substantial improvement in clinical disease activity. In this propensity score-matched sample, similar outcomes were observed for both treatment cohorts

    The comparative effectiveness of abatacept versus anti-tumour necrosis factor switching for rheumatoid arthritis patients previously treated with an anti-tumour necrosis factor

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    OBJECTIVE: We compared the effectiveness of abatacept (ABA) versus a subsequent anti-tumour necrosis factor inhibitor (anti-TNF) in rheumatoid arthritis (RA) patients with prior anti-TNF use. METHODS: We identified RA patients from a large observational US cohort (2/1/2000-8/7/2011) who had discontinued at least one anti-TNF and initiated either ABA or a subsequent anti-TNF. Using propensity score (PS) matching (n:1 match), effectiveness was measured at 6 and 12 months after initiation based on mean change in Clinical Disease Activity Index (CDAI), modified American College of Rheumatology (mACR) 20, 50 and 70 responses, modified Health Assessment Questionnaire (mHAQ) and CDAI remission in adjusted regression models. RESULTS: The PS-matched groups included 431 ABA and 746 anti-TNF users at 6 months and 311 ABA and 493 anti-TNF users at 12 months. In adjusted analyses comparing response following treatment with ABA and anti-TNF, the difference in weighted mean change in CDAI (range 6-8) at 6 months (0.46, 95% CI -0.82 to 1.73) and 12 months was similar (-1.64, 95% CI -3.47 to 0.19). The mACR20 responses were similar at 6 (28-32%, p=0.73) and 12 months (35-37%, p=0.48) as were the mACR50 and mACR70 (12 months: 20-22%, p=0.25 and 10-12%, p=0.49, respectively). Meaningful change in mHAQ was similar at 6 and 12 months (30-33%, p=0.41 and 29-30%, p=0.39, respectively) as was CDAI remission rates (9-10%, p=0.42 and 12-13%, p=0.91, respectively). CONCLUSIONS: RA patients with prior anti-TNF exposures had similar outcomes if they switched to a new anti-TNF as compared with initiation of ABA

    Rational design of monolayers for improved water evaporation mitigation

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    Seven chemically designed monolayer compounds were synthesized and investigated with comparison to the properties and water evaporation suppression ability of 1-hexadecanol and 1-octadecanol. Increasing the molecular weight and polarity of the compound headgroup drastically altered the characteristics and performance of the monolayer at the air/water interface. Contrary to the common expectation the monolayer\u27s lifetime on the water surface decreased with increasing number of ethylene oxy moieties, thus optimal performance for water evaporation suppression was achieved when only one ethylene oxy moiety was used. Replacing the hydroxyl headgroup with a methyl group and with multiple ethylene oxy moieties resulted in a loss of suppression capability, while an additional hydroxyl group provided a molecule with limited performance against water evaporation. Theoretical molecular simulation demonstrated that for exceptional performance, a candidate needs to possess a high equilibrium spreading pressure, the ability to sustain a highly ordered monolayer with a stable isotherm curve, and low tilt angle over the full studied range of surface pressures by simultaneously maintaining H-bonding to the water surface and between the monolayer chains

    Spatial Distribution and Spectral Characteristics of Energetic Electrons in Mercury's Magnetosphere

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    The Energetic Particle Spectrometer (EPS) on the MESSENGER spacecraft, in orbit about Mercury since March 2011, has detected bursts of low- and moderate-energy (tens to hundreds of keV) electrons during portions of most orbits. There have been periods when such bursts were observed regularly on every orbit over a span of several weeks, and other periods when electrons were not observed for several days at a time. We have systematically characterized these energetic events on the basis of particle intensity over the 12-month period since MESSENGER began orbital operations. Now that MESSENGER has sampled most Mercury longitudes and local times, it is evident that the largest burst events were either at high northern latitudes or near local midnight. Lower-energy events were also seen near the equator but were mostly absent in both the dawn and dusk local time sectors. The high-latitude and nightside events are similar in particle intensity, spectra, and pitch angle and are interpreted to be the result of acceleration by the same mechanism. Another group of events occurred upstream of Mercury's bow shock. For two examples of this group of upstream events with good pitch angle coverage, the particles were field-aligned and traveling away from the bow shock. This group of events is interpreted to be similar to upstream events found at Earth during which particles are accelerated at the bow shock and subsequently travel upstream into the solar wind
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